Cellulose is the most abundant polysaccharide on earth. It has a large number of desirable properties. Its low toxicity makes it more useful for a variety of applications. Nowadays, its composites are used in most engineering fields. Composite consists of a polymer matrix and use as a reinforcing material. By reducing the cost of traditional fibers, it has an increasing demand for environment-friendly purposes. The use of these types of composites is inherent in moisture absorption with hindered natural fibers. This determines the reduction of polymer composite material. By appropriate chemical surface treatment of cellulose composite materials, the effect could be diminished. The most modern and advanced techniques and methods for the preparation of cellulose and polymer composites are discussed here. Cellulosic composites show a reinforcing effect on the polymer matrix as pointed out by mechanical characterization. Researchers tried their hard work to study different ways of converting various agricultural by-products into useful eco-friendly polymer composites for sustainable production. Cellulose plays building blocks, that are critical for polymer products and their engineering applications. The most common method used to prepare composites is in-situ polymerization. This help to increase the yields of cellulosic composites with a significant enhancement in thermal stability and mechanical properties. Recently, cellulose composites used as enhancing the incorporation of inorganic materials in multi-functional properties. Furthermore, we have summarized in this review the potential applications of cellulose composites in different fields like packaging, aerogels, hydrogels, and fibers.
Polymer blending has been a facile method to resolve the brittle issue of poly(lactic acid) (PLA). Yet, miscibility becomes the primary concern that would affect the synergy effect of polymer blending. This study aimed to improve the miscibility of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (P34HB) and PLA by lowering their molecular weights via a melt-blending-induced thermal degradation during mechanical mixing to form m-P34HB/PLA blends. The molecular weight of the P34HB was significantly reduced after blending, thereby improving the miscibility of the blends, as evidenced by the shift of glass transition temperatures. Also, simulation based on Flory-Huggins theory demonstrated increased miscibility with decreasing molecular weight of the polymers. Moreover, the thermal gravimetric analysis revealed that the PLA provided a higher shielding effect to the P34HB in the blends prepared by melt-blending than those by solution-blending, that the addition of PLA could retard the chain scission of P34HB and delay its degradation. The addition of m-P34HB at 20 wt% in the blend contributed to a 60-fold enhancement in the elongation at break and an increment of 4.6 folds in the Izod impact strength. The enzymatic degradation using proteinase K revealed the preferential to degrade the PLA in the blends and followed the surface erosion mechanism.
We demonstrate a polymer resonator microfluidic biosensor that overcomes the complex manufacturing procedures required to fabricate traditional devices. In this new format, we show that a gapless light coupling photonic configuration, fabricated in SU8 polymer, can achieve high sensitivity, label-free chemical sensing in solution and high sensitivity biological sensing, at visible wavelengths.
Shape memory polymers (SMPs) are smart and adaptive materials able to recover their shape through an external stimulus. This functionality, combined with the good biocompatibility of polymers, has garnered much interest for biomedical applications. In this review, we discuss the design considerations critical to the successful integration of SMPs for use in vivo. We also highlight recent work on three classes of SMPs: shape memory polymers and blends, shape memory polymer composites, and shape memory hydrogels. These developments open the possibility of incorporating SMPs into device design, which can lead to vast technological improvements in the biomedical field.
Molecular imprinted polymers (MIP) are considered one of the most promising selective and novel separation methods for removal phenolic compound in wastewater treatment. MIP are crosslinked polymeric materials that exhibit high binding capacity and selectivity towards a target molecule (template), purposely present during the synthesis process. In this work MIP were prepared in a bulk polymerization method in acetonitrile using 2,4-dinitrophenol, acrylamide, ethylene glycol dimethacrylate, and benzoyl peroxide as template, functional monomer, cross-linker and initiator, respectively. An adsorption process for removal of nitrophenol using the fabricated MIP was evaluated under various pH and time conditions. The parameters studied for 2,4-dinitrophenol includes adsorption kinetics, adsorption isotherm, and selectivity. The maximum adsorption of nitrophenol by the fabricated MIP was 3.50 mg/g. The adsorption of 2,4-dinitrophenol by the fabricated MIP was found effective at pH 6.0. A kinetics study showed that nitrophenol adsorption follows a second order adsorption rate and the adsorption isotherm data is explained well by the Langmuir model.
Conformational search for the most stable geometry connection of 16 sets of polydopamine (PDA) tetramer subunits has been systematically investigated using density functional theory (DFT) calculations. Our results indicated that the more planar subunits are, the more stable they are. This finding is in good agreement with recent experimental observations, which have suggested that PDA are composed of the nearly planar subunits that appear to be stacked together via the π-π interactions to form graphite-like layered aggregates associated with the balance of the intramolecular hydrogen bonds and steric effects from the indole and catechol moieties. Molecular dynamics (MD) simulations of 16 spherical clusters of the tetramer subunits of PDA in the gas and aqueous phase were performed at 298 K and confirmed the stability of supramolecular tetramer aggregates. The complex formation and binding energy of all 16 clusters are very strong although the shapes of the clusters in aqueous solution are not spherical and are very much different from those in the gas phase. The aggregations of all 16 clusters in aqueous solution were also confirmed from the profiles of the Kratky plot and the radius of gyration of all clusters. Our MD results in both gas phase and aqueous solution pointed out that there are high possibilities of aggregations of the 16 kinds of tetramer subunits although the conformations of each tetramer subunit are not flat. In summary, this work brings an insight into the controversial structure of PDA tetramer units and explains some of the important structural features found in the aqueous phase in comparison to the gas phase.
The generation of free radicals is the key to the photocatalytic efficiency. In this study, the degradation mechanism of photoelectrocatalysis (PEC) membrane could be adequately explained by exploring the generation pathway of different free radicals. The PEC membrane was prepared by gas phase polymerization of poly (3, 4-ethylene dioxythiophene) (PEDOT) on non-woven fabric, industrial filter cloth, ceramic membrane and polyvinylidene fluoride (PVDF) membrane, respectively. Three-dimensional fluorescence test showed that the optimal degradation of mixed or monomer contamination (bovine serum protein, sodium humate, and sodium alginate) was achieved by modified ceramic membrane under PEC condition. As for self-cleaning experiment, the membrane resistance decreased 65.7% when the reaction conditions changed from dark to PEC for 30 min. Combined with the characterization results, PEDOT as photocapacitance extended electron lifetime and promoted free radical generation. This system was mainly dependent on superoxide free radicals (0.01 mmol/L) and singlet oxygen (0.10 mmol/L), which came from energy and electron transfer. Oxygen vacancy could adsorb oxygen to produce superoxide radicals, which was further oxidized to singlet oxygen. In addition, the π-electron conjugated system of PEDOT accelerated the hole transfer and the separation of electrons and holes. Also, this study provided a new view of reactive oxygen species generation mechanism from PEDOT modified membrane.
Mixed matrix membranes (MMMs) were fabricated by the hydrothermal synthesis of ordered mesoporous KIT-6 type silica and incorporating in polyimide (P84). KIT-6 and MMMs were characterized to evaluate morphology, thermal stability, surface area, pore volume, and other characteristics. SEM images of synthesized MMMs and permeation data of CO2 suggested homogenous dispersion of mesoporous fillers and their adherence to the polymer matrix. The addition of KIT-6 to polymer matrix improved the permeability of CO2 due to the increase in diffusivity through porous particles. The permeability was 3.2 times higher at 30% loading of filler. However, selectivity showed a slight decrease with the increase in filler loadings. The comparison of gas permeation results of KIT-6 with the well-known MCM-41 revealed that KIT-6 based MMMs showed 14% higher permeability than that of MMMs composed of mesoporous MCM-41. The practical commercial viability of synthesized membranes was examined under different operating temperatures and mixed gas feeds. Mesoporous KIT-6 silica is an attractive additive for gas permeability enhancement without compromising the selectivity of MMMs. Graphical abstract.
Recently, transdermal monitoring and drug delivery have gained much interest, owing to the introduction of the minimally invasive microneedle (MN) device. The advancement of electroactive MNs electrically assisted in the capture of biomarkers or the triggering of drug release. Recent works have combined conducting polymers (CPs) onto MNs owing to the soft nature of the polymers and their tunable ionic and electronic conductivity. Though CPs are reported to work safely in the body, their biocompatibility in the skin has been insufficiently investigated. Furthermore, during electrical biasing of CPs, they undergo reduction or oxidation, which in practical terms leads to release/exchange of ions, which could pose biological risks. This work investigates the viability and proliferation of skin cells upon exposure to an electrochemically biased MN pair comprising two differently doped poly(3,4-ethylenedioxy-thiophene) (PEDOT) polymers that have been designed for skin sampling use. The impact of biasing on human keratinocytes and dermal fibroblasts was determined at different initial cell seeding densities and incubation periods. Indirect testing was employed, whereby the culture media was first exposed to PEDOTs prior to the addition of this extract to cells. In all conditions, both unbiased and biased PEDOT extracts showed no cytotoxicity, but the viability and proliferation of cells cultured at a low cell seeding density were lower than those of the control after 48 h of incubation.
Exposure of synthetic dye, such as methylene blue (MB), in water bodies led to a serious threat to living things because they are toxic and non-degradable. Amongst the introduced dye removal methods, membrane separation process can be considered a powerful technique for treating dye contamination. However, this method commonly suffered from drawbacks, such as short membrane lifetime, low permeability and selectivity. To overcome these issues, graphene oxide (GO) and titanium dioxide (TiO2) were used as additives to fabricate polyethersulfone (PES)- and polyvinylidene fluoride (PVDF)-based hybrid membranes via non-solvent-induced phase separation method. Prior to membrane fabrication, GO was synthesised via electrochemical exfoliation method assisted by customised triple-tail surfactant. The potential of PES- and PVDF-based hybrid membranes for wastewater treatment has been discussed widely. However, direct comparison between these two polymeric membranes is not critically discussed for MB dye separation application yet. Therefore, this study is aimed at evaluating the performance of different types of polymers (e.g. PES and PVDF) in terms of membrane morphology, properties, dye rejection and antifouling ability. Results showed that the incorporation of GO and TiO2 alters the morphology of the fabricated membranes and affects dye rejection further, as well as their antifouling performance. In contrast with pristine membrane, PES-GO/TiO2 and PVDF-GO/TiO2 possessed high hydrophilicity, as indicated by their low contact angle (67.38° and 62.12°, respectively). Based on this study, PVDF-GO/TiO2 showed higher porosity value (94.88%), permeability (87.32 L/m2hMPa) and MB rejection rate (92.63%), as well as flux recovery ratio value of > 100% as compared with others. Overall, the incorporation of GO and TiO2 with PVDF polymer are proven to be effective hybrid materials of membrane fabrication for dye rejection application in the near future. The polymer material's intrinsic properties can affect the attributes of the fabricated membrane.
Skin sampling is a diagnostic procedure based on the analysis of extracted skin tissues and/or the observation of biomarkers in bodily fluids. Sampling using microneedles (MNs) that minimize invasiveness is gaining attention over conventional biopsy/blood lancet. In this study, new MNs for electrochemically assisted skin sampling are reported, specifically tailored for combined skin tissue biopsy and interstitial fluid (ISF) extraction. To overcome risks associated with using metal MNs, a highly electroactive, mechanically flexible, and biocompatible organic conducting polymer (CP) coated onto plastic is chosen as an alternative. Two different variants of doped poly(3,4-ethylenedioxythiophene) are coated on polymethyl methacrylate and used in combination as a MN pair with subsequent testing via a variety of electrochemical techniques to (i) give real-time information of the MN penetration depth into the skin, and (ii) yield new information on various salts present in the ISF. The MN skin sampler shows the ability to extract ions from the hydrated excised skin as a step towards in vivo ISF extraction. The presence of ions was analyzed using X-ray photoelectron spectroscopy. This added chemical information in conjunction with the existing biomarker analysis increases opportunity for disease/condition detection. For example, in the case of psoriasis, information about salt in the skin is invaluable in combination with pathogenic gene expression for diagnosis.
Carbohydrate polymers-based surface-modified nano-delivery systems have gained significant attention in recent years for enhancing targeted delivery to colon cancer. These systems leverage carbohydrate polymers' unique properties, such as biocompatibility, biodegradability, and controlled release. These properties make them suitable candidates for drug delivery applications. Nano-delivery systems loaded with bioactive compounds are well-studied for targeted colorectal cancer delivery. However, those drugs' target reach is still limited in various nano-delivery systems. To overcome this limitation, surface modification of nanoparticles with carbohydrate polymers like chitosan, pectin, alginate, and guar gum showed enhanced target-reaching capacity along with enhanced anticancer efficacy. Recently, a chitosan-decorated PLGA nanoparticle was constructed with tannic acid and vitamin E and showed long-term release of specific targets along with higher anticancer efficacy. Similarly, Chitosan-conjugated glucuronic acid-coated silica nanoparticles loaded with capecitabine were studied against colon cancer and found to be the pH-responsive controlled release of capecitabine with higher anticancer efficacy. Surface-modified carbohydrate polymers have promising potential for improving colon cancer target delivery. By leveraging the unique properties of these polymers, such as surface modification, pH responsiveness, mucoadhesion, controlled drug release, and combination therapy, researchers are working toward developing more effective and targeted treatment strategies for colon cancer.
Postoperative bleeding following cardiac surgeries is still an issue that deranges the medical resources and cost. The oral and injection administrations of blood coagulation protein, Factor VII (FVII), is effective to stop the bleeding. However, its short half-life has limited the effectiveness of this treatment and frequent FVII intake may distress the patients. Instead, incorporating FVII into synthetic biodegradable polymers such as polycaprolactone (PCL) that is commonly used in drug delivery applications should provide a solution. Therefore, this study aimed to immobilize FVII on PCL membranes through a cross-linkage polydopamine (PDA) grafting as an intermediate layer. These membranes are intended to provide a solution for cardiac bleeding in coagulating blood and sealing the sutured region. The membranes were evaluated in terms of its physio-chemical properties, thermal behavior, FVII release profile and biocompatibility properties. The ATR-FTIR was used to analyze the chemical functionalities of the membranes. Further validation was done with XPS where the appearances of 0.45 ± 0.06% sulfur composition and C-S peak have confirmed the immobilization of FVII on the PCL membranes. The cross-linked FVIIs were viewed in spherical immobilization on the PCL membranes with a size range between 30 and 210 nm. The surface roughness and hydrophilicity of the membranes were enhanced with a slight shift of melting temperature. The PCL-PDA-FVII0.03 and PCL-PDA-FVII0.05 membranes, with wide area of FVII immobilization released approximately only 22% of FVII into the solution within 60 days period and, it is found that the PCL-PDA-FVIIx membranes projected the Higuchi release model with non-Fickian anomalous transport. While the cytotoxic and hemocompatibility analyses showed advance cell viability, identical coagulation time and low hemolysis ratio on the PCL-PDA-FVIIx membranes. The erythrocytes were viewed in polyhedrocyte coagulated structure under SEM visualization. These results validate the biocompatibility of the membranes and its ability to prolong blood coagulation, thus highlighting its potential application as cardiac bleeding sealant.
Enzymes of commercial importance, such as lipase, amylase, laccase, phytase, carbonic anhydrase, pectinase, maltase, glucose oxidase etc., show multifunctional features and have been extensively used in several fields including fine chemicals, environmental, pharmaceutical, cosmetics, energy, food industry, agriculture and nutraceutical etc. The deployment of biocatalyst in harsh industrial conditions has some limitations, such as poor stability. These drawbacks can be overcome by immobilizing the enzyme in order to boost the operational stability, catalytic activity along with facilitating the reuse of biocatalyst. Nowadays, functionalized polymers and composites have gained increasing attention as an innovative material for immobilizing the industrially important enzyme. The different types of polymeric materials and composites are pectin, agarose, cellulose, nanofibers, gelatin, and chitosan. The functionalization of these materials enhances the loading capacity of the enzyme by providing more functional groups to the polymeric material and hence enhancing the enzyme immobilization efficiency. However, appropriate coordination among the functionalized polymeric materials and enzymes of interest plays an important role in producing emerging biocatalysts with improved properties. The optimal coordination at a biological, physical, and chemical level is requisite to develop an industrial biocatalyst. Bio-catalysis has become vital aspect in pharmaceutical and chemical industries for synthesis of value-added chemicals. The present review describes the current advances in enzyme immobilization on functionalized polymers and composites. Furthermore, the applications of immobilized enzymes in various sectors including bioremediation, biosensor and biodiesel are also discussed.
14-3-3σ plays an important role in controlling tumor metabolic reprogramming and cancer cell growth. However, its function is often compromised in many cancers due to its downregulation. Previous studies found that homodimerization of 14-3-3σ is critical for its activity. However, to date, it is not known if stabilization of 14-3-3σ homodimers can improve its activity or prevent its degradation. In our previous work, we have showed that GCP-Lys-OMe is a potential 14-3-3σ homodimer stabilizer. However, its stabilizing effect was not experimentally validated. Therefore, in this study, we have attempted to predict few potential peptides that can stabilize the dimeric form of 14-3-3σ using similar in silico techniques as described previously for GCP-Lys-OMe. Subsequent [1H]-CPMG NMR experiments confirmed the binding of the peptides (peptides 3, 5, 9, and 16) on 14-3-3σ, with peptide 3 showing the strongest binding. Competitive [1H]-CPMG assays further revealed that while peptide 3 does not compete with a 14-3-3σ binding peptide (ExoS) for the protein's amphipathic groove, it was found to improve ExoS binding on 14-3-3σ. When 14-3-3σ was subjected to dynamic light scattering experiments, the 14-3-3σ homodimer was found to undergo dissociation into monomers prior to aggregation. Intriguingly, the presence of peptide 3 increased 14-3-3σ stability against aggregation. Overall, our findings suggest that (1) docking accompanied by MD simulations can be used to identify potential homodimer stabilizing compounds of 14-3-3σ and (2) peptide 3 can slow down 14-3-3σ aggregation (presumably by preventing its dissociation into monomers), as well as improving the binding of 14-3-3σ to ExoS protein.
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-4-hydroxybutyrate) [P(3HB-co-3HV-co-4HB)] terpolymer was produced using Cupriavidus sp. USMAA2-4 via one-step cultivation process through combination of various carbon sources such as 1,4-butanediol or γ-butyrolactone with either 1-pentanol, valeric acid, or 1-propanol. Oleic acid was added to increase the biomass production. The composition of 3HV and 4HB monomers were greatly affected by the concentration of 1,4-butanediol and 1-pentanol. Terpolymers with 3HV and 4HB molar fractions ranging from 2 to 41 mol.% and 5 to 31 mol.%, respectively, were produced by varying the concentration of carbon precursors. The thermal and mechanical properties of the terpolymers containing different proportions of the constituent monomers were characterized using gel permeation chromatography (GPC), DSC, and tensile machine. GPC analysis showed that the molecular weights (M (w)) of the terpolymer produced were within the range of 346 to 1,710 kDa. The monomer compositions of 3HV and 4HB were also found to have great influences on the thermal and mechanical properties of the terpolymer P(3HB-co-3HV-co-4HB) produced.
Poly (p-phenylene vinylene) (PPV) was synthesized from p-xylylene bis(tetrahydrothiophenium chloride) using the Wessling route and characterized by Fourier Transform Infra-Red (FTIR) and UV-visible (UV-VIS) spectroscopic techniques. The significance of thermal treatment along with evolution of precursor polymer to polymer PPV was also studied through these spectroscopic techniques. Thermally Stimulated Current (TSC) measurements indicated the presence of crystallization, sulphonium group which occurred through the evolution from precursor polymer to polymer PPV during thermal treatment.
High melting point polymeric carrier without plasticizer is unacceptable for solid dispersion (SD) by melting method. Combined polymer-plasticizer carrier significantly affects drug solubility and tableting property of SD.
Three isomeric 2[Pd(II)-Ni(II)] metal complexes, derived from indoleninyl meso-substituted dibenzotetraazaannulene, were synthesized. The resulting dimers feature Ni···Ni or, alternatively, Ni···π interactions in staggered or slipped cofacial structures. A remarkable insertion of palladium into two different C-H bonds yielded a 4[Pd(II)-Ni(II)] rectangular complex with dimensions of 8.73 × 10.38 Å.