Lactobacillus plantarum RI 11 was reported recently to be a potential lignocellulosic biomass degrader since it has the capability of producing versatile extracellular cellulolytic and hemicellulolytic enzymes. Thus, this study was conducted to evaluate further the effects of various renewable natural polymers on the growth and production of extracellular cellulolytic and hemicellulolytic enzymes by this novel isolate. Basal medium supplemented with molasses and yeast extract produced the highest cell biomass (log 10.51 CFU/mL) and extracellular endoglucanase (11.70 µg/min/mg), exoglucanase (9.99 µg/min/mg), β-glucosidase (10.43 nmol/min/mg), and mannanase (8.03 µg/min/mg), respectively. Subsequently, a statistical optimization approach was employed for the enhancement of cell biomass, and cellulolytic and hemicellulolytic enzyme productions. Basal medium that supplemented with glucose, molasses and soybean pulp (F5 medium) or with rice straw, yeast extract and soybean pulp (F6 medium) produced the highest cell population of log 11.76 CFU/mL, respectively. However, formulated F12 medium supplemented with glucose, molasses and palm kernel cake enhanced extracellular endoglucanase (4 folds), exoglucanase (2.6 folds) and mannanase (2.6 folds) specific activities significantly, indicating that the F12 medium could induce the highest production of extracellular cellulolytic and hemicellulolytic enzymes concomitantly. In conclusion, L. plantarum RI 11 is a promising and versatile bio-transformation agent for lignocellulolytic biomass.
In this work, mesoporous TiO2-modified ZnO quantum dots (QDs) were immobilised on a linear low-density polyethylene (LLDPE) polymer using a solution casting method for the photodegradation of tetracycline (TC) antibiotics under fluorescent light irradiation. Various spectroscopic and microscopic techniques were used to investigate the physicochemical properties of the floating hybrid polymer film catalyst (8%-ZT@LLDPE). The highest removal (89.5%) of TC (40 mg/L) was achieved within 90 min at pH 9 due to enhanced water uptake by the LDDPE film and the surface roughness of the hybrid film. The formation of heterojunctions increased the separation of photogenerated electron-hole pairs. The QDs size-dependent quantum confinement effect leads to the displacement of the conduction band potential of ZnO QDs to more negative energy values than TiO2. The displacement generates more reactive species with higher oxidation ability. The highly stable film photocatalyst can be separated easily and can be repeatedly used up to 8 cycles without significant loss in the photocatalytic ability. The scavenging test indicates that the main species responsible for the photodegradation was O2●-. The proposed photodegradation mechanism of TC was demonstrated in further detail based on the intermediates detected by LC-time-of-flight/mass spectrometry (LC/TOF-MS).
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.
In the present work, promising proton conducting solid polymer blend electrolytes (SPBEs) composed of chitosan (CS) and methylcellulose (MC) were prepared for electrochemical double-layer capacitor (EDLC) application with a high specific capacitance and energy density. The change in intensity and the broad nature of the XRD pattern of doped samples compared to pure CS:MC system evidencedthe amorphous character of the electrolyte samples. The morphology of the samples in FESEM images supported the amorphous behavior of the solid electrolyte films. The results of impedance and Bode plotindicate that the bulk resistance decreasedwith increasing salt concentration. The highest DC conductivity was found to be 2.81 × 10-3 S/cm. The electrical equivalent circuit (EEC) model was conducted for selected samples to explain the complete picture of the electrical properties.The performance of EDLC cells was examined at room temperature by electrochemical techniques, such as impedance spectroscopy, cyclic voltammetry (CV) and constant current charge-discharge techniques. It was found that the studied samples exhibit a very good performance as electrolyte for EDLC applications. Ions were found to be the dominant charge carriers in the polymer electrolyte. The ion transference number (tion) was found to be 0.84 while 0.16 for electron transference number (tel). Through investigation of linear sweep voltammetry (LSV), the CS:MC:NH4SCN system was found to be electrochemically stable up to 1.8 V. The CV plot revealed no redox peak, indicating the occurrence of charge double-layer at the surface of activated carbon electrodes. Specific capacitance (Cspe) for the fabricated EDLC was calculated using CV plot and charge-discharge analyses. It was found to be 66.3 F g-1 and 69.9 F g-1 (at thefirst cycle), respectively. Equivalent series resistance (Resr) of the EDLC was also identified, ranging from 50.0 to 150.0 Ω. Finally, energy density (Ed) was stabilized to anaverage of 8.63 Wh kg-1 from the 10th cycle to the 100th cycle. The first cycle obtained power density (Pd) of 1666.6 W kg-1 and then itdropped to 747.0 W kg-1 at the 50th cycle and continued to drop to 555.5 W kg-1 as the EDLC completed 100 cycles.
Nanotubular clay minerals, composed of aluminosilicate naturally structured in layers known as halloysite nanotubes (HNTs), have a significant reinforcing impact on polymer matrixes. HNTs have broad applications in biomedical applications, the medicine sector, implant alloys with corrosion protection and manipulated transportation of medicines. In polymer engineering, different research studies utilize HNTs that exhibit a beneficial enhancement in the properties of polymer-based nanocomposites. The dispersion of HNTs is improved as a result of pre-treating HNTs with acids. The HNTs' percentage additive up to 7% shows the highest improvement of tensile strength. The degradation of the polymer can be also significantly improved by doping a low percentage of HNTs. Both the mechanical and thermal properties of polymers were remarkably improved when mixed with HNTs. The effects of HNTs on the mechanical and thermal properties of polymers, such as ultimate strength, elastic modulus, impact strength and thermal stability, are emphasized in this study.
Great efforts have been devoted to the invention of environmental sensors as the amount of water pollution has increased in recent decades. Chitosan, cellulose and nanocrystalline cellulose are examples of biopolymers that have been intensively studied due to their potential applications, particularly as sensors. Furthermore, the rapid use of conducting polymer materials as a sensing layer in environmental monitoring has also been developed. Thus, the incorporation of biopolymer and conducting polymer materials with various methods has shown promising potential with sensitively and selectively toward heavy metal ions. In this feature paper, selected recent and updated investigations are reviewed on biopolymer and conducting polymer-based materials in sensors aimed at the detection of heavy metal ions by optical methods. This review intends to provide sufficient evidence of the potential of polymer-based materials as sensing layers, and future outlooks are considered in developing surface plasmon resonance as an excellent and valid sensor for heavy metal ion detection.
The development of bio-polyol from vegetable oil and its derivatives is gaining much interest from polyurethane industries and academia. In view of this, the availability of methyl oleate derived from palm oil, which is aimed at biodiesel production, provides an excellent feedstock to produce bio-polyol for polyurethane applications. In this recent study, response surface methodology (RSM) with a combination of central composite rotatable design (CCRD) was used to optimise the reaction parameters in order to obtain a maximised hydroxyl value (OHV). Three reaction parameters were selected, namely the mole ratio of epoxidised methyl oleate (EMO) to glycerol (1:5-1:10), the amount of catalyst loading (0.15-0.55%) and reaction temperature (90-150 °C) on a response variable as the hydroxyl value (OHV). The analysis of variance (ANOVA) indicated that the quadratic model was significant at 98% confidence level with (p-value > 0.0001) with an insignificant lack of fit and the regression coefficient (R2) was 0.9897. The optimum reaction conditions established by the predicted model were: 1:10 mole ratio of EMO to glycerol, 0.18% of catalyst and 120 °C reaction temperature, giving a hydroxyl value (OHV) of 306.190 mg KOH/g for the experimental value and 301.248 mg KOH/g for the predicted value. This result proves that the RSM model is capable of forecasting the relevant response. FTIR analysis was employed to monitor the changes of functional group for each synthesis and the confirmation of this finding was analysed by NMR analysis. The viscosity and average molecular weight (MW) were 513.48 mPa and 491 Da, respectively.
This study investigated the potential of chitosan-coated mixed micellar nanocarriers (polyplexes) for codelivery of siRNA and doxorubicin (DOX). DOX-loaded mixed micelles (serving as cores) were prepared by thin film hydration method and coated with chitosan (CS, serving as outer shell), and complexed with multidrug resistance (MDR) inhibiting siRNA. Selective targeting was achieved by folic acid conjugation. The polyplexes showed pH-responsive enhanced DOX release in acidic tumor pH, resulting in higher intracellular accumulation, which was further augmented by downregulation of mdr-1 gene after treatment with siRNA-complexed polyplexes. In vitro cytotoxicity assay demonstrated an enhanced cytotoxicity in native 4T1 and multidrug-resistant 4T1-mdr cell lines, compared to free DOX. Furthermore, in vivo, polyplexes codelivery resulted in highest DOX accumulation and significantly reduced the tumor volume in mice with 4T1 and 4T1-mdr tumors as compared to the free DOX groups, leading to improved survival times in mice. In conclusion, codelivery of siRNA and DOX via polyplexes has excellent potential as targeted drug nanocarriers for treatment of MDR cancers.
This paper presents the efficient synthesis of 2-amino-4H-benzo[b]pyrans using mesoporous poly-melamine-formaldehyde as a polymeric heterogeneous catalyst. According to the principals of green chemistry, the reaction was performed by the planetary ball milling process at ambient and neat conditions. The heterogeneous catalyst could be reused up to five runs with no reducing of catalytic efficiency. A variety of substituted 2-amino-4H-benzo[b]pyrans were obtained in good to excellent yields under eco-friendly conditions. Other advantages of the current methodology include short reaction time, wide substrate-scope, and use of a metal-free polymeric catalyst. Also, the current method avoids the use of hazardous reagents and solvents, tedious workup and multi-step purification. This work revealed that porous organic polymers containing Lewis base sites having acceptor-donner hydrogen bonding functional groups, and high porosity could play a vital role in the promotion of the one-pot multicomponent reactions in the solid-phase synthesis.
An amperometric sensor for L-Cys is described which consists of a glassy carbon electrode (GCE) that was modified with reduced graphene oxide placed in a Nafion film and decorated with palladium nanoparticles (PdNPs). The film was synthesized by a hydrothermal method. The PdNPs have an average diameter of about 10 nm and a spherical shape. The modified GCE gives a linear electro-oxidative response to L-Cys (typically at +0.6 V vs. SCE) within the 0.5 to 10 μM concentration range. Other figures of merit include a response time of less than 2 s, a 0.15 μM lower detection limit (at signal to noise ratio of 3), and an analytical sensitivity of 1.30 μA·μM-1·cm-2. The sensor displays selectivity over ascorbic acid, uric acid, dopamine, hydrogen peroxide, urea, and glucose. The modified GCE was applied to the determination of L-Cys in human urine samples and gave excellent recoveries. Graphical abstract Spherical palladium nanoparticles (PdNPs) on reduced graphene oxide-Nafion (rGO-Nf) films were synthesized using a hydrothermal method. This nanohybrid was used for modifying a glassy carbon electrode to develop a sensor electrode for detecting L-cysteine that has fast response (less than 2 s), low detection limit (0.15 μM), and good sensitivity (0.092 μA μM-1 cm-2).
Polysaccharides are excellent candidates for drug delivery applications as they are available in abundance from natural sources. Polysaccharides such as starch, cellulose, lignin, chitosan, alginate, and tragacanth gum are used to make hydrogels beads. Hydrogels beads are three-dimensional, cross-linked networks of hydrophilic polymers formed in spherical shape and sized in the range of 0.5-1.0 mm of diameter. Beads are formed by various cross-linking methods such as chemical and irradiation methods. Natural polymer-based hydrogels are biocompatible and biodegradable and have inherently low immunogenicity, which makes them suitable for physiological drug delivery approaches. The cross-linked polysaccharide-based hydrogels are environment-sensitive polymers that can potentially be used for the development of "smart" delivery systems, which are capable of control release of the encapsulated drug at a targeted colon site. This topic focuses on various aspects of fabricating and optimizing the cross-linking of polysaccharides, either by a single polysaccharide or mixtures and also natural-synthetic hybrids to produce polymer-based hydrogel vehicles for colon-targeted drug delivery.
Hydroxyapatite (HA) coated implant is more susceptible to bacterial infection as the micro-structure surface which is beneficial for osseointegration, could also become a reservoir for bacterial colonisation. The aim of this study was to introduce the antibacterial effect of silver (Ag) to the biomineralised HA by utilising a polydopamine film as an intermediate layer for Ag and HA immobilisation. Sufficient catechol groups in polydopamine were required to bind chemically stainless steel 316 L, Ag and HA elements. Different amounts of Ag nanoparticles were metallised on the polydopamine grafted stainless steel by varying the immersion time in silver nitrate solution from 12 to 24 h. Another polydopamine layer was then formed on the metallised film, followed by surface biomineralisation in 1.5 Simulated Body Fluid (SBF) solution for 3 days. Several characterisation techniques including X-Ray Photoelectron Spectroscopy, Atomic Force Microscopy, Scanning Electron Microscopy and Contact Angle showed that Ag nanoparticles and HA agglomerations were successfully immobilised on the polydopamine film through an element reduction process. The Ag metallisation at 24 h has killed the viable bacteria with 97.88% of bactericidal ratio. The Ag was ionised up to 7 days which is crucial to prevent bacterial infection during the first stage of implant restoration. The aged functionalised films were considered stable due to less alteration of its chemical composition, surface roughness and wettability properties. The ability of the functionalised film to coat complex and micro scale metal make it suitable for dental and orthopaedic implants application.
The actual in vivo tissue scaffold offers a three-dimensional (3D) structural support along with a nano-textured surfaces consist of a fibrous network in order to deliver cell adhesion and signaling. A scaffold is required, until the tissue is entirely regenerated or restored, to act as a temporary ingrowth template for cell proliferation and extracellular matrix (ECM) deposition. This review depicts some of the most significant three dimensional structure materials used as scaffolds in various tissue engineering application fields currently being employed to mimic in vivo features. Accordingly, some of the researchers' attempts have envisioned utilizing graphene for the fabrication of porous and flexible 3D scaffolds. The main focus of this paper is to evaluate the topographical and topological optimization of scaffolds for tissue engineering applications in order to improve scaffolds' mechanical performances.
Polyethersulfone (PES) based membranes are used for dialysis, but exposure to blood can result in numerous interactions between the blood elements and the membrane. Adsorption and transformation of plasma proteins, activation of blood cells, adherence of platelets and thrombosis reactions against PES membrane can invoke severe blood reactions causing the increase rate of mortality and morbidity of hemodialysis (HD) patients. In order to minimize blood immune response, different biomimetic, zwitterionic, non-ionic, anticoagulant molecules and hydrophilic brushes were immobilized or blended with PES polymers. These additives modified the nature of the membrane, enhanced their biocompatibility and also increased the uremic waste dialysis properties. In this review, current perspectives of the different additives which are used with PES are highlighted in relation with PES membrane-associated blood reactions. The additive's purpose, compatibility, preparation techniques, methods of addition to polymer and influence on the chemistry and performance of hemodialysis membranes are described.
Non-covalent electrostatic interaction between amide nitrogen and carbonyl carbon of shorter chain length of polyvinylpyrrolidone (PVP-k25) was developed with in-house carboxylic oxidized multiwall carbon nanotubes (O-MWCNT) and then blended with Polyethersulfone (PES) polymer. FTIR analysis was utilized to confirm bonding nature of nano-composites (NCs) of O-MWCNT/PVP-k25 and casting membranes. Non-solvent induces phase separation process developed regular finger-like channels in composite membranes whereas pristine PES exhibited spongy entities as studied by cross sectional analysis report of FESEM. Further, FESEM instrument was also utilized to observe the dispersion of O-MWCNT/PVP based nanocomposite (NCs) with PES and membranes leaching phenomena analysis. Contact angle experiments described 24% improvement of hydrophilic behaviour, leaching ratio of additives was reduced to 1.89%, whereas water flux enhanced up to 6 times. Bovine serum albumin (BSA) and lysozyme based antifouling analysis shown up to 25% improvement, whereas 84% of water flux was regained after protein fouling than pristine PES. Anticoagulant activity was reported by estimating prothrombin, thrombin, plasma re-calcification times and production of fibrinogen cluster with platelets-adhesions photographs and hemolysis experiments. Composite membranes exhibited 3.4 and 3 times better dialysis clearance ratios of urea and creatinine solutes as compared to the raw PES membrane.
Poly (citric acid)-grafted-MWCNT (PCA-g-MWCNT) was incorporated as nanofiller in polyethersulfone (PES) to produce hemodialysis mixed matrix membrane (MMM). Citric acid monohydrate was polymerized onto the surface of MWCNTs by polycondensation. Neat PES membrane and PES/MWCNTs MMMs were fabricated by dry-wet spinning technique. The membranes were characterized in terms of morphology, pure water flux (PWF) and bovine serum albumin (BSA) protein rejection. The grafting yield of PCA onto MWCNTs was calculated as 149.2%. The decrease of contact angle from 77.56° to 56.06° for PES/PCA-g-MWCNTs membrane indicated the increase in surface hydrophilicity, which rendered positive impacts on the PWF and BSA rejection of the membrane. The PWF increased from 15.8Lm(-2)h(-1) to 95.36Lm(-2)h(-1) upon the incorporation of PCA-g-MWCNTs due to the attachment of abundant hydrophilic groups that present on the MWCNTs, which have improved the affinity of membrane towards the water molecules. For protein rejection, the PES/PCA-g-MWCNTs MMM rejected 95.2% of BSA whereas neat PES membrane demonstrated protein rejection of 90.2%. Compared to commercial PES hemodialysis membrane, the PES/PCA-g-MWCNTs MMMs showed less flux decline behavior and better PWF recovery ratio, suggesting that the membrane antifouling performance was improved. The incorporation of PCA-g-MWCNTs enhanced the separation features and antifouling capabilities of the PES membrane for hemodialysis application.
This study conducted on the structure of modified acrylamide-based hydrogel by synthesizing the nano composites. The hydrogels employed in this study were provided through a combination of acrylamide monomers, sodium carboxymethyl cellulose (NaCMC) and magnesium oxide (MgO) nanoparticles by crosslinking polymerization. N,N,N',N'-tetramethylethylenediamine and ammonium persulfate as the initiator was applied in the structure of the polymer. Findings of the study considered the nano composites consisting of MgO have the highest swelling ratio compared to pure Aam hydrogels. Thus, MgO is an appropriate nanoparticle to be used in the nano composites. Response surface methodology (RSM) based on a central composite design (CCD Design) was applied to optimize the preparation variables of a hydrogel consisted of MgO, NaCMC. With the swelling ratio for acrylamide-based hydrogel as the response, the effects of two variables, i.e. MgO and NaCMC were investigated. The effects of pH, temperature, MgO, and NaCMC on the drug release were investigated using the CCD design. The predicted appropriate drug release conditions for the hydrogel at the highest rate of temperature (37.50 °C) and pH: 4.10, is at its highest value, while the lower drug release is at temperature 38 °C and pH 3.50. With the desired value of MgO (0.01 g) and amount of NaCMC (0.1 g).
Role of sulfur (S) and nitrogen (N) groups in promoting cell adhesion or commonly known as biocompatibility, is well established, but their role in reducing bacterial attachment and growth is less explored or not well-understood. Natural sulfur-based compounds, i.e. sulfide, sulfoxide and sulfinic groups, have shown to inhibit bacterial adhesion and biofilm formation. Hence, we mimicked these surfaces by plasma polymerizing thiophene (ppT) and air-plasma treating this ppT to achieve coatings with S of similar oxidation states as natural compounds (ppT-air). In addition, the effects of these N and S groups from ppT-air were also compared with the biocompatible amine-amide from n-heptylamine plasma polymer. Crystal violet assay and live and dead fluorescence staining of E. coli and S. aureus showed that all the N and S coated surfaces generated, including ppHA, ppT and ppT-air, produced similarly potent, growth reduction of both bacteria by approximately 65% at 72 h compared to untreated glass control. The ability of osteogenic differentiation in Wharton's jelly mesenchymal stem cells (WJ-MSCs) were also used to test the cell biocompatibility of these surfaces. Alkaline phosphatase assay and scanning electron microscopy imaging of these WJ-MSCs growths indicated that ppHA, and ppT-air were cell-friendly surfaces, with ppHA showing the highest osteogenic activity. In summary, the N and S containing surfaces could reduce bacteria growth while promoting mammalian cell growth, thus serve as potential candidate surfaces to be explored further for biomaterial applications.
A novel series of silver-doped mesoporous bioactive glass/poly(1,8-octanediol citrate) (AgMBG/POC) elastomeric biocomposite scaffolds were successfully constructed by a salt-leaching technique for the first time and the effect of inclusion of different AgMBG contents (5, 10, and 20 wt%) on physicochemical and biological properties of pure POC elastomer was evaluated. Results indicated that AgMBG particles were uniformly dispersed in the POC matrix and increasing the AgMBG concentration into POC matrix up to 20 wt% enhanced thermal behaviour, mechanical properties and water uptake ability of the composite scaffolds compared to those from POC. The 20%AgMBG/POC additionally showed higher degradation rate in Tris(hydroxymethyl)-aminomethane-HCl (Tris-HCl) compared with pure POC and lost about 26% of its initial weight after soaking for 28 days. The AgMBG phase incorporation also significantly endowed the resulting composite scaffolds with efficient antibacterial properties against Escherichia coli and Staphylococcus aureus bacteria while preserving their favorable biocompatibility with soft tissue cells (i.e., human dermal fibroblast cells). Taken together, our results suggest that the synergistic effect of both AgMBG and POC make these newly designed AgMBG/POC composite scaffold an attractive candidate for soft tissue engineering applications.