Engineering Chemistry Volume 3

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Volume 3 of Engineering Chemistry

ISSN print 2813-6527
ISSN web 2813-6535

Full text available online at https://www.scientific.net/book/engineering-chemistry-vol-3/978-3-0364-1338-9

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Table of Contents

Recent Advances on Copper Based Metal Organic Framework as Heterogenous Catalyst Inorganic Coupling Reaction: A Review

Eliza Ahmed, Basappa C. Yallur, Vinayak Adimule, Sheetal R. Batakurki

Synthesis and Characterization of Carbonate Hydroxyapatite from Pinctada Maxima Shell with Short Aging Time for Bone Biomaterial Candidate

Megawati Megawati, Diana Julaidy Patty, Yusril Yusuf

Synthesis, Characterization, Optical and Luminescence Properties of Copper Based Metal Organic Frame Works

Maya Pai, Vinayak Adimule, Basappa C. Yallur, Sheetal Batakurki

Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

Michael Sean P. Deang, Jayke Matthew Fajardo, Dave Taña, Terence Tumolva

Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

Muhammad Amir Jamilludin, I Kadek Hariscandra Dinatha, Apri I. Supii, Juliasih Partini, Dwi Liliek Kusindarta, Yusril Yusuf

The Effect of Antimicrobial Additive on Plastic Deterioration

Buse Dasdemir, Burak Kukcu, Kaan Kanburoglu, Ali Serdar Vanlı, Anıl Akdogan

Keywords Index

Authors Index

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-3/978-3-0364-1338-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 3, pp 1-12

doi: 10.4028/p-4vr580

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2023-01-07

Revised:
2023-02-08

Accepted:
2023-02-13

Online:
2023-06-20

Recent Advances on Copper Based Metal Organic Framework as Heterogenous Catalyst Inorganic Coupling Reaction: A Review

The original version of this paper is available on https://www.scientific.net/EC.3.1.pdf

Eliza Ahmed , Basappa C. Yallur , Vinayak Adimule , Sheetal Batakurki

Department of Chemistry, M. S. Ramaiah University of Applied Sciences, Bangalore-560054, Karnataka, India.

Department of Chemistry, M.S. Ramaiah Institute of Technology (Affiliated to VTU), Bangalore560054, Karnataka, India.

Angadi Institute of Technology and Management (AITM), Savagaon Road, Belagavi 591108. Karnataka, India.

elizahmed66@gmail.com, ORCiD: https://orcid.org/0000-0003-0426-3652

yallurbc@gmail.com, ORCiD: https://orcid.org/0000-0002-9099-7056

adimulevinayak@yahoo.in, ORCiD: https://orcid.org/0000-0002-2198-6601

d sheetalrb@gmail.com,ORCiD:https://orcid.org/0000-0001-6363-173X

Keywords: Catalyst, Homogenous and heterogenous catalyst, Copper metal organic frameworks, coupling reactions

Abstract

In synthetic organic chemistry, use of catalyst to accelerate the rate of reaction leading to high yield product is a common approach practiced by chemists. Numerous homogenous and heterogenous catalyst are widely used in chemical reactions, particularly metal based catalyst are widely used. The properties of metals and their oxides are fine-tuned by size reduction method bringing down to nano scale. Further hybrid materials are used for more specific applications among which metal organic frame works are listed in more number in last ten years. Herein this review focuses on use of metal organic framework in particular Copper metal based organic framework (Cu-MOF). Cu-MOF synthesis, properties and their applications are discussed. A detailed discussion on the use of as a heterogeneous catalyst in various organic reactions.

Introduction

The original version of this paper is available on https://www.scientific.net/EC.3.1.pdf

Transition elements are the most abundant elements that are boon to mankind from mother nature [1]. Transition metals and their alloys are widely used in various industrial applications such as production of parts and engines of various transportation system, in construction of buildings, industrial manufacturing units, used as fertilizers, paints and dyes, medicines, electronic devices, and most importantly many are micro and micronutrients that are required for survival of living organisms [2]. There are about 38 elements in the d- block. These elements have varied valences due to which they can be combined in numerous combination results in compounds with unique chemical and physical properties that re widely used in various industries [3]. In the past few decades use of metal oxides have gained lot of importance microelectronics, gas sensing, biomedical, thermal materials, energy, storage, environmental decontaminations and as catalyst. Various metal oxides [4-8] such as titanium oxide doped with gadolinium copper and zinc oxides [9-16], zirconium [17], chromium [18-20], strontium [21-22], cobalt [23], tin [24], titanium [25], gadolinium [26-29], magnesium [30-31], Tantalum [32], soft magnetic Fe80 doped with cobalt [33], terelium [34], yttrium [35], strontium doped with titanate [36], strontium doped with samarium [37], etc., are widely used in energy materials for semiconductor , solar, photovoltaic, Capacitors, supercapacitors, sensors, bio-sensors, metal additives, photoluminescence [38-40], high performance energy storage device [41], dielectric properties [42]. Metal based catalysts are commonly used by petroleum refining industries, pharmaceutical industries, food industries, and many other chemical manufacturing industries [43]. Out of these application, use of metal oxides as homogenous and heterogenous catalyst in various chemical transformation have become a greener route sustaining the green chemistry requirements at the same have reduce the cost and time
required for completion of reaction with high yield product reducing the laborious work of separation of byproduct which are the major advantages of use of catalyst in industries [44]. However, the cost of manufacturing these catalysts, defect-free, lesser surface area, recyclability and reusability, and most important is poisonous of this catalyst after reaction completion hinders the usage of metal catalyst in reaction [45-46]. In recent years application of nanoscience reports breakthrough research in all aspects of science so do in chemistry, many materials are prepared in nanoscale to enhance their properties such as larger surface area, good conductivity, uniform size and shaped adsorbents to adsorb pollutants or hazardous substances from the environment, nano polymeric materials with high degrees of stiffness, strength, low to high density materials used for specific application in various industries. Further, use of nano catalyst have favored the rate of reaction, remedial to require huge temperature during conversion, high yield of product etc [47-49]. Adimule et al, [50] have reported the use Samarium ( Sm ) ( ) doped nanohybrid photocatalyst in degradation of methylene blue and carbon-di-oxide. Basappa et., al [51] have synthesized MOF for mineralization of pollutants and hydrogen evolution from water. : SrO were prepared by Vinayak Et., al and studied their photoluminescent properties which can be good candidature for high-luminescent devices [52]. decorated with Sm 2 O 3 nanostructure have synthesized by co-precipitation method [47] and studied for their electrical and super capacitive applications. decorated with , , and of Sm 2 O 3 [53-54] were synthesized by co precipitation method. The results indicated that the conductivity of exhibited better electrochemical response than other two samples. Due to change in high dipole moment specially by the samarium a strong local electric field was formed exhibiting maximum specific capacitance of at .

In this context, researchers are working on hybrid nano materials such as metal organic frame works (MOF) [55], covalent organic frame works (CMOF) [56], polymer metal organic frame works (PolyMOF) [57], amorphous porous organic framework (APOF) [58] and nano porous ionic organic networks (NPION) [59]. Structural improvement, increased porosity, high surface size, tunable topological, electrical, and chemical properties have made these resources as excellent choice of advanced materials for vast applications [60].

Figure 1: Various applications of metal organic frameworks

Figure 1. Figure 1: Various applications of metal organic frameworks

Metal organic frame are porous materials composed of organic linker with metal oxide and have attracted by several investigators for their exceptional properties like physico-chemical, tunable electrical, flexible thermal, heterogenous catalytic and mechanical characteristics [61-63]. Poly (3-octyl Thiophene) synthesized with Nickel- strontium titanium trioxide [64] has been found to possess excellent properties required for solar cell applications and also in medical applications such as DNA binding [65]. MOFs have been explored for various applications such as energy storage capacity, semiconducting nature, magnetism, luminescence, sensor technology, gas storage, molecular separation, and catalysis [66] etc. In several studies, fabrication of MOF's nanocomposites like Ag NPs onto UiO-66(Zr) has been done by the impregnation method where in Mahugo et al. prepared Ag@MIL-100(Fe) nanocomposites by employing a different procedure [6768]. Further, the amalgamation of MOFs and metal oxide like zeolite, , graphene, carbon nano tubes etc. made a composite material. Metals such as copper, iron, zinc, vanadium, titanium, samarium, are widely used metals with carboxylic acid, amines as organic linkers. These MOFS are prepared by various methods such as co-precipitation method, thermal method, solvothermal method, ultrasound, microwave, and conventional methods [69-70].

Figure 2: Synthetic Methods of metal organic frameworks.

Figure 2. Figure 2: Synthetic Methods of metal organic frameworks.

Among, various metals copper metal organic framework has been widely used for photocatalyst, heterogenous catalytic applications by synthetic organic chemist. Here in this review presents the synthesis and applications of copper metalorganic frameworks particularly for the organic functional group transformations.
Synthesis of Cu-MOF's Long et al., have synthesized Cu-TDPAT with 2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine (H6TDPAT) by solvothermal process. The FESEM image revels the formation of sized polyhedral shaped with surface area, stable up to . These Cu-TDPAT was used as heterogenous catalyst ( 0.05 mmol ) in the Goldberg-type CN coupling reaction in which of iodobenzene coupled with 5-methyl-2-( )-pyridoneat were coupled in DMSO solvent and base . The reaction conditions were optimized by varying solvent, temperature, base. It was observed that polar solvent DMSO was best suitable for Narylation and enhanced catalyst activity of MOF. The catalyst was recycled and reused for Narylation upto four cycles with being at [71].

Figure 3: Goldberg-type coupling reaction of iodobenzene coupled with 5-methyl-2-( )pyridone at in presence of Cu -TDPAT

Figure 3. Figure 3: Goldberg-type coupling reaction of iodobenzene coupled with 5-methyl-2-( )pyridone at in presence of Cu -TDPAT

Sagarmani et., al have synthesized with two N-methylimidazoles and Benzenedicarboxylic acid resulting in MOF which was used as heterogeneous catalyst (BDC) 1D MOF acts as asolid heterogeneous catalyst and exhibits efficient catalytic activity in intermolecular and intramolecular cross-coupling reactions aziridine derivatives with aryl, amines, thiols and phenols resulting in 90 % yield [72].

Figure 4: C-N, C-S, C-O coupling reaction in presence of in Cu-1D MOF

Figure 4. Figure 4: C-N, C-S, C-O coupling reaction in presence of in Cu-1D MOF

Rajendra Srivastava et. Al [73] have synthesized bimetallic metal-organic framework (MOF) using Benzentricarboxylic acid (BTC) as organic linker with cerium nitrate and copper nitrate hexahydrate. The synthesized was used as heterogenous catalyst in Sonogashira coupling reaction. of MOF was used in coupling reaction offering of 1,2-diphenylethyne carried out in presence of potassium carbonate and methanol: acetonitrile in presence of 20 W light-emitting diodes.

Nam T.S.Phan et., al [74] have synthesized using 4,4' -biphenyl dicarboxylic acid with 4,4' -bipyridine in DMF solvent maintained at by a solvothermal method. This catalyst was used in coupling reaction between 2-hydroxybenzaldehyde and 1,4-dioxane to form 99% of 2-(1,4-dioxan-2-yloxy)benzaldehyde reaction was achieved at lower temperature in presence of catalyst without any side products. Thus, MOF was successfully used as heterogenous catalyst in cross-dehydrogenative coupling reaction.

Figure 5: Cross-dehydrogenative coupling reaction of 2-hydroxybenzaldehyde in presence of MOF

Figure 5. Figure 5: Cross-dehydrogenative coupling reaction of 2-hydroxybenzaldehyde in presence of MOF

Liu et.,al. [75] have synthesized copper nanoparticles encapsulated in carboxy porphyrins organic frameworks. During the synthesis copper was encapsulated in different weight percentages and synthesized catalyst was screened for its catalytic activity in self coupling reaction of terminal alkynes. It was observed that of Cu NPs in PCN-222 had excellent catalytic activity leading to highest 1,4-diphenylbuta-1,3-diyne and2,2,7,7-tetramethylocta-3,5-diyne as selfcoupling products.

Figure 6 : Self coupling reaction in presence of

Figure 6. Figure 6 : Self coupling reaction in presence of

Qin et.,al [76] have synthesized 1,2,4,5-tetra( 2 H -tetrazole-5-yl)-benzene, with CuCN and NH 4 F in DMF and liquid NH3 maintained at for 3 days in a steel bomb. The synthesized MOFs were labelled as ( -MOF-1) and ( -MOF-2) and used as selective catalyst for selective ring opening reaction.

Figure 7: Selective ring opening reaction of 1,2,4,5-tetra(2H-tetrazole-5-yl)-benzene in presence of CuI-MOF-1

Figure 7. Figure 7: Selective ring opening reaction of 1,2,4,5-tetra(2H-tetrazole-5-yl)-benzene in presence of CuI-MOF-1

SB-Cu1 MOF can be successfully prepared by cooperative self-assembly between 1 -benzimidazolyl-3,5-bis(4-pyridyl)benzene (bbp) and CuI 5-bis(4-pyridyl)benzoic acid, 1,2diaminobenzene, phenylpropanolamine

Bagheri et.,al. [77] have synthesized SB-Cu1 MOF by using 1-benzimidazolyl-3,5-bis(4pyridyl)benzene (bbp) linker with diaminobenzene and copper iodide in presence of solvent maintained at room temperature with continuous stirring for 48 h . The synthesized SB-Cu 1 MOF was used as heterogenous catalyst in N- arylation of respective amine (imidazole, pyrrole and aniline) with various aryl halides respectively. Reaction was maintained at for 16 h and in presence of K 2 CO 3 . The SB-Cu1 MOF was recovered and reused up to five cycles without loss of activity and leading to yield of coupling product.

where amine: aniline, pyrrole, imidazole,
Figure 8: N -arylation of N - arylation of respective amine (imidazole, pyrrole and aniline) with aryl halide in presence of SB-Cu1 MOF

Maya Pai et., al [78] have synthesized bimetallic MOF RIT 62-Cu/Pd by microwave process using 4-mercaptobenzoic acid, 2-bromomalonaldehyde and copper nitrate. Around yield is reported through this process. The synthesized MOF RIT 62-Cu/Pd is used as heterogenous catalyst in Still polycondensation of thieno[2,3-b]pyrrol-5-one with three different thiophen donating groups. Polymerization reaction was optimized by varying base, solvent, and temperature. It was observed that polymerization took place at minimum temperature and time resulting in of polymerized product. The catalyst was recovered, recycled, and reused up to three cycles with good yield. However, for sixth cycle the polymerized product yield was moderate indicating that MOF RIT 62 had good activity up to three cycles.

Figure 9 : Stille polycondensation of thieno[2,3-b] pyrrol-5-one in presence of MOF RIT 62-Cu/Pd, K2CO3, toluene

Figure 8. Figure 9 : Stille polycondensation of thieno[2,3-b] pyrrol-5-one in presence of MOF RIT 62-Cu/Pd, K2CO3, toluene

Conclusion

The original version of this paper is available on https://www.scientific.net/EC.3.1.pdf

This review gives an insight on synthesis of Cu-MOF using various organic linkers by coprecipitation method, solvothermal, ultrasound, microvan method etc. The review suggests ways to fine tune the electrical properties of Cu-MOF by suitable dopants. Various applications in Cu-MOF are discussed. One of the most advanced applications of is to behave as heterogenous catalyst. Cu-MOF based heterogenous catalyst are widely used in adsorption of toxic and hazardous chemicals present in the environment, used as economical catalyst in reforming process of petroleum refinery industries. Specifically, use of in organic functional group transformation is explained. Novel hybrid bimetallic catalyst are used in various chemical reaction such as C-C coupling, N-alkylation, redox reaction, specific ring opening reaction, and condensation reactions. However, the choice of suitable organic linker, synthesis process to attain highly porous MOF materials are still a challenge and further the mechanism of these CU-MOFS in chemical transformation needs a detailed study.

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Engineering Chemistry, ISSN: 2813-6535, Vol. 3, pp 13-18

doi: 10.4028/p-08k84g

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2023-02-23

Accepted:
2023-03-12

Online:
2023-06-20

Synthesis and Characterization of Carbonate Hydroxyapatite from Pinctada Maxima Shell with Short Aging Time for Bone Biomaterial Candidate

The original version of this paper is available on https://www.scientific.net/EC.3.13.pdf

Megawati Megawati , Diana Julaidy Patty and Yusril Yusuf

Department of Physics, Faculty of Mathematics and Natural Science, Universitas Gadjah Mada, Yogyakarta, Indonesia

megawati2020@mail.ugm.ac.id, dianapatty.dp@mail.ugm.ac.id, yusril@ugm.ac.id

Keywords: Carbonate hydroxyapatite, P. maxima, short aging time, bone biomaterial

Abstract

Biomaterial products for bone repair are needed to support accelerated tissue healing. This research aimed to synthesize and characterize carbonate hydroxyapatite (CHA) from Pinctada maxima ( . maxima) using the precipitation method with a short aging time, 15 min . CHA was dried with oven-dry at for 12 h (CHA A) and a furnace-dry at for 2 h (CHA B). Short aging time succeeded in producing CHA B-type with lattice parameters and of CHA A is and , while and for CHA B. The high temperature treatment made the diffraction peak indicating CHA more detected and crystallinity increased to . The appearance of bond and diffraction peaks of CHA verified substituted carbonates hydroxyapatite.

Introduction

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Bone is an important organ that supports the body and the attachment of muscles and organs. Bone consists of inorganic mineral components, organic, water, and approximately fat [1]. The main inorganic component of bone is the mineral hydroxyapatite (HA). HA has the chemical formula in the presence of small amounts of carbonate, magnesium, and phosphoric acid. Each HA unit cell has a hexagonal structure (Fig. 1.a) [2-4].

The carbonate content in bone is about depending on the individual's age [5]. Carbonate that is substituted in the HA structure is called Carbonate Hydroxyapatite (CHA). The chemical formula is generally written as indicated that unite cell CHA consist of phosphorus, carbonate, and calcium [6].

The carbonate ion can substitute for HA in three types. CHA A-type is the carbonate ion substituted on the hydroxyl ion ( ), CHA B-type on the phosphate ion ( ), and CHA AB-type on the hydroxyl ion and phosphate ion [7]. CHA B-type is predominantly found in the body and is easier to synthesize because it can be carried out at low temperatures. CHA B-type a planar bivalent ( ) that replaced showed in Fig. 1.b.

Figure 1. Chemical structure and unit cell of HA (a) and CHA B-type (b)[7].

Figure 1. Figure 1. Chemical structure and unit cell of HA (a) and CHA B-type (b)[7].

P. maxima is a biogenic material candidate for the bone because it contains a lot of calcium [8]. The content of calcium carbonate in biogenic materials is quite significant, around . Calcium carbonate ( ) at high temperatures decomposed into calcium oxide ( CaO ) and carbon
gas ( ), as shown in Eq. (1). CaO can be used to synthesize biomaterials such as HA and CHA . CHA can be synthesized from biogenic materials such as egg shells, animal bones, fish bones, and shells.

The precipitation method was used to synthesize CHA because it was easy to perform. Aging time is one of the important factors in the carbonate substitution process in the HA structure. Patty et. al., and Anggraini synthesized CHA from . maxima uses the aging time of . Heating at high temperatures makes forming to produce substituted carbonates.

In this study, the synthesis of CHA was developed using a short aging time to shorten the synthesis time. The time of 15 minutes was chosen because the CHA constituent particles have settled after experiencing precipitation. The rapid aging process accompanied by annealing at high temperatures is expected to produce the desired CHA. CHA with carbonate content can be used for bone biomaterial applications because its composition resembles the natural condition of bone.

Material and Experimental Method

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Material. The materials used for CHA synthesis were . maxima shells, diammonium hydrogen phosphate (Sigma Aldrich), Ammonium bicarbonate (Sigma Aldrich), ammonium hydroxide (Sigma Aldrich), and distilled water.

Experimental Method. The experimental process began with preparing the raw material, . maxima shells. P. maxima shell was decomposed into CaO referring to previous research [9, 10]. CaO was used as a calcium source for CHA synthesis.

Preparation Sample. P. maxima shells were cleaned with water and soaked in acetone for 24 h . The raw were dried and cut into small pieces of approximately . The pieces of shells were ball-milled and sieved. The raw powder was furnaced at for 4 h and then sieved again using a 230 mesh ( size particle) sieve to collect a homogeneous CaO .

Synthesis of CHA. Diammonium hydrogen phosphate was dissolved in 35 ml of distilled water and then stirred at 500 rpm for 30 min . Ammonium bicarbonate was dissolved in 35 ml of distilled water and then stirred at 500 rpm for 30 min . The solution was titrated using burette to solution with rate of approximately .
decomposed from the . maxima was dissolved in 50 ml of distilled water and then stirred at 500 rpm for 30 min . The titration result of and solution titrated using burette to solution with rate of approximately while stirring at 500 rpm in .

The pH solution was maintained at 10 by adding . After titration, the solution was stirred and heated for up to 30 min until homogenous. The solution was aged for 15 min then filtered. The supernatant was dried in the oven at for 12 h (CHA A) to remove moisture and annealed in furnaces at for 2 h (CHA B) to form the CHA structure more complete.

Characterization. The samples were characterized using Fourier transform infrared (FTIR) (Thermo Scientific Nicolet iS10) at the LPPT UGM Unit 1 with a range of wave number of 650 to determine functional vibrational groups. X-ray diffraction (XRD) (Shimadzu, R600) with was performed at the Chemistry Laboratory, FMIPA, UGM, to determine the crystal structure of CHA. Scanning electron microscope-energy dispersive X-ray (SEM-EDX) (JEOL, JSM-6510LA) was conducted at LPPT UGM to determine the morphology and content of CHA samples.

Results and Discussion

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FTIR Spectra. The FTIR of CaO (Fig. 2.b) decomposition of raw . maxima showed a sharp peak in the indicating the stretching vibration of the bond [11]. Absorption also appears at
indicating the presence of bonds, while low absorption at indicates the presence of vibrations from bonds [12]. The high temperature treatment made . maxima decomposed, so the bonds are more specific due to the contribution of compounds.

The FTIR results of CHA showed absorption similar to previous studies (Fig. 2.a) [9]. CHA (Fig. 2.b) showed a sharp peak at 1013-1020 region indicating vibration from bond [13]. Absorbance at and are stretching and bending vibrations of the bond [14]. Absorbance also appeared at 3360 and are characteristic vibrations of the bond [5], [15].

The absorption indicating O-H in CHA A has a low absorption intensity at while CHA B shifted to with a higher and sharper intensity. This bond contributes to the hydroxyl in the CHA structure. The presence of C-O absorption in CHA A indicates that oven-dry has succeeded in substituting carbonates into the CHA. After high temperature treatment (CHA B), O-H absorption sharped, then bond intensity decreased. During high temperature treatment, the particles vibrated so that the carbonate could substitute the sample by replacing the phosphate position to form CHA B-type [5, 13, 16]. Presence absorbance of , and bonds like structure of CHA in Fig. 1.b indicated that CHA has successfully formed.

Figure 2. FTIR of CHA from previous studies [9] (a), FTIR sample CaO, CHA A, and CHA B (b), and diffraction of CHA A and CHA B.

Figure 2. Figure 2. FTIR of CHA from previous studies [9] (a), FTIR sample CaO, CHA A, and CHA B (b), and diffraction of CHA A and CHA B.

X-Ray Diffraction. The structure of CHA has similarities with HA which has main peaks at the hkl index , and according to JCPDS 09-0432 and CHA B-type at JCPDS 19-0272. CHA A has diffraction at angle positions (211), , and . These peaks indicate the formation of the CHA structure.

CHA B has diffraction at angle positions , (213), , and . The main diffraction peak formed in CHA shifted from the diffraction peak HA indicating the presence of carbonate ion substitution in the HA structure [13]. The high temperature heating process makes more diffraction peaks and the width between the diffraction peaks gets narrower. The narrower peak indicates the better CHA structure. The presence of carbonate substitution makes the peaks at (211) and (300) coincide each other.

Table 1 the results from the XRD diffraction analysis data using data on the main diffraction peaks. CHA A has lattice parameters and of and , respectively, while CHA B is and . CHA A and CHA B have a larger lattice parameter than the reference HA, while the lattice parameter CHA A is smaller. This condition is appropriate with the characteristic of CHA

B-type, where the lattice parameter is smaller while the parameter is larger than the HA reference [6, 13].

Table 1. XRD parameter of CHA.

Sample | Lattice parameter (Å) | c/a | Crystallite size, L (nm) | Volume unit cell, V (g/cm³) | Microstrain, ∈ (°) | Crystallinity, Xc (%)
a | c
HA Ref. | 9.418 | 6.884 | 0.730 | - | - | - | -
CHA A | 9.382 | 6.964 | 0.743 | 26.09 | 1592.334 | 0.006 | 95.37
CHA B | 9.451 | 6.962 | 0.736 | 45.09 | 1615.644 | 0.004 | 97.87

The lattice parameter ; crystallite size ; Volume unit cell ; microstrain ; and crystallinity ; FWHM is the full width at half maximum.

The annealing process at for 2 h caused the particles forming the CHA to vibrate and integrate to form the CHA structure. During the annealing process, the carbonate ion undergoes substitution to replace the phosphate ion position. This situation makes the lattice parameter decrease while the lattice parameter increases so that the ratio parameter of CHA B to be closer to the value of the reference than CHA A .

High-temperature treatment makes the micro and nano grains of HA to be integrated and makes the particles experience compaction. This makes the crystallite size in CHA B increased to 45.09 nm , while the volume unit cell increased to compared to CHA A. A low microstrain was detected at and , which indicated a very small crystal defect [11]. The crystallinity of furnace-dried CHA is higher than that of oven-dried CHA up to .

The diffraction peaks indicated the presence of CHA with lattice parameters decreased and increased indicating that the synthesis was confirmed to CHA B-type. This result is strengthened by the FTIR result, which confirmed the presence of , and bonds.

Figure 3. Morphology and content from SEM-EDX result of CaO, CHA A, and CHA B.

Figure 3. Figure 3. Morphology and content from SEM-EDX result of CaO, CHA A, and CHA B.

Morphology Properties. The SEM and EDX result of CaO and CHA results are shown in Fig. 3. The CaO has solid particles. The EDX results show that the main content is calcium up to and carbon as much as . This high calcium content supports its use as the main ingredient in the synthesis of CHA.

CHA A showed uniform grains with grain sizes of approximately . High temperature treatment made the morphology of CHA B has an irregular square shape with a slick surface. The grain diameter of approximately . This result is confirmed by the FTIR and XRD results
analysis previously which reported that after high temperature treatment, CHA is more detected and indicating carbonate substituted in the HA structure.

Table 2. Molar ratio of CHA.

Sample | Ca (%) | P (%) | n Ca (mol) | n P (mol) | Ratio* (Ca/P)
CHA A | 35.29 | 12.70 | 0.88 | 0.41 | 2.15
CHA B | 33.89 | 12.56 | 0.85 | 0.41 | 2.09

*Molar ratio and
The EDX results showed that all CHA samples contained calcium and phosphate. The molar ratio of CHA is presented in Table 2. The calcium and phosphate content in CHA A was higher than CHA B so ratio ( ) of CHA A is 2.15 while CHA B is 2.09 . High temperature treatment causes the calcium and phosphate content decreased. This condition happened because the carbonate substituted in the phosphate site, so the phosphate content decreased then ( ) in CHA was higher than HA.

This result is also validated by the FTIR results of CHA which showed the absorption intensity of bonds decreased while bonds increased. The XRD results also showed lattice parameter decreased while lattice parameter increased indicating CHA B-type. The results of CHA B-type are similar to the results of the previous CHA which can be used for bone repair such scaffold in bone tissue engineering [9].

Summary

The original version of this paper is available on https://www.scientific.net/EC.3.13.pdf

CHA synthesized from . maxima with short aging time of 15 min succeeded has major diffraction peaks (002), (211), and (300) indicating the formation of a CHA structure. CHA A had lattice parameters and are and , while CHA B was and that indicating CHA B-type. The substituted carbonate was evident from the presence of FTIR absorption at and indicating the bond. CHA A has ratio ( ) is 2.15 while CHA B is 2.09 occurs because of the carbonate content in the CHA. The high temperature treatment increased crystallite size increased up to 45.09 nm and crystallinity up to . This result indicates that synthetic CHA can be used for applications in biomaterials such as bone repair.

Acknowledgements

The original version of this paper is available on https://www.scientific.net/EC.3.13.pdf

The authors would like to thank the Ministry of Education, Culture, Research, and Technology, Republic of Indonesia, for the PTM Grant (1956/UN1/DITLIT/Dit-Lit/PT.01.03/2022) and the Indonesian Endowment Fund for Education (KET-78/LPDP.3/2022) for financial support, and the Laboratory of Material Physics and Electronics, Integrated Research and Testing Laboratory at the University Gadjah Mada, Indonesia.

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The original version of this paper is available on https://www.scientific.net/EC.3.13.pdf

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This ePub file was created using machine-generated methods and automated software to convert the source text into an ePub format and may contain formatting inconsistencies from the original version. Formatting may vary depending on the device used.

The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-3/978-3-0364-1338-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 3, pp 19-30

doi: 10.4028/p-533xs2

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2023-01-04

Revised:
2023-02-09

Accepted:
2023-02-13

Online:
2023-06-20

Synthesis, Characterization, Optical and Luminescence Properties of Copper Based Metal Organic Frame Works

The original version of this paper is available on https://www.scientific.net/EC.3.19.pdf

Maya Pai , Vinayak Adimule , Basappa C. Yallur , Sheetal Batakurki

¹Department of Chemistry, M. S. Ramaiah University of Applied Sciences, Bangalore-560054, Karnataka, India.

Angadi Institute of Technology and Management (AITM), Savagaon Road, Belagavi 591108. Karnataka, India.

Department of Chemistry, M.S. Ramaiah Institute of Technology (Affiliated to VTU), Bangalore- 560054, Karnataka, India.

mayapai7@gmail.com, adimulevinayak@yahoo.in, yallurbc@gmail.com, d sheetalrb@gmail.com

Abstract

Herein, we report synthesis of two new copper metal organic frameworks. The organic linkers were terephthalic acid with 6-Dihydroimidazo[2,1-b]thiazole-2-carbaldehyde and terephthalic acid with 3-benzothiazol-2-yl-malonaldehyde used in the copper nano metal organic framework (MOF). Both the Cu-MOF's were characterized by XRD, UV-vis spectroscopy and FTIR. XRD crystallographic studies revealed the presence of copper metal at at . Tauc plots were simulated to calculate the band gap of both Cu-MOF's and result indicated the band gap energy of Cu-MOF 1 at 3.31 eV and for Cu-MOF 2 was at 3.57 eV . The UV-Visible absorption studies indicated two bands for Cu-MOF 1 and Cu-MOF 2 at 326 nm . However, the second band in Cu MOF 1 at 509 nm was slightly shifted to higher wavelength at 516 nm in Cu-MOF 2 due to the extension of transition. The photoluminescent properties of both Cu-MOF's indicated a strong band at 505 nm . Thus, the optical properties of both the Cu-MOF's infers that these can be a promising semiconductor material for various electronic applications.

Introduction

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In recent years, material scientist are widely using the metal oxides as dopants to obtain desired optoelectronic properties. Various metals such as titanium oxide [1-2] doped with gadolinium [3-5], chromium oxide [6-7], strontium [8-10], zirconium doped along with yttrium [11-12], smarium oxide [13-14],chromium [15-16], titanate doped with strontium [17-19], yttrium on zinc oxide [20], titanium doped on nickel [21], titanium magnesium strontium [22], strontinum deposited on cadmium oxide [23], biosyntesised copper oxide [24], Tantalium oxide[25], tereliumoxide [26], yttrium doped on zirconium [27],smarium doped on terellium [28], zinc oxide [29-30] with copper oxide [31], iron oxide [32-34], copper oxide [34-37], were used as dopants. Metal organic frameworks (MOF's) [38] are hybrid crystalline porous materials synthesized by using organic linkers coordinated to metal ions that attain specific porosity [39]. Metals and its oxideshave diversified properties that includes electrical and magnetic properties whereas organic ligands do possess unique chemical and physical features [40]. Thus, when a unique combination of metal and organic linker are synthesized together results in materials with unique chemical, physical, electrical, and magnetic properties that can be used for various applications [41-44] such as field of electronics sensors [45], magnetism [46], adsorption of pollutants [47] medical research [48] and etc. Metal organic frameworks are widely used in various applications [49] due to their unique properties such as unique specific porous nature which are resulted as porous coordination polymers and leading to material that can easily bind or trap the other metals or organic molecules through either absorption or adsorption or through any weak force associated with elements present in the organic linkers. Their unique surface area ranging from 1000 to [50] makes them as a material of choice for adsorption of gases such as

Co 2 , ammonia, greenhouse gases etc., storage of gases such as hydrogen [51-52], methanol in various industries, also used in drug delivery system, also due to their antimicrobial property are widely used in surgical bandages etc., [53-56]. Further, fine tunability of electrochemical properties of MOF's by doping with suitable dopants, are widely used in semiconductor applications. Nevertheless, MOFs are also used as hybrid heterogenous catalyst for numerous oxidation [57-58], reduction [59] and coupling reactions [60]. The most common metal ions used in MOFs are Zinc, Copper [61-62], iron [63], Zirconium [64], titanium [65], Scandium [66], vanadium [67], chromium [68], nickel [69], manganese [70], samarium [71], cobalt [72], while the common organic linkers can be classified into aromatic acids such as terephthalic acid [73], benzoic acid [74], trimeric acid [75], or 2methylimidazole, benzene-1,3,5-tricarboxylic [76] acid, [1,1'-biphenyl]-4,4'-dicarboxylic acid,[1,1':4',1"-terphenyl]-4,4"-dicarboxylic acid [ 77], 4,4'-(ethyne-1,2-diyl)dibenzoic acid,pyrene-2,7-dicarboxylic acid [78] have been excessively used as organic linkers [79]. MOFs are synthesized [80-81] by Conventional electric (CE) heating, microwave (MW) heating, electrochemistry (EC), mechanochemistry (MC), and ultrasonic (US) methods and good crystallinity, porous size, control over morphology and thermally stable MOF are being obtained using this method. Yaghi et.al [82] discussed slow diffusion of reacted with in presence of triethylamine (TEA) for a week time that produced MOF-2, MOF-3, MOF-5. The present study deals with Cu based MOFs synthesized by solvothermal method and further, prepared and rGO (Reduced Graphene Oxide) were dispersed in MOFs-nanocomposite through stirring method and studied band gap variation.
Herein we have reported the two Cu-MOF's starting from 6-Dihydroimidazo thiazole-2carbaldehyde and terephthalic acid resulting in Cu-MOF 1 and 3-benzothiazol-2-yl-malonaldehyde and terephthalic acid resulting in Cu -MOF 2. Both the Cu-MOF's are characterized by FT-IR, XRD and UV-visible spectrophotometer. The optical and photoluminescence studies were carried out for the synthesized of Cu-MOF's.

Experimental

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Materials: All the chemicals and reagents procured from Avra Synthesis Private Ltd, Spectro Chem Ltd., Sigma Aldrich, India and used without any further purifications. 1,1,3,3-tetramethoxy propane 99% (Sigma Aldrich), Imidazolidinethione, 99% (Sigma Aldrich), 2-Mercaptobenzothiazole, 99% (Spectro Chem), Terephthalic acid 98% (Avra Synthesis Private Ltd), Cu (NO3)2.3H2O 98% (SigmaAldrich Ltd).
Instrumentation: The morphological analysis for the synthesized MOFs were caried out by using powder X ray diffractometer (Bruker, Germany) fitted with D8-fine focus ceramic X-ray tube, Cu source radiation at room temperature. The presence of various organic functional group in the MOFs were studied using Fourier transformed infrared spectrometer (Bruker-Alpha, Germany). The optical properties of MOFs were studied by recording the maximum absorption using UV-Visible absorption Spectrometer (Spector 210 plus).
Preparation of 2-bromomalonaldehyde: Starting material 2-bromomalonaldehyde was prepared using the procedure given in literature. To a 100 ml of aqueous solution of 1, 1, 3, 3tetramethoxypropane ( ), concentrated was added and stirred until it forms homogeneous solution, wherein temperature of the reaction mixture was maintained below and later bromine solution was added drop wise slowly and stirring was continued for another 30 minutes. Then, reaction mixture was concentrated under vacuum maintaining temperature below until thick slurry was obtained, and further washed using 200 mL cold water, 100 ml of cold dichloromethane and dried in vacuum. Yield: , MP: (Lit: ).
Preparation of 5,6-Dihydroimidazo[2,1-b]thiazole-2-carbaldehyde: To a stirred solution of imidazolidinethione in ethanol was added an ethanol solution of 2bromomalonaldehyde dropwise over a period of 15 minutes and stirring continued for an hour at room temperature and then at for two hours. The yellow color solid obtained was filtered and washed several times with acetone, then dried under vacuum. Reaction completion was monitored on TLC. Yield: .

Preparation of 3-benzothiazol-2-yl-malonaldehyde: To a stirred solution of 2mercaptobenzothiazole in acetonitrile, 2-bromomalonaldehyde was added drop wise for a period of 15 minutes. Kept for vigorous stirring at room temperature for an hour at room temperature and at for two hours in vacuum for the removal of solvent. Acetone was added and the pale colored solid was filtered, washed by acetone and further the compound obtained was dried in vacuum. Yield: . The synthesis of Cu-MOF's are as shown in Fig.1.

Figure 1. Preparation of Cu-MOF's: compound 1 and 2.

Figure 1. Figure 1. Preparation of Cu-MOF's: compound 1 and 2.

Result and Discussion

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UV-Visible Spectral studies:

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Fig. 2. UV-visible spectrum of Cu-MOF 1 and Cu-MOF 2.

Fig. 2. UV-visible spectrum of Cu-MOF 1 and Cu-MOF 2.

Figure 2 indicates the UV-visible spectra of the synthesized Cu-MOF's. The Cu-MOF 1 showed two absorption bands at 326 nm and 509 nm whereas Cu-MOF 2 showed absorption bands at 326 nm and 516 nm . Both the absorption bands recorded may corresponds to the and excitation attributing the interaction between the oxygen of the organic framework [83] and apparently due to the optical transition of organic ligands to that of copper metal charge transfer. Increase in wavelength in Cu-MOF 2, attributed to the of phenyl ring thus decreasing the energy required between the two transition states [84].

FT-IR Spectral Analysis:

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Figure 3: FT-IR spectrum of Cu-MOF 1, Cu-MOF 2, terephthalic acid and 5-7 dihyroimidazo [2,1-b]thiazole-3-carbaldehyde

Figure 3. Figure 3: FT-IR spectrum of Cu-MOF 1, Cu-MOF 2, terephthalic acid and 5-7 dihyroimidazo [2,1-b]thiazole-3-carbaldehyde

Figure 3 shown the terephthalic acid, 5-7 dihyroimidazo [2,1-b]thiazole-3-carbaldehyde, Cu-MOF 1 and Cu MOF 2. The presence of str band were observed in both terephthalic acid and 5-7 dihyroimidazo [2,1-b]thiazole-3-carbaldehyde [85]. A sharp carbonyl stretching was observed at and Ald C-H stretching band at 2944 cm -1 for 5-7 dihyroimidazo [2,1-b]thiazole-3carbaldehyde. However, in Cu-MOF 1 and Cu-MOF 2, all these characteristic bands i,e the O-H str band, carbonyl stretching band and Ald C-H stretching band disappeared upon formation of coordination bond with copper. In Cu -MOF 1 and Cu -MOF 2, the alkene str was observed at bending at . In Cu-MOF 2, the presence of Ar C-H stretching was observed at .

XRD diffraction studies

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The phase purity and crystallinity of synthesized Cu-MOFs were identified with the XRD diffraction studies as shown in Fig 4. The A sharp arrow headed tripods with amorphous type of nature of peaks were observed due to the presence of pure copper with a cubic face centered structure. In both the

Cu-MOFs the peaks values i,e at attributed to planes at (020), (040) (035) respectively for copper crystal planes which agrees with the JCPDS No.89-4897 [85]. Many such sharp peaks were observed between at to . Most of the peaks match with the literature reported as JCPDS card no. 89-2838 and 04-0836 for copper [86]. The crystallite size of Cu-MOFs were calculated using Scherrer equation.

where K is crystallite shape constant ( 0.94 ), is full width at half maximum, is wavelength of X ray radiation and is glancing angle. The crystalline particle sizes were observed between .

Figure 4. XRD patterns of Cu-MOF 1 and Cu-MOF 2.

Figure 4. Figure 4. XRD patterns of Cu-MOF 1 and Cu-MOF 2.

Photoluminescence features of Cu-MOFs

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Figure 5 infers the photoluminescence properties of Cu-MOFs. A sharp intense peak was observed at was observed for both Cu -MOF 1 and Cu -MOF 2 contributing to the excitation of copper metals ions along with the ligands. A small shoulder peak was observed at 756 nm for both Cu-MOF 1 and Cu-MOF 2 respectively. The obtained photoluminescent properties are in accordance with the literature [87].

Figure 5: Photoluminescence spectrum of and .

Figure 5. Figure 5: Photoluminescence spectrum of and .

Optical properties

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Band gap analysis: The UV-visible absorption spectra was carried out using 210 plus UV-Visible absorption Spectrometer. Tauc plots were obtained from simplifying equation 2 [88]. Graphically the bandgap energy was obtained by extrapolating the tangential line intersecting x axis at as shown in Figure 6. The band gap energy for was recorded at 3.31 eV and that of 2 at 3.57 eV . Structurally presence of phenyl ring didn't have impact on the band gap energy.

Figure 6. The energy band gaps of a) Cu-MOF 1 and Cu-MOF 2

Figure 6. Figure 6. The energy band gaps of a) Cu-MOF 1 and Cu-MOF 2

Conclusion

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This work reports the synthesis of copper based nano metal organic frame works starting from starting from terephthalic acid with 6-Dihydroimidazo[2,1- ]thiazole-2-carbaldehyde and 3-benzothiazol-2-yl-malonaldehyde. The synthesized Cu-MOF's were confirmed by a presence of sharp absorption band at 326 nm and broad shoulder band at 509 nm for Cu-MOF 1. A similar band was observed at 326 nm and 516 nm for Cu-MOF 2. An increase in 16 nm for the second band in Cu-MOF 2 was due to enhanced in transition. Further, the absence of Ald C-H stretching band and carbonyl stretching band in FT-IR spectroscopy of both Cu-MOF's resulted must be a co-ordination bond formed between the copper metal and the oxygen of aldehyde group. The XRD pattern of Cu-MOF's showed a sharp peak at for copper crystals with a cubic faced centered structure. The photoluminescent spectrum revealed a sharp band at 505 nm for both Cu-MOF's. Band gap energy of Cu-MOF's were calculated by using Tauc plots. The band gap energy for Cu-MOF 1 was calculated to be at 3.14 eV whereas for Cu-MOF 2 the band gap energy was 3.57 eV . This study results that the both Cu-MOF's are promising material for semiconductors, provided further optimization of band gap energy can be carried out to achieve a band gap energy of 1 to 0.5 eV for semiconductor applications. Further, to reduce the band gap, the synthesized Cu -MOF will be doped with metal oxides and screened for their sensory and photoluminescent applications.

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Engineering Chemistry, ISSN: 2813-6535, Vol. 3, pp 31-36

doi: 10.4028/p-9cv3vh

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2023-02-27

Accepted:
2023-03-12

Online:
2023-06-20

Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

The original version of this paper is available on https://www.scientific.net/EC.3.31.pdf

DEANG Michael Sean , FAJARDO Jayke Matthew , TAÑA Dave and TUMOLVA Terence

¹Department of Chemical Engineering, University of the Philippines Diliman, Quezon City, Philippines

mpdeang@up.edu.ph, jcfajardo5@up.edu.ph, dctana@up.edu.ph, tptumolva@up.edu.ph

Keywords: hydrogel, agar, carrageenan, drug release, vitamin

Abstract

A phycocolloidal hydrogel patch is studied as a potential material for the transdermal delivery device for vitamin B12. The vitamin release kinetics from an agar/ κ-carrageenan hydrogel blend as a function of mass ratio and vitamin loading. Concentration measurements were done using a colorimetric method, and the experimental data were fitted into the Korsmeyer-Peppas model, Peppas-Sahlin model, and Berens-Hopfenberg model. From the curve fitting, parameters such as first-order polymer relaxation constant and diffusivity constant were obtained. The results showed that for the Korsmeyer-Peppas model and the Peppas-Sahlin model, the release mechanism followed Fickian diffusion predominantly. On the other hand, the Berens-Hopfenberg model fit shows that the release mechanism predominantly follows non-Fickian diffusion and may need to be modified.

Introduction

The original version of this paper is available on https://www.scientific.net/EC.3.31.pdf

Recently, there have been a growing interest in the use of hydrogels as a carrier medium for the topical application of vitamins, such as the study on the gel-to-epidermal permeation of Vitamin C (ascorbic acid), which is a naturally occurring, powerful antioxidant with numerous benefits to the skin [1]. While there have been many studies on alginate hydrogels being used for drug delivery, most of them deal with oral administration or injection. On the other hand, there have been several reports on alginate hydrogels used as wound dressing; alginate, a naturally is extensively used because of its nontoxicity, excellent water absorption capacity, hemostatic property, and non-immunogenicity [2]; however, most are primarily focused on the use of therapeutic agents that promote wound healing such as Ag nanoparticles and iodine. Thus, there is still a need to further study the sorption and drug release properties of phycocolloids to determine their potential for topical application of vitamins.

Several models have been established on the kinetics of drug release from polymeric systems, such as the Korsmeyer-Peppas, Berens-Hopfenberg, and Higuchi models [2]. However, there is limited research specifically on the release of vitamin B12 from a phycocolloidal hydrogel blend for transdermal delivery applications: for instance, Jin, et al. studied the diffusion mechanism of vitamin B12 in polyacrylic acid and copolymers of acrylic acid and N-vinyl pyrrolidinone hydrogels [3] using Peppas models but only focused on performing permeation tests. On the other hand, there have been studies such as those conducted by Rossi, et al. on agar-carbomer hydrogel blends for the diffusivity and release of ethosuximide [4] and by Li , et al. on the gelling behavior and drug release performance of agar/ κ-carrageenan mixed hydrogels [5] that did not include mathematical modelling of drug release kinetics. Because drug diffusivity is significantly affected by drug-polymer interaction and by polymer network structure, it is necessary to establish sorption kinetic parameters inherent to every specific polymer system for the purpose of drug delivery material design. Establishing a mathematical model to correlate the release of vitamins to hydrogel blend formulation parameters such as mixing ratio and loading allows for optimization and improved product performance.

This study focuses on the mathematical modelling of the vitamin B12 diffusivity and release using Fickian and first-order polymer relaxation parameters for a hydrogel blend of agar and -carrageenan. The modelling fit aims to establish the material behavior of the agar/ -carrageenan as well as its potential as a topical drug delivery device for vitamin B12.

Experimental

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Hydrogel Blend Preparation. Mixtures of agar/ -carrageenan powder ( ) were dissolved in distilled water at to a set biopolymer concentration of , while the vitamin B12 powder was stirred into the solution at different concentrations ( ). The polymer solutions were then poured into molds and allowed to set at room temperature for 12-18 hours. Finally, the set vitamin-loaded hydrogel samples were then placed in a drying oven at .

Drug Release Measurement. Concentration of released vitamin were measured using simple colorimetry setup. A dried vitamin-loaded hydrogel was cut into a circular shape of 23 mm diameter and placed on top of a beaker filled to the brim with 8.61 mL of disodium phosphate-citric acid buffer ( pH 7.4 ). The concentration of the vitamin B12 solution was determined from calibration lines generated from measuring the absorbance of the beaker solution with the released vitamin B12 against that of a blank solution.

Mathematical Modelling. Vitamin release kinetics modelling was done by fitting the experimental data on concentration and equilibrium concentration to the Korsmeyer-Peppas (Eq. 1), Peppas-Sahlin (Eq. 2), and Berens-Hopfenberg (Eq. 3) models. The Generalized Reduced Gradient (GRG) and the least-squares algorithm were employed to calculate the model parameters. Data fitting calculations and plotting were done using MS Excel® and Visual Basic Analysis.

Results and Discussion

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Korsmeyer-Peppas. As shown in Table 1, the values for the model parameters generated by the Korsmeyer-Peppas model at order, specifically at loading, it is observed that the values ranged from 0.48 to 0.58 among different mass ratios. Thus, it can be assumed that the drug release mechanism as defined by this model equation approximately follows Fickian diffusion ( ). The vitamin release data fitted into the Korsmeyer-Peppas model with are observed to give values for parameter as listed in Table 2 for varying loading and mass ratios. Based on the observed values, it is concluded that the Fickian diffusion assumption is valid for the loading, with the diffusion coefficient ranging from 0.265 to 0.290 across all variations. It is also observed that as vitamin loading is increased, the Fickian model fit becomes less accurate, which implies a decrease in drug mobility at higher concentration.

Table 1. Best fit parameters of release data from the Korsmeyer-Peppas model at different agar fractions and vitamin loading.

| agar fraction
| 0.25 | 0.50 | 0.75 | 1.0
n | 0.541 | 0.499 | 0.580 | 0.479
R² | 0.991 | 0.992 | 0.993 | 0.995

Fig. 1 shows the correlation between the predicted versus actual values were generated to validate the Korsmeyer-Peppas model at order. To summarize, the model best fitted release data at loading, as it is evident that the value increases as agar fraction is increased.

Table 2. Best fit parameters of release data modelled on the Korsmeyer-Peppas model at .

| 1× loading | 1.5× loading | 2× loading
agar fraction | K | R² | K | R² | K | R²
0.25 | 0.271 | 0.990 | 0.290 | 0.988 | 0.288 | 0.983
0.50 | 0.277 | 0.992 | 0.287 | 0.983 | 0.282 | 0.977
0.75 | 0.277 | 0.991 | 0.290 | 0.985 | 0.265 | 0.986
1.00 | 0.295 | 0.994 | 0.269 | 0.985 | 0.271 | 0.977

Figure 1. Predicted versus actual values using Korsmeyer-Peppas model for (a) 0.25, (b) 0.50, (c) 0.75, and (d) 1.0 agar fractions at loading.

Figure 1. Figure 1. Predicted versus actual values using Korsmeyer-Peppas model for (a) 0.25, (b) 0.50, (c) 0.75, and (d) 1.0 agar fractions at loading.

Peppas-Sahlin. Table 3 shows the vitamin release data fit using the Peppas-Sahlin model to approximate the contribution of the Fickian and non-Fickian diffusion behavior in the release of vitamin B12 from the agar/carrageenan hydrogel. Following the study of Mircioiu, et al. [6], since the hydrogel is a thin film with a twice diameter-to-thickness ( ) ratio of 105, a value of 0.5 for of may be assumed, which implies that diffusion mechanism follows Fickian behavior while any non-Fickian deviations shall be attributed to hydrogel relaxation ( ).

The obtained data show that is greater than , implying that Fickian diffusion is the dominant release mechanism. These findings for the Peppas-Sahlin model parameters are somewhat consistent with the analysis of the release kinetics using the Korsmeyer-Peppas model, but with non-Fickian behavior now being accounted for by the model equation.

Table 3. Best fit parameters of release data modeled on the Peppas-Sahlin model at .

agar fraction | 1× Loading | 1.5× Loading | 2× Loading
| k₁ | k₂ | R² | k₁ | k₂ | R² | k₁ | k₂ | R²
0.25 | 0.258 | 0.005 | 0.991 | 0.289 | 0 | 0.988 | 0.248 | 0.014 | 0.984
0.50 | 0.290 | 0.063 | 0.992 | 0.229 | 0.020 | 0.983 | 0.184 | 0.034 | 0.982
0.75 | 0.230 | 0.016 | 0.992 | 0.277 | 0.005 | 0.985 | 0.193 | 0.025 | 0.989
1.00 | 0.319 | -0.008 | 0.995 | 0.222 | 0.016 | 0.987 | 0.142 | 0.045 | 0.977

One theory suggests that Fickian behavior is explained by the unbound water molecules present in micro and macrovoids of the rubbery agar/carrageenan hydrogel blend that are highly mobile and can easily penetrate the rubbery network [7, 8]. The unbound water serves as transport carrier for vitamin B12, which does not have ionizable groups and, therefore, has weak interactions with water and the 3D hydrogel matrix [9]. In effect, the mass transfer becomes primarily a concentration-driven mechanism but with the assistance of stress relaxation (which affects the size of pores and voids).

Fig. 2 shows the correlation between the predicted versus actual values were generated to validate the Peppas-Sahlin model at . Based on the data plots, it can be concluded that the experimentally observed vitamin release behavior is in good agreement with the predictions made by the Peppas-Shalin model.

Figure 2. Predicted versus actual values using Peppas-Sahlin model for (a) 0.25 , (b) 0.50 , (c) 0.75, and (d) 1.0 agar fractions at loading.

Figure 2. Figure 2. Predicted versus actual values using Peppas-Sahlin model for (a) 0.25 , (b) 0.50 , (c) 0.75, and (d) 1.0 agar fractions at loading.

Berens-Hopfenberg. Using the 13-hour vitamin B12 release data, parameters for the diffusivity constant per square thickness ( ), fraction attributed to Fickian diffusion ( ), and first-order relaxation constant were determined. Tables 4-6 summarizes the obtained parameters, while Fig. 3 shows the best-fit plots for loading. Since every hydrogel sample is approximated as a thin film/disk, the Berens-Hopfenberg model has been modified to fit the geometry.

Table 4. Best fit parameters of release data using the Berens-Hopfenberg model at loading.

agar fraction | D/L² | x (E10) | kR (E03) | R²
0.25 | 0.1247 | 1.83 | 3.3 | 0.995
0.50 | 0.0007 | 3.9E8 | 3.4 | 0.994
0.75 | 0.0595 | 18.1 | 3.4 | 0.993
1.00 | 0.0197 | 5.8E8 | 3.9 | 0.995

Table 5. Best fit parameters of release data using the Berens-Hopfenberg model at loading.

agar fraction | D/L² | x (E10) | kR (E03) | R²
0.25 | 0.0000 | 3.83 | 0.0039 | 0.989
0.50 | 0.0015 | 0.0 | 0.2215 | 0.990
0.75 | 0.0595 | 1.2E8 | 0.0038 | 0.987
1.00 | 0.0197 | 0 | 0.0032 | 0.991

Table 6. Best fit parameters of release data using the Berens-Hopfenberg model at loading.

agar fraction | D/L² | x (E-10) | kR (E-03) | R²
0.25 | 0.1247 | 0.0 | 3.7 | 0.987
0.50 | 0.0197 | 0.0 | 3.4 | 0.981
0.75 | 0.0595 | 8.6E7 | 3.0 | 0.989
1.00 | 0.0197 | 0.0 | 3.1 | 0.977

Fig. 3. vs. time plots for Berens-Hopfenberg model at (a) 0.25 ,(b) 0.50 , (c) 0.75 , and (d) 1.0 agar fractions at loading.

Fig. 3. vs. time plots for Berens-Hopfenberg model at (a) 0.25 ,(b) 0.50 , (c) 0.75 , and (d) 1.0 agar fractions at loading.

No discernible trend can be observed from the obtained for the parameters using the experimental data at different loading coefficients and agar mass fractions; however, one observable trend is the
relatively low values for the Fickian fraction for all loading coefficients and agar mass fractions. This modelling result from Berens-Hopfenberg curve fitting is somehow not in agreement with the those obtained from the Korsmeyer-Peppas and Peppas-Sahlin model predictions (since a low value indicates that non-Fickian diffusion is the dominant mechanism for the vitamin B12 release). One possible reason for this deviation may be attributed to the derivation of the Berens-Hopfenberg model equation: unlike the Korsmeyer-Peppas and the Peppas-Sahlin equations, the Berens-Hopfenberg equation is based on the weighted sum of Fick's second law of diffusion and the first-order polymer relaxation model. Both differential equations are solved using boundary conditions for of an inward (i.e., absorptive) solute transport, where polymer chain disentanglement occurs with the influx of water into the hydrogel; thus, despite the observed high values (as shown in Fig. 3), the model used in this study may possibly not accurately describe the irreversible stress relaxation that is occurring with the outward transport and release of vitamin B12 from the hydrogel blend.

Summary

The original version of this paper is available on https://www.scientific.net/EC.3.31.pdf

Vitamin B12 release for agar/ -carrageenan hydrogel blend may be mathematically modeled using the Korsmeyer-Peppas and Peppas-Sahlin, while the Berens-Hopfenberg model may need to be further modified in order to accurately describe the physical system. Assuming stationary boundaries, the parameters for diffusivity and first-order polymer relaxation constant were determined. For the Korsmeyer-Peppas model, since the values for are mostly greater than 0.5 , the diffusion mechanism is described by anomalous non-Fickian diffusion, which involves both diffusion and relaxation. The Peppas-Sahlin model was used to approximate the individual contributions of these two types of diffusion. Curve fitting of the experimental data consistently suggests that Fickian diffusion is dominant. Modelling the release data onto the Berens-Hopfenberg equation resulted to contradictions with the findings of the two other models since the equation was designed to describe inward diffusion and not release; thus, revision and further validation are strongly recommended.

Acknowledgment

The original version of this paper is available on https://www.scientific.net/EC.3.31.pdf

This work was funded by the UP System Enhanced Creative Work and Research Grant (ECWRG-2020-2-19R).

References

The original version of this paper is available on https://www.scientific.net/EC.3.31.pdf

N.J. Starr, K.A. Hamid, J. Wibawab, I. Marlow, M. Bell, L. Pérez-García, D.A. Barrett and D.J. Scurr: Int. J. Pharm. 563 (2019), pp. 21-29.

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L. Jin, P. Lu, H. You, Q. Chen and J. Dong: Int. J. Pharm. 371 (2009), pp. 82-88.

F. Rossi, M. Santoro, T. Casalini, P. Veglianese, M. Masi and G. Perale: Int. J. Mol. Sci. 12 (2011), pp. 3394-3408.

L. Li, J. Zhao, Y. Sun, F. Yu and J. Ma: Chem. Eng. J. 372 (2019), pp. 1091-1103

C. Mircioiu, V. Voicu, V. Anuta, A. Tudose, C. Celia, D. Paolino, M. Fresta, R. Sandulovici and I. Mircioiu: Pharmaceutics 11 (2019), pp. 140.

H. Ardebili, J. Zhang and M.G. Pecht: Characterization of encapsulant properties. Encapsulation Technologies for Electronic Applications (William Andrew, NY, 2019).

A. Abruzzo. Chitosan based hydrogels for transmucosal drug delivery. Doctoral dissertation, University of Bologna ().

M.A. Fauzi, P. Pudjiastuti, A.C. Wibowo and E. Hendradi: Polymers 23, 16 (2021), pp. 2666.

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The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-3/978-3-0364-1338-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 3, pp 37-43

doi: 10.4028/p-497n8w

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2023-02-23

Accepted:
2023-03-12

Online:
2023-06-20

Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

The original version of this paper is available on https://www.scientific.net/EC.3.37.pdf

Muhammad Amir Jamilludin , I Kadek Hariscandra Dinatha , Apri I. Supii , Juliasih Partini , Dwi Liliek Kusindarta and Yusril Yusuf

¹Department of Physics, Faculty of Mathematics and Natural Science, Gadjah Mada University, Indonesia

Research Centre for Marine and Bioindustry, National Research and Innovation Agency, Indonesia

Department of Anatomy, Faculty of Veterinary Medicine, Gadjah Mada University, Indonesia

muhammadamirjamilludin@mail.ugm.ac.id, ikadekhariscandradinatha@mail.ugm.ac.id, aprisupii@yahoo.co.id, djuliasih@ugm.ac.id, eindarta@ugm.ac.id, yusril@ugm.ac.id

Keywords: Calcination, calcium carbonate, calcium oxide, sea urchin shell.

Abstract

Calcium carbonate ( ) has been taken from sea urchin (Diadema setosum) shell and calcinated at several temperatures to obtain calcium oxide (CaO). X-Ray Fluorescence Spectroscopy (XRF) revealed that the powder from this shell had a high Ca level, which increased at a higher temperature. Fourier Transform Infrared Spectroscopy (FTIR) spectra agreed to an increase in Ca level that showed the presence of CaO at and ; otherwise, disappeared. Using Scanning Electron Microscopy (SEM), the powder morphology was more homogeneous at and than at lower temperatures. This morphology was encouraged by decreasing particle size, indicating compound decomposition in the powder and Ca leaved. This decomposition was confirmed by an Energy Dispersive X-ray Spectroscopy (EDS) analysis that showed increased Ca content with higher mass and atomic level at a higher temperature.

Introduction

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Sea urchin (Diadema setosum) shell is the source of Ca in the form of calcium carbonate , which highly potential for synthesizing CHAp[1], like other natural shells such as common cockle shell[2], cockle shell[3], and oyster shell[4] with high of Ca level. Calcium ( Ca ) contribute to several functions in the human body[5]. Ca can be used for biomedical purposes, even several environmental technologies[6,7]. In other applications, is decomposed into calcium oxide ( CaO ), which shows potential as biomaterials for bone and teeth implants[8]. Transforming into CaO needed a calcination process with calcination temperature that depended on the nature of the compounds before the shell was calcinated[9]. In the previous study, the abalone mussel shell had a Ca level of before calcination at , and the Ca level increased up to . In another study, green mussel shell has been reported Ca level at calcination temperature , then increase until at which higher and potential as a precursor for hydroxyapatite synthesis, at this calcination temperature indicated breaking of chemical bond of into CaO is faster, confirmed by infrared spectra analysis[11]. Calcination temperature can affect the characteristics and phase transition of . Previous research has studied the effect of calcination temperature at for aquatic materials, including oyster shells, mussel shells, and cuttlebone, and obtained optimum material conditions[12]. Another study reported that crab shell was calcinated at a temperature of and obtained appropriate material for synthesizing hydroxyapatite[13]. In this study, sea urchin shell was used as raw materials. We analyzed the effects of calcination temperature on the powder's chemical and morphological characteristics derived from the shell.

Materials and Methods

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Synthesis of CaO Powder. Sea urchin shells were taken from Bali. The shells were washed with distilled water and boiled for 30 minutes, then sun-dried for 8 hours. The shells were soaked in acetone for 24 hours and then sun-dried for 6 hours. As dried, to obtain powder, the shells were milled for 30 seconds in 3 times repetition. The powder was calcined in a furnace for 6 hours with temperature variations of , and to obtain pure CaO .

Characterization of Powder. The chemical composition of powders was characterized by X-Rays Fluorescence (XRF [RIGAKU-NEX + QuanTEZ]), including atomic level. The functional group of powders were characterized by FTIR (Thermo Nicolet iS10, Japan); this FTIR characterization used a range of wavenumber . The morphology of powders was observed using Scanning Electron Microscopy (SEM, Joel JSM-6510LA-1400, Japan) with an accelerating voltage of 15 kV and magnification of 1000 times. Powders' particle size distribution was calculated using ImageJ by measuring 60 random particles. To determine the composition of calcium and other compounds in powders, used Energy Dispersive X-ray Spectroscopy (EDS) that included while performing SEM.

Results and Discussions

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The Ca level of the powders was characterized using XRF. As shown in Table 1, calcinated powder at and had the highest Ca level; with the same value. Ca level significantly increased when calcination temperature increased, but at , the increase became slow. Fig. 1(a)-(d) shows that the powders had an increasing intensity of while calcination temperature increased, which confirmed the increase in Ca level. As shown in Fig. 1(a) and (b), the intensity of the Ca-Kα peak slightly increased. As in Fig. 1(c) and (d), the increase in intensity peak was significant compared with lower temperature. Sr impurity remained at a superficial level in all temperatures, not more than .

Table 1. Percentage of Ca level.

Powder at variation of calcination temperature | Ca level (%)
600 °C | 93.39 ± 0.10
800 °C | 94.79 ± 0.05
900 °C | 96.01 ± 0.02
1100 °C | 96.06 ± 0.02

Figure 1. XRF spectra of calcinated powders at (a) , (b) , (c) , and (d) .

Figure 1. Figure 1. XRF spectra of calcinated powders at (a) , (b) , (c) , and (d) .

Fig. 2 shows FTIR spectra of the powders. It is shown in Fig. 2(a) and (b) that calcinated powder at and had a bond functional group of and at the same position, bond at , and , and bond at , indicated the presence of . The positions of the bond functional group were close to references of the bond functional group . The transmittance of and bonds increased while calcination temperature increased, which meant the level decreased. The bond disappeared, then another bond appeared at at , and the transmittance became lower at . OH - stretching functional group appeared for the first time at at calcination temperature , and transmittance became lower at higher calcination temperature, which confirmed the increase of CaO level according to the OH group. CaO bond functional group was present at at , and the transmittance became lower at , which meant the CaO level increased. The increase in CaO was not significant; this could be seen in Fig. 2(c) and (d).

This result concluded that was decomposed into CaO triggered by the calcination process, with as the minimum temperature for the decomposition process[10]. received heat, causing atoms to move faster. This condition led breaking process of the chemical bond into CaO and ; at higher calcination temperature chemical bond is broken more quickly[11,16,17].

Figure 2. FTIR spectra of calcinated powders at (a) , (b) , (c) , and (d) .

Figure 2. Figure 2. FTIR spectra of calcinated powders at (a) , (b) , (c) , and (d) .

Fig. 3(a1,a2)-(d1,d2) shows the powders' morphology and particle size distribution characterized using SEM. It is shown that calcinated powder at higher temperatures caused smaller particle sizes. As shown in Fig. 3(a1,a2), the particle distribution was heterogeneous at , and the particle size was large, about . Fig. 3(b1,b2) shows that particles had been reduced into smaller particles size of but remained with irregular and ununiform shapes at . As seen in Fig. 3(c1,c2)(d1,d2), the particles quickly became homogeneous and orderly distributed at higher calcination temperatures, at and , with smaller particle sizes up to . But at those
temperatures, the particles had interconnected and agglomerated shapes in a solid structure, indicating optimum calcination temperatures. This particle size reduction defined particle compounds' decomposition at the atomic level, indicating that the calcination process released and created cavities[10]. It could be seen at ; cavities created are more than . In those temperatures, the distribution and size of particles were almost the same or slight differed compared with lower temperatures.

Figure 3. SEM analysis of calcinated powders at (a1,a2) , (b1,b2) , (c1,c2) , and .

Figure 3. Figure 3. SEM analysis of calcinated powders at (a1,a2) , (b1,b2) , (c1,c2) , and .

Fig. 4 show the EDS spectra of the powders. It is shown in Fig. 4(a)-(d) that at higher calcination temperatures, and had a higher peak, which meant the Ca level was increasing. The mass and atom count percentage of Ca obtained during characterization was performed in Table 2, which shows an increasing value which confirms the decomposition process of another compound and leaves Ca caused decreasing in particle size in SEM analysis. While the temperature was raised, decomposition occurred faster; this heat helped optimize decomposition[18]. At and , the increase of Ca was low, indicating a slower decomposition process.

Figure 4. EDS analysis of calcinated powders at (a) , (b) , (c) , and (d) .

Figure 4. Figure 4. EDS analysis of calcinated powders at (a) , (b) , (c) , and (d) .

Table 2. Percentage of Ca mass and atom.

Powder at variation of calcination temperature | Ca mass (%) | Ca atom (%)
600 °C | 36.07 | 17.57
800 °C | 41.37 | 21.66
900 °C | 48.31 | 27.40
1100 °C | 50.63 | 29.05

Conclusions

The original version of this paper is available on https://www.scientific.net/EC.3.37.pdf

In this experiment, CaO was synthesized from sea urchin shells through calcination. The XRF analysis showed the powder had the highest Ca level, up to at and . FTIR results revealed changes in functional groups indicated phase transition from into was present for the first time at , and Ca level became higher at . The infrared spectra showed that was possibly being minimum calcination temperature for CaO appearance through the decomposition process. SEM results showed particle distribution became more homogeneous and orderly distributed in higher calcination temperatures with smaller particle sizes, indicating the decomposition of powder leaving Ca content. This SEM analysis was confirmed by the EDS result that showed the percentage of Ca increased while calcination temperature increased. From all those analysis results, increasing Ca was fast until and became slow when it reached . This high Ca content encourages the possibility for biomaterial application, certainly in the synthesis of hydroxyapatite (HAp) or carbonated hydroxyapatite (CHAp).

Acknowledgement

The original version of this paper is available on https://www.scientific.net/EC.3.37.pdf

The authors thank PMDSU scholarship for financial support in this research and the Ministry of Education and Culture Republic of Indonesia for the grant (1995/UNI/DITLIT/DitLit/PT.01.03/2022), also Research Centre for Marine and Bioindustry for sea urchin resource. The authors acknowledge been worked with technical assistance and using research instruments and testing facilities of the Laboratory for Research and Testing Universitas Gadjah Mada, Indonesia.

References

The original version of this paper is available on https://www.scientific.net/EC.3.37.pdf

I. K. Januariyasa and Y. Yusuf, "Porous carbonated hydroxyapatite-based scaffold using simple gas foaming method," Journal of Asian Ceramic Societies, vol. 8, no. 3, pp. 634-641, Jul. 2020, doi: 10.1080/21870764.2020.1770938.

A. Aminatun et al., "Biopolymer-based polycaprolactone-hydroxyapatite scaffolds for bone tissue engineering," International Journal of Polymeric Materials and Polymeric Biomaterials, 2021, doi: 10.1080/00914037.2021.2018315.

Y. Rizkayanti and Y. Yusuf, "Effect of Temperature on Synthesis of Hydroxyapatite from Cockle Shells (Anadara Granosa)," 2018.

Almukarrama and Y. Yusuf, "Development Carbonated Hydroxyapatite Powders from Oyster Shells (Crassostrea gigas) by Sintering Time Controlling," in IOP Conference Series: Materials Science and Engineering, Jul. 2019, vol. 546, no. 4. doi: 10.1088/1757-899X/546/4/042001.

G. Cormick and J. M. Belizán, "Calcium intake and health," Nutrients, vol. 11, no. 7. MDPI AG, Jul. 01, 2019. doi: 10.3390/nu11071606.

P. Terzioğlu, H. Öğüt, and A. Kalemtaş, "Natural calcium phosphates from fish bones and their potential biomedical applications," Materials Science and Engineering C, vol. 91. Elsevier Ltd, pp. 899-911, Oct. 01, 2018. doi: 10.1016/j.msec.2018.06.010.

J. A. Currie, N. R. Harrison, L. Wang, M. I. Jones, and M. S. Brooks, "A preliminary study of processing seafood shells for eutrophication control," Asia-Pacific Journal of Chemical Engineering, vol. 2, no. 5, pp. 460-467, Sep. 2007, doi: 10.1002/apj. 82.

V. K. Mishra, S. K. Srivastava, B. P. Asthana, and D. Kumar, "Structural and Spectroscopic Studies of Hydroxyapatite Nanorods Formed via Microwave-Assisted Synthesis Route,"Journal of the American Ceramic Society, vol. 95, no. 9, pp. 2709-2715, Sep. 2012, doi: 10.1111/j.15512916.2012.05134.x.

N. Suwannasingha, A. Kantavong, S. Tunkijjanukij, C. Aenglong, H. B. Liu, and W. Klaypradit, "Effect of calcination temperature on structure and characteristics of calcium oxide powder derived from marine shell waste," Journal of Saudi Chemical Society, vol. 26, no. 2, Mar. 2022, doi: 10.1016/j.jscs.2022.101441.

M. Sari, P. Hening, Chotimah, I. D. Ana, and Y. Yusuf, "Porous structure of bioceramics carbonated hydroxyapatite-based honeycomb scaffold for bone tissue engineering," Materials Today Communications, vol. 26, Mar. 2021, doi: 10.1016/j.mtcomm.2021.102135.

M. Sari and Y. Yusuf, "Synthesis and characterization of hydroxyapatite based on green mussel shells (perna viridis) with the variation of stirring time using the precipitation method," in IOP Conference Series: Materials Science and Engineering, Nov. 2018, vol. 432, no. 1. doi: 10.1088/1757-899X/432/1/012046.

S. Soisuwan, J. Phommachant, W. Wisaijorn, and P. Praserthdam, "The Characteristics of Green Calcium Oxide Derived from Aquatic Materials," Procedia Chemistry, vol. 9, pp. 53-61, 2014, doi: 10.1016/j.proche.2014.05.007.

B. N. Bhattacharjee, V. K. Mishra, S. B. Rai, O. Parkash, and D. Kumar, "Structure of Apatite Nanoparticles Derived from Marine Animal (Crab) Shells: An Environment-Friendly and CostEffective Novel Approach to Recycle Seafood Waste," ACS Omega, vol. 4, no. 7, pp. 1275312758, Jul. 2019, doi: 10.1021/acsomega.9b00134.

S. Rujitanapanich, P. Kumpapan, and P. Wanjanoi, "Synthesis of hydroxyapatite from oyster shell via precipitation," in Energy Procedia, 2014, vol. 56, no. C, pp. 112-117. doi: 10.1016/j.egypro.2014.07.138.

J. H. Shariffuddin, M. I. Jones, and D. A. Patterson, "Greener photocatalysts: Hydroxyapatite derived from waste mussel shells for the photocatalytic degradation of a model azo dye wastewater," Chemical Engineering Research and Design, vol. 91, no. 9, pp. 1693-1704, Sep. 2013, doi: 10.1016/j.cherd.2013.04.018.

M. Sari, P. Hening, Chotimah, I. D. Ana, and Y. Yusuf, "Bioceramic hydroxyapatite-based scaffold with a porous structure using honeycomb as a natural polymeric Porogen for bone tissue engineering," Biomaterials Research, vol. 25, no. 1, Dec. 2021, doi: 10.1186/s40824-021-00203z.

H. A. Permatasari and Y. Yusuf, "Characteristics of Carbonated Hydroxyapatite Based on Abalone Mussel Shells (Halioitis asinina) Synthesized by Precipitation Method with Aging Time Variations," in IOP Conference Series: Materials Science and Engineering, Jul. 2019, vol. 546, no. 4. doi: 10.1088/1757-899X/546/4/042031.

M. Sari and Y. Yusuf, "Synthesis and Characterization of Hydroxyapatite based on Green Mussel Shells (Perna viridis) with Calcination Temperature Variation Using the Precipitation Method," 2018.

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The original version of this eBook is available on https://www.scientific.net/book/engineering-chemistry-vol-3/978-3-0364-1338-9

Engineering Chemistry, ISSN: 2813-6535, Vol. 3, pp 45-50

doi: 10.4028/p-r0xur7

© 2023 The Author(s). Published by Trans Tech Publications Ltd, Switzerland.

Submitted:
2023-02-07

Accepted:
2023-03-11

Online:
2023-06-20

The Effect of Antimicrobial Additive on Plastic Deterioration

The original version of this paper is available on https://www.scientific.net/EC.3.45.pdf

B.Dasdemir , B.Kukcu , K.Kanburoglu , A.S.Vanli and A.Akdogan

Mesan Lock Inc., Silivri, Istanbul, Turkey

Yıldız Technical University, Department of Mechanical Engineering, Istanbul, Turkey

busedasdemir@essentra.com, burakkukcu@essentra.com, kaankanburoglu@essentra.com, svanli@yildiz.edu.tr, enomak@yildiz.edu.tr

Keywords: Industrial Locks, Hygienic Requirements, Polymeric Materials, Antimicrobial Additives.

Abstract

The Covid-19 virus, which started in 2019 and has taken the whole world under its influence has negatively affected normal living conditions and accordingly, increased awareness to prevent anti-microbial diseases transmitted by contact. In almost all sectors, precautions have been taken considering the transmission of diseases by contact. As a requirement of our age, they enrich their product ranges by developing new methods and making innovations for companies whose sector is dominated by industrial locks, hinges, and handles, both in terms of hygienic product design and in terms of the raw material of the part used in production. For example, it is preferable that the products in the air-conditioning sector have anti-microbial properties. The evaluation of the effect of microorganisms on plastic raw materials and the determination of whether this effect causes future deterioration in plastic materials has been examined in our article. Currently, the products supplied to the sectors are products produced from raw materials such as PA6 GFR30, ABS, PA6, which are available on the market. It is aimed to provide anti-microbial properties of products in accordance with the needs of the sector and the era by changing the raw material used or adding additives in certain proportions to the raw material.

Introduction

The original version of this paper is available on https://www.scientific.net/EC.3.45.pdf

Industrial polymers are common materials used in manufacturing o0f toys, packaging, and many households producing such as disposable plates, spoons, and forks. Plastic materials are easy to use and clean products. However, it is a suitable environment for bacterial growth in reuse because plastic can biodegrade and its carbon can be used as food by fungi and bacteria [1].

Bacteria and microbes on plastic products cause biological deterioration. Biodegradation is defined as the situation in which an undesirable change in the color, strength, or mass of the product occurs. Plastic products can be modified as antimicrobial with the additives used to prevent biological degradation. Antimicrobials are used in a wide range of plastic applications [2]. We can find the properties of these additives in the related standards like ISO Plastics - Evaluation of the action of microorganisms [3]. In the standard, the colonization of microorganisms on the surface of the plastic product, the deterioration of plastics that create a nutritious environment for microorganisms, and the biological deterioration of the product are examined. The function of the antibacterial additives is to prevent the growth of bacteria, mold, and pathogenic microorganisms by .

Depending on the conditions of the pandemic process, studies have been initiated to make antimicrobial products for preference and to fulfill the supply of them on the market [4]. Locks, gaskets, handles, etc. used in the air handling unit sector. Studies are carried out on the condition that products such as products comply with the above-mentioned standard by using different raw materials or by adding additives to the raw material used. The antimicrobial additive material used because of the criteria provided by this standard reduces the proliferation of the organisms specified in the product and the biological deterioration of the plastic.

By using antibacterial additives, it is aimed to prevent the proliferation of microorganisms in the products, as well as to support the antibacterial feature by designing the environments where
microorganisms can adhere and multiply, by designing such environments at a minimum level. The main points to be considered in terms of design can be considered as follows.

The part should not have indentations and protrusions that can create the necessary habitat for the reproduction and living of microorganisms such as water and dust. The surfaces should be as flat as possible, away from sharp recesses and sharp protrusions as much as possible. The recesses will create a suitable environment for the proliferation of microorganisms. Since there are no recesses and sharp surfaces that will create this environment, it will be ensured that water, dust, and similar substances that will cause the proliferation of microorganisms will not stick on the surface.

Sharp transitions should be avoided as much as possible. The examples we made are examples of the lever locks available in Mesan lock Inc. (Fig. 1). Sharp corners and lines may contain substances such as dust and dirt and may create an environment for the growth of microorganisms. However, the round design will keep the accumulation of such factors to a minimum due to its rounded lines. Accordingly, the new lever lock design we have designed has been optimally adapted to the abovementioned features (Fig. 2).

Figure 1. A Sharp Corner Designed Industrial Lock Inc.

Figure 1. Figure 1. A Sharp Corner Designed Industrial Lock Inc.

Figure 2. A Round Corner Designed Industrial Lock Inc.

Figure 2. Figure 2. A Round Corner Designed Industrial Lock Inc.

Our aim in this work is to offer a product in compliance with antimicrobial standards by choosing the appropriate additive to the plastic raw material ensuring optimum mixing.

Antimicrobial Additive. Products made from Plastic materials are easy to clean and use. However, it is a suitable environment for bacterial growth in reuse. There is a general belief in society that plastic materials are not hygienic products. Therefore, it is aimed to give antibacterial properties to plastic products by using additives. Antimicrobial additives are auxiliary materials that enable the
final product to have antimicrobial product properties by adding a certain amount into the plastic products currently used and dispersing them homogeneously. Thanks to these additives, the formation of bacteria and fungi on the product are prevented by [5]. Heavy metals including silver, zinc, copper, mercury, tin, lead, bismuth, cadmium, chromium, and thallium among the metallic elements have antibacterial capabilities, and the exchange with these metals endows inorganic polymers like zeolites and zirconium with antibacterial activity [6]. Silver-supported zirconium phosphate or silica gel's antibacterial properties aren't brought on by the release of silver ions, but rather by the catalytic action of silver, which causes oxygen to be activated [7,8]. Silver is the most widely used technology as an antibacterial agent in the world due to its historical success, broad performance spectrum, many materials and applications suitability for use are the main factors.

The additive brought to a surface during the production process includes the specific antimicrobial active, such as silver, and can be formulated as a concentrated powder, liquid suspension or masterbatch pellet, depending on the target material and production process.

In this study, an additive containing 15% granular glass with silver ions concentration, which was added to the PA6 GFR 30 raw material, was used. The additive material was turned into masterbatch pellets and mixed homogeneously in PA6 GFR 30.

Case Study

The original version of this paper is available on https://www.scientific.net/EC.3.45.pdf

This study, it is aimed to add a certain number of additives to the plastic raw materials, which are most widely used in industrial lock sectors, to gain antimicrobial properties. This experiment was performed in accordance with ISO 846 : 2019 Plastics - Evaluation of the action of microorganisms standard procedure A, including identification, and visual and microscopic evaluations.

Before the PA6 GFR 30 raw material entered the test environment, the test samples were prepared by mixing the antimicrobial additive in certain percentages homogeneously with the raw material. Then, PA6 GFR30 material, which added a certain percentage of antimicrobial additives, was tested. We can consider the experiment in two stages. The first of these stages is the growth test, that is, the test in which the resistance of the raw material against mold is examined and the resistance tests against bacteria.

Experiment 1 Fungal-Growth Test. Before starting the experiment, the surfaces of the prepared test samples were cleaned with ethanol, and then the microbes detailed below were exposed and their incubation periods were observed. The observation period for this experiment was 4 weeks. As the first, Aspergillus Niger van Tieghem's characteristics are given in Table 1. As the second, Penicillium funiculosum's characteristics are given in Table 2. Additionally, Paecilomyces variotii's and Trichoderma virens's characteristics are given in Table 3. Finally, Chaetomium globosum's characteristics are given in Table 4.

Table 1. Aspergillus Niger van Tieghem's characteristics [9].

Product Category | Fungi
Strain Designation | 4247 [AM 324, CBS 131.52, CBS 769.97, DSM 1957, IFO 6341, IMI 45551, J. Friedrich A98, KCC F-0086, NRRL 334, QM 324, QM 4S8, Steinberg, TC 215-4247, WB 334]
Type strain | No
Genome sequenced strain | Yes

Table 2. Penicillium funiculosum's characteristics [9].

Product Category | Fungi
Strain Designation | IMI 114933 [CBS 631.66, CEB 3296.31, IAM 7013]
Type Strain | Yes
Classification | Fungi, Dikarya, Ascomycota, Pezizomycotina, Eurotiomycetes, Eurotiomycetidae, Eurotiales, Trichocomaceae, Talaromyces

Table 3. Paecilomyces variotii's and Trichoderma virens's characteristics [9].

Table 4 . Chaetomium globosum's characteristics [9].

Product Category | Fungi
Strain Designation | QM 459 [1042.4, CBS 148.51, CBS 161.52, CEB 1218.1, CEB 1218.2, CECT 2701, DSM 1962, IFO 6347, IMI 45550, MUCL 1984, NRRL 1870, UPSC 3159, VTT D-81079]
Type Strain | No
Genome Sequenced Strain | Yes

During this 4-week period, mold resistance of the above-mentioned Fungi was observed in the piece. This process is illustrated visually. In the image you see on the left, there is an antimicrobial added plastic sample sent before the test starts. On the right, there is a sample image that has not changed at all (that is, it passed the test and gave a positive result) as a result of the 4 -week test period (Fig. 3).

Figure 3. Fungal-Growth Test Illustration.

Figure 4. Figure 3. Fungal-Growth Test Illustration.

The meanings of the intensity grades used for the evaluation of mold growth are given in Table 5.

Table 5. Intensity Grade Evaluations [10].

Intensity | Evaluation
0 | no growth visible under microscopic inspection
1a | no growth visible with the naked eye, but growth clearly visible under the microscope, up to 25 % of the sample surface overgrown
1b | no growth visible with the naked eye, but growth clearly visible under the microscope, up to 50 % of the sample surface overgrown
1c | no growth visible with the naked eye, but growth clearly visible under the microscope, more than 50 % of the sample surface overgrown
2 | growth visible with the naked eye, up 25 % of the sample surface overgrown
3 | growth visible with the naked eye, up 50 % of the sample surface overgrown
4 | considerable growth, more than 50 % of the sample surface overgrown
5 | strong growth, whole sample surface overgrown

The findings found as a result of the mold resistance test (growth test) are detailed as follows. It was observed that the raw material prepared with the additive did not show any change in color or structure compared to the uninoculated sterile sample and control samples. No mold formation could be detected on the sample surface, even under microscopic examination. The growth density was determined as " 0 ". Overall evaluation growth intensity is also determined as " 0 ".

Experiment 2 Bacteria Resistance Test. The test is done according to above mentioned "Plastics -evaluation of the action of microorganisms" standard, procedure C, including identification, visual and microscopic evaluation [3]. For this experiment, the surface of the test pieces was cleaned again with 70% ethanol.

Material prepared with the additive did not show any change in color or structure compared to the uninoculated sterile sample and control samples. No mold formation could be detected on the sample surface, even under microscopic examination. The growth density was determined as " 0 ".

As a result of our experiments, it was observed that the optimum ratio determined for the PA6 GFR30 raw material piece with antimicrobial additives was .

Summary

The original version of this paper is available on https://www.scientific.net/EC.3.45.pdf

Microbe growth and raw material degradation create problems in many sectors. For this reason, antimicrobial additives are gaining value day by day. With the spread of the coronavirus around the world, customers' interest in antimicrobial products is increasing. As this need for customers increased, companies started to add antimicrobial additives at certain rates to their products. In this study, we examined the effect of 6% antimicrobial additive added to PA6 GFR30 raw material by observing bacteria and mold formations. According to the results of our mold and bacteria growth experiments, no mold or bacteria growth was observed in the handle lock products produced in our company as a result of mixing the masterbatch containing silver ion glass powder with PA6 GFR30 raw material. Companies producing antimicrobial products with PA6 GFR30 raw material will increase their costs and produce inefficiently because of using more than additives. Therefore, it is important for engineers to make decisions based on the results we have shown in our study. By making design improvements and adding additive raw materials to the products in the right ratio, it is possible to stop the reproduction of microbes and ensure that they do not stick to the surfaces .

References

The original version of this paper is available on https://www.scientific.net/EC.3.45.pdf

Özden D. Plastik Biyodegradasyonu: Genel Sorunlar ve Biyoteknolojik Çözümler. International Journal of Life Sciences and Biotechnology, 2021. 4(2): p. 324-339

Niall D'arcy: Antimicrobials in Plastics: A Global Review, Plastics, Additives and Compounding Vol. 3 (2001) p.12-15.

ISO 846:2019 Plastics-Evaluation of the action of microorganisms, Standard.

Minghu L. Lukas B. Christiane L.N. Marc G.A. Wiliam A.A. and Boxin Z.: Antimicrobial polymeric composites for high-touch surfaces in healthcare applications: Current Opinion in Biomedical Engineering Vol. 22, June 2022.

Polymer Additives Used to Enhance Material Properties for Medical Device Applications, Vinny R. Sastri, Plastics in Medical Devices (Third Edition), 2022

X.Zhao: Antibacterial bioactive materials, Bioactive Materials in Medicine. (2011) p.97-123

Niira R. Yamamoto T. and Uchida S.: Aerosols containing antimicrobial zeolite. Jpn Kikai Tokyo Koho. Japanese Patent. 1988;63(250):325.

Hiyama K. Muriyasu N. and Omuri T. Antibacterial effect of Ag and Zn-Zeolite and bacteriostatic action of Ag- and Zn-Zeolite kneaded polyethylene films. Antibacterial Agents. 1995; 23(4): 197-203.

(Test Result)

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Keywords Index

A

Agar Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

Antimicrobial Additives The Effect of Antimicrobial Additive on Plastic Deterioration

B

Bone Biomaterial Synthesis and Characterization of Carbonate Hydroxyapatite from Pinctada Maxima Shell with Short Aging Time for Bone Biomaterial Candidate

C

Calcination Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

Calcium Carbonate Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

Calcium Oxide Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

Carbonate Hydroxyapatite Synthesis and Characterization of Carbonate Hydroxyapatite from Pinctada Maxima Shell with Short Aging Time for Bone Biomaterial Candidate

Carrageenan Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

Catalyst Recent Advances on Copper Based Metal Organic Framework as Heterogenous Catalyst Inorganic Coupling Reaction: A Review

Copper Metal Organic Frameworks Recent Advances on Copper Based Metal Organic Framework as Heterogenous Catalyst Inorganic Coupling Reaction: A Review

Coupling Reactions Recent Advances on Copper Based Metal Organic Framework as Heterogenous Catalyst Inorganic Coupling Reaction: A Review

D

Drug Release Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

H

Homogenous And Heterogenous Catalyst Recent Advances on Copper Based Metal Organic Framework as Heterogenous Catalyst Inorganic Coupling Reaction: A Review

Hydrogel Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

Hygienic Requirements The Effect of Antimicrobial Additive on Plastic Deterioration

I

Industrial Locks The Effect of Antimicrobial Additive on Plastic Deterioration

P

P. Maxima Synthesis and Characterization of Carbonate Hydroxyapatite from Pinctada Maxima Shell with Short Aging Time for Bone Biomaterial Candidate

Polymeric Materials The Effect of Antimicrobial Additive on Plastic Deterioration

S

Sea Urchin Shell Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

Short Aging Time Synthesis and Characterization of Carbonate Hydroxyapatite from Pinctada Maxima Shell with Short Aging Time for Bone Biomaterial Candidate

V

Vitamin Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

Authors Index

A

Adimule, V. Recent Advances on Copper Based Metal Organic Framework as Heterogenous Catalyst Inorganic Coupling Reaction: A Review; Synthesis, Characterization, Optical and Luminescence Properties of Copper Based Metal Organic Frame Works

Ahmed, E. Recent Advances on Copper Based Metal Organic Framework as Heterogenous Catalyst Inorganic Coupling Reaction: A Review

Akdogan, A. The Effect of Antimicrobial Additive on Plastic Deterioration

B

Batakurki, S. Recent Advances on Copper Based Metal Organic Framework as Heterogenous Catalyst Inorganic Coupling Reaction: A Review; Synthesis, Characterization, Optical and Luminescence Properties of Copper Based Metal Organic Frame Works

D

Dasdemir, B. The Effect of Antimicrobial Additive on Plastic Deterioration

Deang, M. Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

Dinatha, I. Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

F

Fajardo, J. Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

J

Jamilludin, M. Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

K

Kanburoglu, K. The Effect of Antimicrobial Additive on Plastic Deterioration

Kukcu, B. The Effect of Antimicrobial Additive on Plastic Deterioration

Kusindarta, D. Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

M

Megawati, M. Synthesis and Characterization of Carbonate Hydroxyapatite from Pinctada Maxima Shell with Short Aging Time for Bone Biomaterial Candidate

P

Pai, M. Synthesis, Characterization, Optical and Luminescence Properties of Copper Based Metal Organic Frame Works

Partini, J. Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

Patty, D. Synthesis and Characterization of Carbonate Hydroxyapatite from Pinctada Maxima Shell with Short Aging Time for Bone Biomaterial Candidate

S

Supii, A. Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell

T

Taña, D. Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

Tumolva, T. Kinetics Modelling of Vitamin B12 Release in an Agar/k-Carrageenan Hydrogel Blend

V

Vanlı, A. The Effect of Antimicrobial Additive on Plastic Deterioration

Y

Yallur, B. Recent Advances on Copper Based Metal Organic Framework as Heterogenous Catalyst Inorganic Coupling Reaction: A Review; Synthesis, Characterization, Optical and Luminescence Properties of Copper Based Metal Organic Frame Works

Yusuf, Y. Synthesis and Characterization of Carbonate Hydroxyapatite from Pinctada Maxima Shell with Short Aging Time for Bone Biomaterial Candidate; Chemical and Morphological Analysis of Calcium Oxide (CaO) Powder from Sea Urchin (Diadema setosum) Shell