Amphiphilic block copolymers are widely utilized in the design of formulations owing to their unique physicochemical properties, flexible structures and functional chemistry. Amphiphilic polymeric micelles (APMs) formed from such copolymers have gained attention of the drug delivery scientists in past few decades for enhancing the bioavailability of lipophilic drugs, molecular targeting, sustained release, stimuli-responsive properties, enhanced therapeutic efficacy and reducing drug associated toxicity. Their properties including ease of surface modification, high surface area, small size, and enhanced permeation as well as retention (EPR) effect are mainly responsible for their utilization in the diagnosis and therapy of various diseases. However, some of the challenges associated with their use are premature drug release, low drug loading capacity, scale-up issues and their poor stability that need to be addressed for their wider clinical utility and commercialization. This review describes comprehensively their physicochemical properties, various methods of preparation, limitations followed by approaches employed for the development of optimized APMs, the impact of each preparation technique on the physicochemical properties of the resulting APMs as well as various biomedical applications of APMs. Based on the current scenario of their use in treatment and diagnosis of diseases, the directions in which future studies need to be carried out to explore their full potential are also discussed.
The synergetic effect of nitrogen-rich and CO2-philic filler and polymer in mixed matrix-based membranes (MMMs) can separate CO2 competently. The introduction of well-defined nanostructured porous fillers of pores close to the kinetic diameter of the gas molecule and polymer matrix compatibility is a challenge in improving the gas transportation characteristics of MMMs. This study deals with the preparation of porphyrin filler and the polysulfone (PSf) polymer MMMs. The fillers demonstrated uniform distribution, uniformity, and successful bond formation. MMMs demonstrated high thermal stability with a glass transition temperature in the range of 480-610 °C. The porphyrin filler exhibited microporous nature with the presence of π-π bonds and Lewis's basic functionalities between filler-polymer resulted in a highly CO2-philic structure. The pure and mixed gas permeabilities and selectivity were successfully improved and surpass the Robeson's upper bound curve's tradeoff. Additionally, the temperature influence on CO2 permeability revealed lower activation energies at higher temperatures leading to the gas transport facilitation. This can be granted consistency and long-term durability in polymer chains. These results highlight the unique properties of porphyrin fillers in CO2 separation mixed matrix membranes and offer new knowledge to increase comprehension of PSf performance under various contents or environments.
Marine microbes provide an important resource to discover new chemical compounds with biological activities beneficial to drug discovery. In our study, two new polyene macrolides, pyranpolyenolides A (1) and B (2), and one new natural cyclic peptide (9), together with two known polyenes (7 and 8) and three known cyclic peptides (10-12), were isolated from a culture of the marine Streptomyces sp. MS110128. In addition, four new polyene macrolides, pyranpolyenolides C-F (3-6), were identified as olefin geometric isomers that were most likely produced by photochemical conversion during the cultivation or isolation procedures. The pyranpolyenolides are 32-membered macrolides endowed with a conjugated tetraene and several pairs of 1,3-dihydroxyl groups. Pyranpolyenolides that contain a hydropyran group have not been previously reported. Four cyclic peptides (9-12) showed significant activities against Bacillus subtilis, Staphylococcus aureus, and methicillin-resistant S. aureus with supporting MIC values ranging from 0.025 to 1.25 μg/mL. These cyclic peptides containing piperazic moieties showed moderate activities with MIC values of 12.5 μg/mL against Bacille Calmette Guerin (BCG), an attenuated form of the bovine. Additionally, cyclic peptide 12 showed moderate antifungal activity against Candida albicans with an MIC value of 12.5 μg/mL. KEY POINTS: • Discovery of new polyenes and cyclic peptides from a marine-derived Actinomycete. • Cyclic peptides containing piperazic moieties exhibited good antibacterial activity.
Crystallinity plays a vital role in the pharmaceutical industry. It affects drug manufacturing, development processes, and the stability of pharmaceutical dosage forms. An objective of this study was to measure and analyze the carbamazepine (CBZ) crystallinity before and after formulation. Moreover, it intended to determine the extent to which the crystallinity of CBZ would affect the drug loading, the particle size, and the release of CBZ from the microparticles. The CBZ microparticles were prepared by encapsulating CBZ in ethyl cellulose (EC) polymer using a solvent evaporation method. EC was used here as a release modifier polymer and polyvinyl alcohol (PVA) as an aqueous phase stabilizer. Factorial design was used to prepare the CBZ microparticle formulations, including polymer concentration, solvent (dichloromethane, ethyl acetate), PVA concentrations factor, the homogenization time, and homogenization speed. The crystallinity of CBZ was calculated utilizing differential scanning calorimetry (DSC) thermal analysis. The crystallinity was calculated from the enthalpy of CBZ. Enthalpy was analyzed from the area under the curve peak of CBZ standard and CBZ-loaded microparticles. DSC and ATR-FTIR assessed the possible interaction between CBZ and excipients in the microparticle. The prepared CBZ microparticles showed various changes in the crystallinity rate of CBZ. The changes in the rate of CBZ crystallinity had different effects on the particle size, the drug loading, and the release of CBZ from the polymer. Statistically, all studied factors significantly affected the crystallinity of CBZ after formulation to microparticles.
The effect of incorporating different loadings of oil palm bio-ash nanoparticles from agriculture waste on the properties of phenol-formaldehyde resin was investigated in this study. The bio-ash filler was used to enhance the performance of phenol-formaldehyde nanocomposites. Phenol-formaldehyde resin filled with oil palm bio-ash nanoparticles was prepared via the in-situ polymerization process to produce nanocomposites. The transmission electron microscope and particle size analyzer result revealed that oil palm bio-ash nanoparticles had a spherical geometry of 90 nm. Furthermore, X-ray diffraction results confirmed the formation of crystalline structure in oil palm bio-ash nanoparticles and phenol-formaldehyde nanocomposites. The thermogravimetric analysis indicated that the presence of oil palm bio-ash nanoparticles enhanced the thermal stability of the nanocomposites. The presence of oil palm bio-ash nanoparticles with 1% loading in phenol-formaldehyde resin enhanced the internal bonding strength of plywood composites. The scanning electron microscope image revealed that phenol-formaldehyde nanocomposites morphology had better uniform distribution and dispersion with 1% oil palm bio-ash nanoparticle loading than other phenol-formaldehyde nanocomposites produced. The nanocomposite has potential use in the development of particle and panel board for industrial applications.
Toxic metals in the industrial wastewaters have been liable for drastic pollution hence a powerful and economical treatment technology is needed for water purification. For this reason, some pure cellulosic materials were derived from waste fiber to obtain an economical adsorbent for wastewater treatment. Conversion of cellulose into grafting materials such as poly(methyl acrylate)-grafted cellulose was performed by free radical grafting process. Consequently, poly(hydroxamic acid) ligand was produced from the grafted cellulose. The intermediate products and poly(hydroxamic acid) ligand were analyzed by FT-IR, FE-SEM, TEM, EDX, and XPS spectroscopy. The adsorption capacity (qe) of some toxic metals ions by the polymer ligand was found to be excellent, e.g., copper capacity (qe) was 346.7 mg·g-1 at pH 6. On the other hand, several metal ions such as cobalt chromium and nickel also demonstrated noteworthy sorption capacity at pH 6. The adsorption mechanism obeyed the pseudo second-order rate kinetic model due to the satisfactory correlated experimental sorption values (qe). Langmuir model isotherm study showed the significant correlation coefficient with all metal ions (R2 > 0.99), indicating that the single or monolayer adsorption was the dominant mode on the surface of the adsorbent. This polymer ligand showed good properties on reusability. The result shows that the adsorbent may be recycled for 6 cycles without any dropping of starting sorption capabilities. This polymeric ligand showed outstanding toxic metals removal magnitude, up to 90-99% of toxic metal ions can be removed from industrial wastewater.
The polymer solar cells also known as organic solar cells (OSCs) have drawn attention due to their cynosure in industrial manufacturing because of their promising properties such as low weight, highly flexible, and low-cost production. However, low η restricts the utilization of OSCs for potential applications such as low-cost energy harvesting devices. In this paper, OSCs structure based on a triple-junction tandem scheme is reported with three different absorber materials to enhance the absorption of photons which in turn improves the η, as well as its correlating performance parameters. The investigated structure gives the higher value of η = 14.33% with Jsc = 16.87 (mA/m2), Voc = 1.0 (V), and FF = 84.97% by utilizing a stack of three different absorber layers with different band energies. The proposed structure was tested under 1.5 (AM) with 1 sun (W/m2). The impact of the top, middle, and bottom subcells' thickness on η was analyzed with a terse to find the optimum thickness for three subcells to extract high η. The optimized structure was then tested with different electrode combinations, and the highest η was recorded with FTO/Ag. Moreover, the effect of upsurge temperature was also demonstrated on the investigated schematic, and it was observed that the upsurge temperature affects the photovoltaic (PV) parameters of the optimized cell and η decreases from 14.33% to 11.40% when the temperature of the device rises from 300 to 400 K.
A large amount of wastewater is typically discharged into water bodies and has extremely harmful effects to aquatic environments. The removal of heavy metals from water bodies is necessary for the safe consumption of water and human activities. The demand for seafood has considerably increased, and millions of tons of crustacean waste are discarded every year. These waste products are rich in a natural biopolymer known as chitin. The deacetylated form of chitin, chitosan, has attracted attention as an adsorbent. It is a biocompatible and biodegradable polymer that can be modified and converted to various derivatives. This review paper focuses on relevant literature on strategies for chemically modifying the biopolymer and its use in the removal of heavy metals from water and wastewater. The different aspects of chitosan-based derivatives and their preparation and application are elucidated. A list of chitosan-based composites, along with their adsorptivity and experimental conditions, are compiled.
The objective of this work was to study the influence of cellulose nanofibrils (CNF) on the physical, mechanical, and thermal properties of Jatropha oil-based waterborne polyurethane (WBPU) nanocomposite films. The polyol to produce polyurethane was synthesized from crude Jatropha oil through epoxidation and ring-opening method. The chain extender, 1,6-hexanediol, was used to improve film elasticity by 0.1, 0.25, and 0.5 wt.% of CNF loading was incorporated to enhance film performance. Mechanical performance was studied using a universal test machine as specified in ASTM D638-03 Type V and was achieved by 0.18 MPa at 0.5 wt.% of CNF. Thermal gravimetric analysis (TGA) was performed to measure the temperature of degradation and the chemical crosslinking and film morphology were studied using Fourier-transform infrared spectroscopy (FTIR) and field emission scanning electron microscopy (FESEM). The results showed that when the CNF was incorporated, it was found to enhance the nanocomposite film, in particular its mechanical and thermal properties supported by morphology. Nanocomposite film with 0.5 wt.% of CNF showed the highest improvement in terms of tensile strength, Young's modulus, and thermal degradation. Although the contact angle decreases as the CNF content increases, the effect on the water absorption of the film was found to be relatively small (<3.5%). The difference between the neat WPBU and the highest CNF loading film was not more than 1%, even after 5 days of being immersed in water.
Researchers and companies have increasingly been drawn to biodegradable polymers and composites because of their environmental resilience, eco-friendliness, and suitability for a range of applications. For various uses, biodegradable fabrics use biodegradable polymers or natural fibers as reinforcement. Many approaches have been taken to achieve better compatibility for tailored and improved material properties. In this article, PBS (polybutylene succinate) was chosen as the main topic due to its excellent properties and intensive interest among industrial and researchers. PBS is an environmentally safe biopolymer that has some special properties, such as good clarity and processability, a shiny look, and flexibility, but it also has some drawbacks, such as brittleness. PBS-based natural fiber composites are completely biodegradable and have strong physical properties. Several research studies on PBS-based composites have been published, including physical, mechanical, and thermal assessments of the properties and its ability to replace petroleum-based materials, but no systematic analysis of up-to-date research evidence is currently available in the literature. The aim of this analysis is to highlight recent developments in PBS research and production, as well as its natural fiber composites. The current research efforts focus on the synthesis, copolymers and biodegradability for its properties, trends, challenges and prospects in the field of PBS and its composites also reviewed in this paper.
The development of advanced composite materials has taken center stage because of its advantages over traditional materials. Recently, carbon-based advanced additives have shown promising results in the development of advanced polymer composites. The inter- and intra-laminar fracture toughness in modes I and II, along with the thermal and electrical conductivities, were investigated. The HMWCNTs/epoxy composite was prepared using a multi-dispersion method, followed by uniform coating at the mid-layers of the CF/E prepregs interface using the spray coating technique. Analysis methods, such as double cantilever beam (DCB) and end notched flexure (ENF) tests, were carried out to study the mode I and II fracture toughness. The surface morphology of the composite was analyzed using field emission scanning electron microscopy (FESEM). The DCB test showed that the fracture toughness of the 0.2 wt.% and 0.4 wt.% HMWCNT composite laminates was improved by 39.15% and 115.05%, respectively, compared with the control sample. Furthermore, the ENF test showed that the mode II interlaminar fracture toughness for the composite laminate increased by 50.88% and 190%, respectively. The FESEM morphology results confirmed the HMWCNTs bridging at the fracture zones of the CF/E composite and the improved interlaminar fracture toughness. The thermogravimetric analysis (TGA) results demonstrated a strong intermolecular bonding between the epoxy and HMWCNTs, resulting in an improved thermal stability. Moreover, the differential scanning calorimetry (DSC) results confirmed that the addition of HMWCNT shifted the Tg to a higher temperature. An electrical conductivity study demonstrated that a higher CNT concentration in the composite laminate resulted in a higher conductivity improvement. This study confirmed that the demonstrated dispersion technique could create composite laminates with a strong interfacial bond interaction between the epoxy and HMWCNT, and thus improve their properties.
In this review, the potential of natural fiber and kenaf fiber (KF) reinforced PLA composite filament for fused deposition modeling (FDM) 3D-printing technology is highlighted. Additive manufacturing is a material-processing method in which the addition of materials layer by layer creates a three-dimensional object. Unfortunately, it still cannot compete with conventional manufacturing processes, and instead serves as an economically effective tool for small-batch or high-variety product production. Being preformed of composite filaments makes it easiest to print using an FDM 3D printer without or with minimum alteration to the hardware parts. On the other hand, natural fiber-reinforced polymer composite filaments have gained great attention in the market. However, uneven printing, clogging, and the inhomogeneous distribution of the fiber-matrix remain the main challenges. At the same time, kenaf fibers are one of the most popular reinforcements in polymer composites. Although they have a good record on strength reinforcement, with low cost and light weight, kenaf fiber reinforcement PLA filament is still seldom seen in previous studies. Therefore, this review serves to promote kenaf fiber in PLA composite filaments for FDM 3D printing. To promote the use of natural fiber-reinforced polymer composite in AM, eight challenges must be solved and carried out. Moreover, some concerns arise to achieve long-term sustainability and market acceptability of KF/PLA composite filaments.
We present a novel synthesis strategy termed delayed linker addition (DLA) to synthesize hybrid zeolitic-imidazolate frameworks containing unsubstituted imidazolate linkers (Im) with SOD topology (hereafter termed Im/ZIF-8). Im linker incorporation can create larger voids and apertures, which are important properties for gas storage and separation. To date, there have been only a handful of reports of Im linkers incorporated into ZIF-8 frameworks, typically requiring arduous and complicated post synthesis approaches. DLA, as reported here, is a simple one-step synthesis strategy allowing high incorporation of Im linker into the ZIF-8 framework while still retaining its SOD topology. We fabricated mixed-matrix membranes (MMMs) with 6FDA-DAM polymer and Im/ZIF-8 obtained via DLA as a filler. The Im/ZIF-8-containing MMMs showed excellent performance for both propylene/propane and n-butane/i-butane separation, displaying permeability and ideal selectivity well above the polymer upper bound. Moreover, highly detailed molecular simulations shed light to the aperture size and flexibility response of Im/ZIF-8 and its improved diffusivity as compared to ZIF-8.
Thermoplastic starch composites have attracted significant attention due to the rise of environmental pollutions induced by the use of synthetic petroleum-based polymer materials. The degradation of traditional plastics requires an unusually long time, which may lead to high cost and secondary pollution. To solve these difficulties, more petroleum-based plastics should be substituted with sustainable bio-based plastics. Renewable and natural materials that are abundant in nature are potential candidates for a wide range of polymers, which can be used to replace their synthetic counterparts. This paper focuses on some aspects of biopolymers and their classes, providing a description of starch as a main component of biopolymers, composites, and potential applications of thermoplastics starch-based in packaging application. Currently, biopolymer composites blended with other components have exhibited several enhanced qualities. The same behavior is also observed when natural fibre is incorporated with biopolymers. However, it should be noted that the degree of compatibility between starch and other biopolymers extensively varies depending on the specific biopolymer. Although their efficacy is yet to reach the level of their fossil fuel counterparts, biopolymers have made a distinguishing mark, which will continue to inspire the creation of novel substances for many years to come.
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).
Nowadays, pultruded glass fiber-reinforced polymer composite (PGFRPC) structures have been used widely for cross-arms in high transmission towers. These composite structures have replaced cross-arms of conventional materials like wood due to several factors, such as better strength, superior resistance to environmental degradation, reduced weight, and comparatively cheaper maintenance. However, lately, several performance failures have been found on existing cross-arm members, caused by moisture, temperature changes in the atmosphere, and other environmental factors, which may lead to a complete failure or reduced service life. As a potential solution for this problem, enhancing PGFRPC with honeycomb-filled composite structures will become a possible alternative that can sustain a longer service life compared to that of existing cross-arms. This is due to the new composite structures' superior performance under mechanical duress in providing better stiffness, excellence in flexural characteristics, good energy absorption, and increased load-carrying capacity. Although there has been a lack of previous research done on the enhancement of existing composite cross-arms in applications for high transmission towers, several studies on the enhancement of hollow beams and tubes have been done. This paper provides a state-of-the-art review study on the mechanical efficiency of both PGFRPC structures and honeycomb-filled composite sandwich structures in experimental and analytical terms.
This report shows a simple solution cast methodology to prepare plasticized polyvinyl alcohol (PVA)/methylcellulose (MC)-ammonium iodide (NH4I) electrolyte at room temperature. The maximum conducting membrane has a conductivity of 3.21 × 10-3 S/cm. It is shown that the number density, mobility and diffusion coefficient of ions are enhanced by increasing the glycerol. A number of electric and electrochemical properties of the electrolyte-impedance, dielectric properties, transference numbers, potential window, energy density, specific capacitance (Cs) and power density-were determined. From the determined electric and electrochemical properties, it is shown that PVA: MC-NH4I proton conducting polymer electrolyte (PE) is adequate for utilization in energy storage device (ESD). The decrease of charge transfer resistance with increasing plasticizer was observed from Bode plot. The analysis of dielectric properties has indicated that the plasticizer is a novel approach to increase the number of charge carriers. The electron and ion transference numbers were found. From the linear sweep voltammetry (LSV) response, the breakdown voltage of the electrolyte is determined. From Galvanostatic charge-discharge (GCD) measurement, the calculated Cs values are found to drop with increasing the number of cycles. The increment of internal resistance is shown by equivalent series resistance (ESR) plot. The energy and power density were studied over 250 cycles that results to the value of 5.38-3.59 Wh/kg and 757.58-347.22 W/kg, respectively.
Polyoctopamine (POct), an amine-functionalised non-conducting polymer, as the transducer layer in an electrochemical biosensor, is presented. This polymer offers versatile covalent coupling either through thiol linker conjugation, carboxyl or aldehyde functional groups without the requirement of pre- or post-surface activation. The colorectal cancer biomarker carcinoembryonic antigen (CEA) was selected as the target analyte, whilst an antibody and a synthetic binding protein, an Affimer, were used as distinct bioreceptors to demonstrate the versatility of polyoctopamine as a transducer polymer layer for oriented immobilisation of the bioreceptors. The electrodeposited polymer layer was characterised using cyclic voltammetry, electrochemical impedance spectroscopy, and on-sensor chemiluminescent blotting. The performance of optimised POct-based biosensors were tested in spiked human serum. Results showed that the electropolymerisation of octopamine on screen printed gold electrode generates a thin polymer film with low resistance. Close proximity of the immobilised bioreceptors to the transducer layer greatly enhanced the sensitivity detection. The sensitivity of the smaller monomeric bioreceptor (Affimer, 12.6 kDa) to detect CEA was comparable to the dimeric antibody (150 kDa) with limit of detection at 11.76 fM which is significantly lower than the basal clinical levels of 25 pM. However, the Affimer-based sensor had a narrower dynamic range compared to the immunosensor (1-100 fM vs. 1 fM - 100 nM, respectively). All electrochemical measurements were done in less than 5 min with small sample volumes (10 μl). Hence, polyoctopamine features a simple fabrication of impedimetric biosensors using amine-functionalisation technique, provides rapid response time with enhanced sensitivity and label-free detection.
Nucleic acid segregation and compartmentalization were likely essential functions that primitive compartment systems resolved during evolution. Recently, polyester microdroplets generated from dehydration synthesis of various α-hydroxy acids (αHA) were suggested as potential primitive compartments. Some of these droplets can differentially segregate and compartmentalize organic dyes, proteins, and nucleic acids. However, the previously studied polyester microdroplets included limited αHA chemical diversity, which may not reflect the chemical diversity available in the primitive Earth environment. Here, we increased the chemical diversity of polyester microdroplet systems by combinatorially adding an αHA monomer with a basic side chain, 4-amino-2-hydroxybutyric acid (4a2h), which was incorporated with different ratios of other αHAs containing uncharged side chains to form combinatorial heteropolyesters via dehydration synthesis. Incorporation of 4a2h in the polymers resulted in the assembly of some polyester microdroplets able to segregate fluorescent RNA or potentially acquire intrinsic fluorescent character, suggesting that minor modifications of polyester composition can significantly impact the functional properties of primitive compartments. This study suggests one process by which primitive chemical systems can increase diversity of compartment "phenotype" through simple modifications in their chemical composition.
Nuclear radiation shielding capabilities for a glass series 20Bi2O3 - xPbO - (80 - 2x)B2O3 - xGeO2 (where x = 5, 10, 20, and 30 mol%) have been investigated using the Phy-X/PSD software and Monte Carlo N-Particle transport code. The mass attenuation coefficients (μm) of selected samples have been estimated through XCOM dependent Phy-X/PSD program and MCNP-5 code in the photon-energy range 0.015-15 MeV. So obtained μm values are used to calculate other γ-ray shielding parameters such as half-value layer (HVL), mean-free-path (MFP), etc. The calculated μm values were found to be 71.20 cm2/g, 76.03 cm2/g, 84.24 cm2/g, and 90.94 cm2/g for four glasses S1 to S4, respectively. The effective atomic number (Zeff)values vary between 69.87 and 17.11 for S1 or 75.66 and 29.11 for S4 over 0.05-15 MeV of photon-energy. Sample S4, which has a larger PbO/GeO2 of 30 mol% in the bismuth-borate glass, possesses the lowest MFP and HVL, providing higher radiation protection efficiency compared to all other combinations. It shows outperformance while compared the calculated parameters (HVL and MFP) with the commercial shielding glasses, different alloys, polymers, standard shielding concretes, and ceramics. Geometric Progression (G-P) was applied for evaluating the energy absorption and exposure buildup factors at energies 0.015-15 MeV with penetration depths up to 40 mfp. The buildup factors showed dependence on the MFP and photon-energy as well. The studied samples' neutron shielding behavior was also evaluated by calculating the fast neutron removal cross-section (ΣR), i.e. found to be 0.139 cm-1 for S1, 0.133 cm-1 for S2, 0.128 cm-1 for S3, and 0.12 cm-1 for S4. The results reveal a great potential for using a glass composite sample S4 in radiation protection applications.