Displaying publications 61 - 80 of 100 in total

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  1. A urea precursor to synthesize carbon nitride with mesoporosity for enhanced activity in the photocatalytic removal of phenol
    Lee SC, Lintang HO, Yuliati L
    Chem Asian J, 2012 Sep;7(9):2139-44.
    PMID: 22733646 DOI: 10.1002/asia.201200383
    A urea precursor was used for the first time to prepare mesoporous carbon nitride (MCN) by a thermal polymerization process with silica nanospheres as a hard template. Although the prepared MCN samples have similar structures and optical properties, it was revealed that the specific surface area, pore-size distribution, and morphology of the MCN samples depend on the initial mass ratio of urea to silica. Compared to the bulk carbon nitride (BCN) that only gave 20% phenol removal (6 h of irradiation), the activities can be enhanced up to 74% on MCN samples for photocatalytic removal of phenol under visible-light irradiation. The highest conversion was obtained on MCN with an initial mass ratio of urea to silica of 5, which has high surface area of 191 m(2) g(-1) and a nanoporous structure with uniform pore-size distribution of 7 nm. In addition to the high activity, the MCN sample also showed high photocatalytic stability.
    Matched MeSH terms: Polymerization
  2. Preparation, characterization and properties of core-shell cobalt ferrite/polycaprolactone nanomagnetic biomaterials
    Khoo KS, Nur Farhana Amari, Tan CY, Shahidan Radiman, Redzuwan Yahaya, Muhamad Samudi Yasir
    Sains Malaysiana, 2013;42:167-173.
    Combination of magnetic and biocompatible materials to form core-shell nanomaterials has been widely used in medical fields. These core-shell magnetic biomaterials have a great potential for magnetic fluid hyperthermia (MFH) treatment to remedy cancer. The aims of this study were to investigate the production of core-shell cobalt ferrite/polycaprolactone (CoFe2O4/PCL) nanomaterials with different ratios of cobalt ferrite to caprolactone, to study the effects of using polymer in reducing the agglomerations between particles and to determine the structure, morphology, thermal and magnetic properties of these core-shell nanomaterials. The core-shell nanomaterials were produced by in situ polymerization method. The formation of the CoFe2O4/PCL was investigated by means of Fourier transform infrared spectroscopy (FTIR), x-ray diffractometer (XRD) and transmission electron microscopy (TEM). Its thermal properties were determined by using thermogravimetric analyzer (TGA). The vibrating sample magnetometer (VSM) was used to reveal the magnetic properties. The results for the XRD and FTIR spectra demonstrated the formation of cobalt ferrite and polycaprolactone in core-shell nanomaterials. From the TEM results, it was seen that the core-shell CoFe2O4/PCL nanomaterials were best formed at a ratio of CoFe2O4 to monomer caprolactone mixtures of 1:4.
    Matched MeSH terms: Polymerization
  3. Fulltext Effect of Preparation Methods on the Tensile, Morphology and Solar Energy Conversion Efficiency of RGO/PMMA Nanocomposites
    Kee SY, Munusamy Y, Ong KS, Lai KC
    Polymers (Basel), 2017 Jun 18;9(6).
    PMID: 30970908 DOI: 10.3390/polym9060230
    In this study, reduced graphene oxide (RGO)/polymethyl methacrylate (PMMA) nanocomposites were prepared by employing in situ polymerization and solution blending methods. In terms of mechanical properties, RGO loading increased the Young's modulus but decreased the elongation at break for RGO/PMMA nanocomposites. Tensile strength for solution blended RGO/PMMA nanocomposites increased after adding 0.5 wt % RGO, which was attributed to the good dispersion of RGO in the nanocomposites as evidenced from SEM and TEM. Solar energy conversion efficiency measurement results showed that the optimum concentration of RGO in the RGO/PMMA nanocomposites was found to be 1.0 wt % in order to achieve the maximum solar energy conversion efficiency of 25%. In the present study, the solution blended nanocomposites exhibited better overall properties than in situ polymerized nanocomposites owing to the better dispersion of RGO in solution blending. These findings would contribute to future work in search of higher conversion efficiency using nanocomposites.
    Matched MeSH terms: Polymerization
  4. Fulltext Membraneless polyester microdroplets as primordial compartments at the origins of life
    Jia TZ, Chandru K, Hongo Y, Afrin R, Usui T, Myojo K, et al.
    Proc Natl Acad Sci U S A, 2019 08 06;116(32):15830-15835.
    PMID: 31332006 DOI: 10.1073/pnas.1902336116
    Compartmentalization was likely essential for primitive chemical systems during the emergence of life, both for preventing leakage of important components, i.e., genetic materials, and for enhancing chemical reactions. Although life as we know it uses lipid bilayer-based compartments, the diversity of prebiotic chemistry may have enabled primitive living systems to start from other types of boundary systems. Here, we demonstrate membraneless compartmentalization based on prebiotically available organic compounds, α-hydroxy acids (αHAs), which are generally coproduced along with α-amino acids in prebiotic settings. Facile polymerization of αHAs provides a model pathway for the assembly of combinatorially diverse primitive compartments on early Earth. We characterized membraneless microdroplets generated from homo- and heteropolyesters synthesized from drying solutions of αHAs endowed with various side chains. These compartments can preferentially and differentially segregate and compartmentalize fluorescent dyes and fluorescently tagged RNA, providing readily available compartments that could have facilitated chemical evolution by protecting, exchanging, and encapsulating primitive components. Protein function within and RNA function in the presence of certain droplets is also preserved, suggesting the potential relevance of such droplets to various origins of life models. As a lipid amphiphile can also assemble around certain droplets, this further shows the droplets' potential compatibility with and scaffolding ability for nascent biomolecular systems that could have coexisted in complex chemical systems. These model compartments could have been more accessible in a "messy" prebiotic environment, enabling the localization of a variety of protometabolic and replication processes that could be subjected to further chemical evolution before the advent of the Last Universal Common Ancestor.
    Matched MeSH terms: Polymerization
  5. Fulltext Synthesis and Thermal Properties of Acrylonitrile/Butyl Acrylate/Fumaronitrile and Acrylonitrile/Ethyl Hexyl Acrylate/Fumaronitrile Terpolymers as a Potential Precursor for Carbon Fiber
    Jamil SNAM, Daik R, Ahmad I
    Materials (Basel), 2014 Sep 01;7(9):6207-6223.
    PMID: 28788187 DOI: 10.3390/ma7096207
    A synthesis of acrylonitrile (AN)/butyl acrylate (BA)/fumaronitrile (FN) and AN/EHA (ethyl hexyl acrylate)/FN terpolymers was carried out by redox polymerization using sodium bisulfite (SBS) and potassium persulphate (KPS) as initiator at 40 °C. The effect of comonomers, BA and EHA and termonomer, FN on the glass transition temperature (Tg) and stabilization temperature was studied using Differential Scanning Calorimetry (DSC). The degradation behavior and char yield were obtained by Thermogravimetric Analysis. The conversions of AN, comonomers (BA and EHA) and FN were 55%-71%, 85%-91% and 76%-79%, respectively. It was found that with the same comonomer feed (10%), the Tg of AN/EHA copolymer was lower at 63 °C compared to AN/BA copolymer (70 °C). AN/EHA/FN terpolymer also exhibited a lower Tg at 63 °C when compared to that of the AN/BA/FN terpolymer (67 °C). By incorporating BA and EHA into a PAN system, the char yield was reduced to ~38.0% compared to that of AN (~47.7%). It was found that FN reduced the initial cyclization temperature of AN/BA/FN and AN/EHA/FN terpolymers to 228 and 221 °C, respectively, in comparison to that of AN/BA and AN/EHA copolymers (~260 °C). In addition, FN reduced the heat liberation per unit time during the stabilization process that consequently reduced the emission of volatile group during this process. As a result, the char yields of AN/BA/FN and AN/EHA/FN terpolymers are higher at ~45.1% and ~43.9%, respectively, as compared to those of AN/BA copolymer (37.1%) and AN/EHA copolymer (38.0%).
    Matched MeSH terms: Polymerization
  6. Fulltext Multiphasic Reaction Modeling for Polypropylene Production in a Pilot-Scale Catalytic Reactor
    Jakir Hossain Khan M, Azlan Hussain M, Mujtaba IM
    Polymers (Basel), 2016 Jun 14;8(6).
    PMID: 30979325 DOI: 10.3390/polym8060220
    In this study, a novel multiphasic model for the calculation of the polypropylene production in a complicated hydrodynamic and the physiochemical environments has been formulated, confirmed and validated. This is a first research attempt that describes the development of the dual-phasic phenomena, the impact of the optimal process conditions on the production rate of polypropylene and the fluidized bed dynamic details which could be concurrently obtained after solving the model coupled with the CFD (computational fluid dynamics) model, the basic mathematical model and the moment equations. Furthermore, we have established the quantitative relationship between the operational condition and the dynamic gas⁻solid behavior in actual reaction environments. Our results state that the proposed model could be applied for generalizing the production rate of the polymer from a chemical procedure to pilot-scale chemical reaction engineering. However, it was assumed that the solids present in the bubble phase and the reactant gas present in the emulsion phase improved the multiphasic model, thus taking into account that the polymerization took place mutually in the emulsion besides the bubble phase. It was observed that with respect to the experimental extent of the superficial gas velocity and the Ziegler-Natta feed rate, the ratio of the polymer produced as compared to the overall rate of production was approximately in the range of 9%⁻11%. This is a significant amount and it should not be ignored. We also carried out the simulation studies for comparing the data of the CFD-dependent dual-phasic model, the emulsion phase model, the dynamic bubble model and the experimental results. It was noted that the improved dual-phasic model and the CFD model were able to predict more constricted and safer windows at similar conditions as compared to the experimental results. Our work is unique, as the integrated developed model is able to offer clearer ideas related to the dynamic bed parameters for the separate phases and is also capable of computing the chemical reaction rate for every phase in the reaction. Our improved mutiphasic model revealed similar dynamic behaviour as the conventional model in the initial stages of the polymerization reaction; however, it diverged as time progressed.
    Matched MeSH terms: Polymerization
  7. Fulltext Dataset in characterization of the polymer produced using different method of synthesis polychloromethylstyrene (PCMS) with clay and without clay
    Ismail N, Nazri NK, Abdullah AA, Wan Nik WMN, Wright LJ
    Data Brief, 2021 Feb;34:106738.
    PMID: 33521179 DOI: 10.1016/j.dib.2021.106738
    Polychloropolymethylstyrene (PCMS) polymers were synthesized with clay Cloisite and without clay Cloisite and chloromethylstyrene (CMS) combine with styrene (1:1) v/v or known as copolymer and clay Cloisite by the polymerization process. The attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectra of each polymer synthesized are reported. The spectra of IR shows the different value of the wavenumber and intensity for each set of different sample. The spectra can be as a reference for others to use in synthesizing this polymer and clay Cloisite for different type of application.
    Matched MeSH terms: Polymerization
  8. Fulltext Cobalt Oxide Nanograins and Silver Nanoparticles Decorated Fibrous Polyaniline Nanocomposite as Battery-Type Electrode for High Performance Supercapattery
    Iqbal J, Numan A, Omaish Ansari M, Jafer R, Jagadish PR, Bashir S, et al.
    Polymers (Basel), 2020 Nov 27;12(12).
    PMID: 33261072 DOI: 10.3390/polym12122816
    In this study, silver (Ag) and cobalt oxide (Co3O4) decorated polyaniline (PANI) fibers were prepared by the combination of in-situ aniline oxidative polymerization and the hydrothermal methodology. The morphology of the prepared Ag/Co3O4@PANI ternary nanocomposite was studied by scanning electron microscopy and transmission electron microscopy, while the structural studies were carried out by X-ray diffraction and X-ray photoelectron spectroscopy. The morphological characterization revealed fibrous shaped PANI, coated with Ag and Co3O4 nanograins, while the structural studies revealed high purity, good crystallinity, and slight interactions among the constituents of the Ag/Co3O4@PANI ternary nanocomposite. The electrochemical performance studies revealed the enhanced performance of the Ag/Co3O4@PANI nanocomposite due to the synergistic/additional effect of Ag, Co3O4 and PANI compared to pure PANI and Co3O4@PANI. The addition of the Ag and Co3O4 provided an extended site for faradaic reactions leading to the high specific capacity. The Ag/Co3O4@PANI ternary nanocomposite exhibited an excellent specific capacity of 262.62 C g-1 at a scan rate of 3 mV s-1. The maximum energy and power density were found to be 14.01 Wh kg-1 and 165.00 W kg-1, respectively. The cyclic stability of supercapattery (Ag/Co3O4@PANI//activated carbon) consisting of a battery type electrode demonstrated a gradual increase in specific capacity with a continuous charge-discharge cycle until ~1000 cycles, then remained stable until 2500 cycles and later started decreasing, thereby showing the cyclic stability of 121.03% of its initial value after 3500 cycles.
    Matched MeSH terms: Polymerization
  9. Fulltext Hydrothermally Assisted Synthesis of Porous Polyaniline@Carbon Nanotubes-Manganese Dioxide Ternary Composite for Potential Application in Supercapattery
    Iqbal J, Ansari MO, Numan A, Wageh S, Al-Ghamdi A, Alam MG, et al.
    Polymers (Basel), 2020 Dec 05;12(12).
    PMID: 33291451 DOI: 10.3390/polym12122918
    In this study, ternary composites of polyaniline (PANI) with manganese dioxide (MnO2) nanorods and carbon nanotubes (CNTs) were prepared by employing a hydrothermal methodology and in-situ oxidative polymerization of aniline. The morphological analysis by scanning electron microscopy showed that the MnO2 possessed nanorod like structures in its pristine form, while in the ternary PANI@CNT/MnO2 composite, coating of PANI over CNT/MnO2, rods/tubes were evidently seen. The structural analysis by X-ray diffraction and X-ray photoelectron spectroscopy showed peaks corresponding to MnO2, PANI and CNT, which suggested efficacy of the synthesis methodology. The electrochemical performance in contrast to individual components revealed the enhanced performance of PANI@CNT/MnO2 composite due to the synergistic/additional effect of PANI, CNT and MnO2 compared to pure MnO2, PANI and PANI@CNT. The PANI@CNT/MnO2 ternary composite exhibited an excellent specific capacity of 143.26 C g-1 at a scan rate of 3 mV s-1. The cyclic stability of the supercapattery (PANI@CNT/MnO2/activated carbon)-consisting of a battery type electrode-demonstrated a gradual increase in specific capacity with continuous charge-discharge over ~1000 cycles and showed a cyclic stability of 119% compared to its initial value after 3500 cycles.
    Matched MeSH terms: Polymerization
  10. Fulltext Novel, one-step synthesis of zwitterionic polymer nanoparticles via distillation-precipitation polymerization and its application for dye removal membrane
    Ibrahim GPS, Isloor AM, Inamuddin, Asiri AM, Ismail N, Ismail AF, et al.
    Sci Rep, 2017 Nov 21;7(1):15889.
    PMID: 29162869 DOI: 10.1038/s41598-017-16131-9
    In this work, poly(MBAAm-co-SBMA) zwitterionic polymer nanoparticles were synthesized in one-step via distillation-precipitation polymerization (DPP) and were characterized. [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) as monomer and N, N'-methylene bis(acrylamide) (MBAAm) as cross-linker are used for the synthesis of nanoparticles. As  far as our knowledge, this is the first such report on the synthesis of poly(MBAAm-co-SBMA) nanoparticles via DPP. The newly synthesized nanoparticles were further employed for the surface modification of polysulfone (PSF) hollow fiber membranes for dye removal. The modified hollow fiber membrane exhibited the improved permeability (56 L/ m2 h bar) and dye removal (>98% of Reactive Black 5 and >80.7% of Reactive orange 16) with the high permeation of salts. Therefore, the as-prepared membrane can have potential application in textile and industrial wastewater treatment.
    Matched MeSH terms: Polymerization
  11. Fulltext Removal of metal ions and humic acids through polyetherimide membrane with grafted bentonite clay
    Hebbar RS, Isloor AM, Prabhu B, Inamuddin, Asiri AM, Ismail AF
    Sci Rep, 2018 03 16;8(1):4665.
    PMID: 29549259 DOI: 10.1038/s41598-018-22837-1
    Functional surfaces and polymers with branched structures have a major impact on physicochemical properties and performance of membrane materials. With the aim of greener approach for enhancement of permeation, fouling resistance and detrimental heavy metal ion rejection capacity of polyetherimide membrane, novel grafting of poly (4-styrenesulfonate) brushes on low cost, natural bentonite was carried out via distillation-precipitation polymerisation method and employed as a performance modifier. It has been demonstrated that, modified bentonite clay exhibited significant improvement in the hydrophilicity, porosity, and water uptake capacity with 3 wt. % of additive dosage. SEM and AFM analysis showed the increase in macrovoides and surface roughness with increased additive concentration. Moreover, the inclusion of modified bentonite displayed an increase in permeation rate and high anti-irreversible fouling properties with reversible fouling ratio of 75.6%. The humic acid rejection study revealed that, PEM-3 membrane having rejection efficiency up to 87.6% and foulants can be easily removed by simple hydraulic cleaning. Further, nanocomposite membranes can be significantly employed for the removal of hazardous heavy metal ions with a rejection rate of 80% and its tentative mechanism was discussed. Conspicuously, bentonite clay-bearing poly (4-styrenesulfonate) brushes are having a synergistic effect on physicochemical properties of nanocomposite membrane to enhance the performance in real field applications.
    Matched MeSH terms: Polymerization
  12. Synthesis and properties of poly(hydroxamic acid) from crosslinked poly(methacrylate)
    Haron MJ, Wan Md ZW, Desa MZ, Kassim A
    Talanta, 1994 May;41(5):805-7.
    PMID: 18966002
    Poly(hydroxamic acid) chelating ion-exchange resin was prepared from crosslinked poly(methacrylate) beads. The starting polymer was prepared by a suspension polymerization of methacrylate and divinyl benzene. Conversion of the ester groups into the hydroxamic acid was carried out by treatment with hydroxylamine in an alkaline solution. Hydroxamic acid capacity of the product was 2.71 mmol/g. The resin exhibited high affinity towards Fe(III) and Pb ions and its capacities for Fe(III), Pb, Cu, Ni and Co ions were pH dependent. The ability of the resin to carry out the separation of Fe(III)CuCo/Ni and PbNi ions is also reported.
    Matched MeSH terms: Polymerization
  13. Lipase catalyzed ultrasonic synthesis of poly-4-hydroxybutyrate-co-6-hydroxyhexanoate
    Gumel AM, Annuar MS, Chisti Y
    Ultrason Sonochem, 2013 May;20(3):937-47.
    PMID: 23231942 DOI: 10.1016/j.ultsonch.2012.09.015
    Four different lipases were compared for ultrasound-mediated synthesis of the biodegradable copolymer poly-4-hydroxybutyrate-co-6-hydroxyhexanoate. The copolymerization was carried out in chloroform. Of the enzymes tested, Novozym 435 exhibited the highest copolymerization rate, in fact the reaction rate was observed to increase with about 26-fold from 30 to 50°C (7.9×10(-3)Ms(-1)), sonic power intensity of 2.6×10(3)Wm(-2) and dissipated energy of 130.4Jml(-1). Copolymerization rates with the Candida antarctica lipase A, Candida rugosa lipase, and Lecitase Ultra™ were lower at 2.4×10(-4), 1.3×10(-4) and 3.5×10(-4)Ms(-1), respectively. The catalytic efficiency depended on the enzyme. The efficiency ranged from 4.15×10(-3)s(-1)M(-1) for Novozym 435-1.48×10(-3)s(-1)M(-1) for C. rugosa lipase. Depending on the enzyme and sonication intensity, the monomer conversion ranged from 8.2% to 48.5%. The sonication power, time and temperature were found to affect the rate of copolymerization. Increasing sonication power intensity from 1.9×10(3) to 4.5×10(3)Wm(-2) resulted in an increased in acoustic pressure (P(a)) from 3.7×10(8) to 5.7×10(8)Nm(-2) almost 2.4-3.7 times greater than the acoustic pressure (1.5×10(8)Nm(-2)) that is required to cause cavitation in water. A corresponding acoustic particle acceleration (a) of 9.6×10(3)-1.5×10(4)ms(-2) was calculated i.e. approximately 984-1500 times greater than under the action of gravity.
    Matched MeSH terms: Polymerization
  14. Fulltext Electrical conductivity of anionic surfactant-doped polypyrrole nanoparticles prepared via emulsion polymerization
    Ghalib, H., Abdullah, I., Daik, R.
    Pertanika Journal of Science & Technology, 2013;21(2):459-472.
    MyJurnal
    Conducting polypyrrole (PPy) nanoparticles were synthesized by chemical oxidative polymerization of pyrrole in aqueous solution containing ferric sulfate (Fe2(SO4)3), anionic surfactants (sodium dodecylbenzene-sulfonate (NaDBS) or sodium dodecyl sulfate (SDS)), 1-pentanol as the oxidant, dopant and co-emulsifier, respectively. The polymerization was carried out at 0 ºC and 25 ºC. Fourier transform infrared spectroscopy (FTIR) and elemental analysis indicated that anionic surfactants were successfully incorporated into the PPy backbone. Incorporation of anionic surfactants caused enhanced electrical conductivity, increased yield, decreased the size of particles as well as improved the thermal stability of the resultant PPy. The presence of anionic surfactant seems to inhibit undesirable side reactions so as to improve the regularity of the PPy backbone. Globular PPy particles were obtained with diameter ranged from 40 to 118 nm as revealed by field emission scanning electron microscopy (FE-SEM) and conductivity of 7.89×10-4 –2.35×10-2 S cm-1, as measured using impedance analyzer. It was found that polymerization at low temperature (0 ºC) produced PPy particles with smaller size and higher conductivity. The sodium dodecyl sulfate-doped PPy (SDS-doped PPy) exhibited higher conductivity than that of the sodium dodecylbenzenesulfonate-doped PPy (NaDBS-doped PPy), due to the bulkiness of NaDBS as compared to SDS.
    Matched MeSH terms: Polymerization
  15. Studies on the effects of titanate and silane coupling agents on the performance of poly (methyl methacrylate)/barium titanate denture base nanocomposites
    Elshereksi NW, Ghazali MJ, Muchtar A, Azhari CH
    J Dent, 2017 Jan;56:121-132.
    PMID: 27916635 DOI: 10.1016/j.jdent.2016.11.012
    OBJECTIVES: This study aimed to fabricate and characterise silanated and titanated nanobarium titanate (NBT) filled poly(methyl methacrylate) (PMMA) denture base composites and to evaluate the behaviour of a titanate coupling agent (TCA) as an alternative coupling agent to silane. The effect of filler surface modification on fracture toughness was also studied.

    METHODS: Silanated, titanated and pure NBT at 5% were incorporated in PMMA matrix. Neat PMMA matrix served as a control. NBT was sonicated in MMA prior to mixing with the PMMA. Curing was carried out using a water bath at 75°C for 1.5h and then at 100°C for 30min. NBT was characterised via Fourier transform-infrared spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and Brunauer-Emmett-Teller (BET) analysis before and after surface modification. The porosity and fracture toughness of the PMMA nanocomposites (n=6, for each formulation and test) were also evaluated.

    RESULTS: NBT was successfully functionalised by the coupling agents. The TCA exhibited the lowest percentage of porosity (0.09%), whereas silane revealed 0.53% porosity. Statistically significant differences in fracture toughness were observed among the fracture toughness values of the tested samples (p<0.05). While the fracture toughness of untreated samples was reduced by 8%, an enhancement of 25% was achieved after titanation. In addition, the fracture toughness of the titanated samples was higher than the silanated ones by 10%.

    CONCLUSION: Formation of a monolayer on the surface of TCA enhanced the NBT dispersion, however agglomeration of silanated NBT was observed due to insufficient coverage of NBT surface. Such behaviour led to reducing the porosity level and improving fracture toughness of titanated NBT/PMMA composites. Thus, TCA seemed to be more effective than silane.

    CLINICAL SIGNIFICANCE: Minimising the porosity level could have the potential to reduce fungus growth on denture base resin to be hygienically accepTable Such enhancements obtained with Ti-NBT could lead to promotion of the composites' longevity.

    Matched MeSH terms: Polymerization
  16. Fulltext Molecular Differentiated Initiator Reactivity in the Synthesis of Poly(caprolactone)-Based Hydrophobic Homopolymer and Amphiphilic Core Corona Star Polymers
    Deng E, Nguyen NT, Hild F, Hamilton IE, Dimitrakis G, Kingman SW, et al.
    Molecules, 2015 Nov 09;20(11):20131-45.
    PMID: 26569198 DOI: 10.3390/molecules201119681
    Macromolecules that possess three-dimensional, branched molecular structures are of great interest because they exhibit significantly differentiated application performance compared to conventional linear (straight chain) polymers. This paper reports the synthesis of 3- and 4-arm star branched polymers via ring opening polymerisation (ROP) utilising multi-functional hydroxyl initiators and Sn(Oct)2 as precatalyst. The structures produced include mono-functional hydrophobic and multi-functional amphiphilic core corona stars. The characteristics of the synthetic process were shown to be principally dependent upon the physical/dielectric properties of the initiators used. ROP's using initiators that were more available to become directly involved with the Sn(Oct)₂ in the "in-situ" formation of the true catalytic species were observed to require shorter reaction times. Use of microwave heating (MWH) in homopolymer star synthesis reduced reaction times compared to conventional heating (CH) equivalents, this was attributed to an increased rate of "in-situ" catalyst formation. However, in amphiphilic core corona star formation, the MWH polymerisations exhibited slower propagation rates than CH equivalents. This was attributed to macro-structuring within the reaction medium, which reduced the potential for reaction. It was concluded that CH experiments were less affected by this macro-structuring because it was disrupted by the thermal currents/gradients caused by the conductive/convective heating mechanisms. These gradients are much reduced/absent with MWH because it selectively heats specific species simultaneously throughout the entire volume of the reaction medium. These partitioning problems were overcome by introducing additional quantities of the species that had been determined to selectively heat.
    Matched MeSH terms: Polymerization
  17. Fulltext Application of Zwitterions in Forward Osmosis: A Short Review
    Chiao YH, Sengupta A, Ang MBMY, Chen ST, Haan TY, Almodovar J, et al.
    Polymers (Basel), 2021 Feb 15;13(4).
    PMID: 33672026 DOI: 10.3390/polym13040583
    Forward osmosis (FO) is an important desalination method to produce potable water. It was also used to treat different wastewater streams, including industrial as well as municipal wastewater. Though FO is environmentally benign, energy intensive, and highly efficient; it still suffers from four types of fouling namely: organic fouling, inorganic scaling, biofouling and colloidal fouling or a combination of these types of fouling. Membrane fouling may require simple shear force and physical cleaning for sufficient recovery of membrane performance. Severe fouling may need chemical cleaning, especially when a slimy biofilm or severe microbial colony is formed. Modification of FO membrane through introducing zwitterionic moieties on the membrane surface has been proven to enhance antifouling property. In addition, it could also significantly improve the separation efficiency and longevity of the membrane. Zwitterion moieties can also incorporate in draw solution as electrolytes in FO process. It could be in a form of a monomer or a polymer. Hence, this review comprehensively discussed several methods of inclusion of zwitterionic moieties in FO membrane. These methods include atom transfer radical polymerization (ATRP); second interfacial polymerization (SIP); coating and in situ formation. Furthermore, an attempt was made to understand the mechanism of improvement in FO performance by zwitterionic moieties. Finally, the future prospective of the application of zwitterions in FO has been discussed.
    Matched MeSH terms: Polymerization
  18. PHA synthase (PhaC): interpreting the functions of bioplastic-producing enzyme from a structural perspective
    Chek MF, Hiroe A, Hakoshima T, Sudesh K, Taguchi S
    Appl Microbiol Biotechnol, 2019 Feb;103(3):1131-1141.
    PMID: 30511262 DOI: 10.1007/s00253-018-9538-8
    Polyhydroxyalkanoates (PHAs) are biopolymers synthesized by a wide range of bacteria, which serve as a promising candidate in replacing some conventional petrochemical-based plastics. PHA synthase (PhaC) is the key enzyme in the polymerization of PHA, and the crystal structures were successfully determined using the catalytic domain of PhaC from Cupriavidus necator (PhaCCn-CAT) and Chromobacterium sp. USM2 (PhaCCs-CAT). Here, we review the beneficial mutations discovered in PhaCs from a structural perspective. The structural comparison of the residues involved in beneficial mutation reveals that the residues are near to the catalytic triad, but not inside the catalytic pocket. For instance, Ala510 of PhaCCn is near catalytic His508 and may be involved in the open-close regulation, which presumably play an important role in substrate specificity and activity. In the class II PhaC1 from Pseudomonas sp. 61-3 (PhaC1Ps), Ser325 stabilizes the catalytic cysteine through hydrogen bonding. Another residue, Gln508 of PhaC1Ps is located in a conserved hydrophobic pocket which is next to the catalytic Asp and His. A class I, II-conserved Phe420 of PhaCCn is one of the residues involved in dimerization and its mutation to serine greatly reduced the lag phase. The current structural analysis shows that the Phe362 and Phe518 of PhaC from Aeromonas caviae (PhaCAc) are assisting the dimer formation and maintaining the integrity of the core beta-sheet, respectively. The structure-function relationship of PhaCs discussed in this review will serve as valuable reference for future protein engineering works to enhance the performance of PhaCs and to produce novel biopolymers.
    Matched MeSH terms: Polymerization
  19. Fulltext Asymmetric Open-Closed Dimer Mechanism of Polyhydroxyalkanoate Synthase PhaC
    Chek MF, Kim SY, Mori T, Tan HT, Sudesh K, Hakoshima T
    iScience, 2020 May 22;23(5):101084.
    PMID: 32388399 DOI: 10.1016/j.isci.2020.101084
    Biodegradable polyester polyhydroxyalkanoate (PHA) is a promising bioplastic material for industrial use as a replacement for petroleum-based plastics. PHA synthase PhaC forms an active dimer to polymerize acyl moieties from the substrate acyl-coenzyme A (CoA) into PHA polymers. Here we present the crystal structure of the catalytic domain of PhaC from Chromobacterium sp. USM2, bound to CoA. The structure reveals an asymmetric dimer, in which one protomer adopts an open conformation bound to CoA, whereas the other adopts a closed conformation in a CoA-free form. The open conformation is stabilized by the asymmetric dimerization and enables PhaC to accommodate CoA and also to create the product egress path. The bound CoA molecule has its β-mercaptoethanolamine moiety extended into the active site with the terminal SH group close to active center Cys291, enabling formation of the reaction intermediate by acylation of Cys291.
    Matched MeSH terms: Polymerization
  20. Fulltext Thixotropic Supramolecular Pectin-Poly(Ethylene Glycol) Methacrylate (PEGMA) Hydrogels
    Chan SY, Choo WS, Young DJ, Loh XJ
    Polymers (Basel), 2016 Nov 18;8(11).
    PMID: 30974681 DOI: 10.3390/polym8110404
    Pectin is an anionic, water-soluble polymer predominantly consisting of covalently 1,4-linked α-d-galacturonic acid units. This naturally occurring, renewable and biodegradable polymer is underutilized in polymer science due to its insolubility in organic solvents, which renders conventional polymerization methods impractical. To circumvent this problem, cerium-initiated radical polymerization was utilized to graft methoxy-poly(ethylene glycol) methacrylate (mPEGMA) onto pectin in water. The copolymers were characterized by ¹H nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA), and used in the formation of supramolecular hydrogels through the addition of α-cyclodextrin (α-CD) to induce crosslinking. These hydrogels possessed thixotropic properties; shear-thinning to liquid upon agitation but settling into gels at rest. In contrast to most of the other hydrogels produced through the use of poly(ethylene glycol) (PEG)-grafted polymers, the pectin-PEGMA/α-CD hydrogels were unaffected by temperature changes.
    Matched MeSH terms: Polymerization
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