Cyclodextrin (CD) and its derivatives are receiving attention as a new-generation adsorbent for water pollution treatment due to their external hydrophilic and internal hydrophobic properties. Among types of CD, β-Cyclodextrin (βCD) has been a material of choice with a proven track record for a range of utilities in distinct domains, owing to its unique cage-like structural conformations and inclusion complex-forming ability, especially to mitigate emerging contaminants (ECs). This article outlines βCD composites in developing approaches of their melds and composites for purposes such as membranes for removal of the ECs in aqueous setups have been explored with emphasis on recent trends. Electrospinning has bestowed an entirely different viewpoint on polymeric materials, comprising βCD, in the framework of diverse functions across a multitude of niches. Besides, this article especially discusses βCD polymer composite membrane-based removal of contaminants such as pharmaceutical substances, endocrine disruptors chemicals, and dyes. Finally, in this article, the challenges and future directions of βCD-based adsorbents are discussed, which may shed light on pragmatic commercial applications of βCD polymer composite membranes.
In this work, we reported the synthesis, characterization and adsorption study of two β-cyclodextrin (βCD) cross-linked polymers using aromatic linker 2,4-toluene diisocyanate (2,4-TDI) and aliphatic linker 1,6-hexamethylene diisocyanate (1,6-HDI) to form insoluble βCD-TDI and βCD-HDI. The adsorption of 2,4-dinitrophenol (DNP) on both polymers as an adsorbent was studied in batch adsorption experiments. Both polymers were well characterized using various tools that include Fourier transform infrared spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller analysis and scanning electron microscopy, and the results obtained were compared with the native βCD. The adsorption isotherm of 2,4-DNP onto polymers was studied. It showed that the Freundlich isotherm is a better fit for βCD-TDI, while the Langmuir isotherm is a better fit for βCD-HMDI. The pseudo-second-order kinetic model represented the adsorption process for both of the polymers. The thermodynamic study showed that βCD-TDI polymer was more favourable towards 2,4-DNP when compared with βCD-HDI polymer. Under optimized conditions, both βCD polymers were successfully applied on various environmental water samples for the removal of 2,4-DNP. βCD-TDI polymer showed enhanced sorption capacity and higher removal efficiency (greater than 80%) than βCD-HDI (greater than 70%) towards 2,4-DNP. The mechanism involved was discussed, and the effects of cross-linkers on βCD open up new perspectives for the removal of toxic contaminants from a body of water.
siRNA technology presents a helpful means of gene silencing in mammalian cells. Advancement in the field includes enhanced attentiveness in the characterization of target and off-target effects employing suitable controls and gene expression microarrays. These will permit expansion in the measurement of single and multiple target combinations and also permit comprehensive efforts to understand mammalian cell processes. Another fact is that the delivery of siRNA requires the creation of a nanoparticulate vector with controlled structural geometry and surface modalities inside the targeted cells. On the other hand, dendrimers represent the class of carrier system where massive control over size, shape and physicochemical properties makes this delivery vector exceptional and favorable in genetic transfection applications. The siRNA therapeutics may be incorporated inside the geometry of the density controlled dendrimers with the option of engineering the structure to the specific needs of the genetic material and its indication. The existing reports on the siRNA carrying and deliverance potential of dendrimers clearly suggest the significance of this novel class of polymeric architecture and certainly elevate the futuristic use of this highly branched vector as genetic material delivery system.
The Prins cyclization of styrene (SE) with paraformaldehyde (PFCHO) was conducted with mesoporous ZnAlMCM-41 catalysts for the synthesis of 4-phenyl-1,3-dioxane (4-PDO) using a liquid phase heterogeneous catalytic method. For a comparison study, the Prins cyclization reaction was also conducted over different nanoporous catalysts, e.g. mesoporous solid acid catalysts, AlMCM-41(21) and ZnMCM-41(21), and microporous catalysts, USY, Hβ, HZSM-5, and H-mordenite. The recyclable mesoporous ZnAlMCM-41 catalysts were reused in this reaction to evaluate their catalytic stabilities. Since ZnAlMCM-41(75) has higher catalytic activity than other solid acid catalysts, washed ZnAlMCM-41(75)/W-ZnAlMCM-41(75) was prepared using an efficient chemical treatment method and used with various reaction parameters to find an optimal parameter for the highly selective synthesis of 4-PDO. W-ZnAlMCM-41(75) was also used in the Prins cyclization of olefins with PFCHO and formalin (FN, 37% aqueous solution of formaldehyde (FCHO)) under different reaction conditions to obtain 1,3-dioxanes, which are widely used as solvents or intermediates in organic synthesis. Based on the nature of catalysts used under different reaction conditions, a reasonable plausible reaction mechanism for the Prins cyclization of SE with PFCHO is proposed. Notably, it can be seen from the catalytic results of all catalysts that the W-ZnAlMCM-41(75) catalyst has higher 4-PDO selectivity with exceptional catalytic activity than other microporous and mesoporous catalysts.
In this report, we demonstrate that continuous improvement in XPS instruments and the calibration standards as well
as analysis with standard component-fitting procedures can be used to determine the binding energies of compounds
containing phosphorus and sulfur of different oxidation states with higher confidence. Based on such improved XPS
analyses, the binding energies (BEs) of S2p signals for sulfur of increasing oxidation state are determined to be 166-167.5
eV for S=O in dimethyl sulfoxide, 168.1 eV for S=O2
in polysulfone, 168.4 eV for SO3
in polystyrene sulfonate and 168.8
eV for SO4
in chondroitin sulfate. The BEs of P2p signals show the following values: 132.9 eV for PO3
in triisopropyl
phosphite, 133.3 eV for PO4
in glycerol phosphate, 133.5 eV for PO4
in sodium tripolyphosphate and 134.0 eV for PO4
in sodium hexametaphosphate. These results showed that there are only small increases in the binding energy when
additional oxygen atoms are added to the S-O chemical group. A similar result is obtained when the fourth oxygen or
poly-phosphate environment is added to the phosphorus compound. These BE values are useful to researchers involved
in identifying oxidation states of phosphorus and sulfur atoms commonly observed on modified surfaces and interfaces
found in applications such as biomaterials, super-capacitors and catalysis.
Ultrafiltration grade polysulfone-based mixed matrix membranes (MMMs) incorporated with two-dimensional boron nitride nanosheet (BNNS) was prepared via phase inversion method. The amount of BN incorporated was varied and the influence on membrane morphology, contact angle, surface charge, as well as water permeability and humic acid rejection were investigated. Results revealed that the addition of BN to the membrane matrix resulted in profound increase in water permeability (almost tripled to that of neat PSf) and humic acid rejection due to the increase in pore size and surface negative charge. Beyond the morphological changes imparted by the inclusion of BNNS, we postulated that the presence of BNNS within the membrane matrix also contribute to the enhancement in flux and rejection based on surface-slip and selective interlayer transport. Despite the favourable augmentation of water transport and filtration performance, the MMMs suffered with fouling problem due to the entrapment of foulant within the enlarged pores and the membrane valleys. Its inherent adsorptive character could be a disadvantage when utilized as membrane filler.
Catalytic cracking of high-density polyethylene (HDPE) over fluid catalytic cracking (FCC) catalysts (1:6 ratio) was carried out using a laboratory fluidized bed reactor operating at 450 degrees C. Two fresh and two steam deactivated commercial FCC catalysts with different levels of rare earth oxide (REO) were compared as well as two used FCC catalysts (E-Cats) with different levels of metal poisoning. Also, inert microspheres (MS3) were used as a fluidizing agent to compare with thermal cracking process at BP pilot plant at Grangemouth, Scotland, which used sand as its fluidizing agent. The results of HDPE degradation in terms of yield of volatile hydrocarbon product are fresh FCC catalysts>steamed FCC catalysts approximately used FCC catalysts. The thermal cracking process using MS3 showed that at 450 degrees C, the product distribution gave 46 wt% wax, 14% hydrocarbon gases, 8% gasoline, 0.1% coke and 32% nonvolatile product. In general, the product yields from HDPE cracking showed that the level of metal contamination (nickel and vanadium) did not affect the product stream generated from polymer cracking. This study gives promising results as an alternative technique for the cracking and recycling of polymer waste.
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.
Many studies have been done using recycled waste materials to minimise environmental problems. It is a great opportunity to explore mechanical recycling and the use of recycled and virgin blend as a material to produce new products with minimum defects. In this study, appropriate processing parameters were considered to mould the front panel housing part using R0% (virgin), R30% (30% virgin: 70% recycled), R40% (40% virgin: 60% recycled) and R50% (50% virgin: 50% recycled) of Polycarbonate (PC). The manufacturing ability and quality during preliminary stage can be predicted through simulation analysis using Autodesk Moldflow Insight 2012 software. The recommended processing parameters and values of warpage in x and y directions can also be obtained using this software. No value of warpage was obtained from simulation studies for x direction on the front panel housing. Therefore, this study only focused on reducing the warpage in the y direction. Response Surface Methodology (RSM) and Genetic Algorithm (GA) optimisation methods were used to find the optimal processing parameters. As the results, the optimal ratio of recycled PC material was found to be R30%, followed by R40% and R50% materials using RSM and GA methods as compared to the average value of warpage on the moulded part using R0%. The most influential processing parameter that contributed to warpage defect was packing pressure for all materials used in this study.
Epoxidised Natural Rubber (ENR) is now a commercially available polymer produced by chemical modification of natural rubber. Currently, three types of ENR are commercially available, and these are ENR 10, ENR 25, and ENR 50 with 10%, 25%, and 50% mol epoxidation, respectively. Studies on prevulcanisation of ENR 50 and postvulcanisation of the latex films were carried out. The objective of this study was to develop ENR 50 that could be dipped easily in coagulant dipping solution to produce dipped products. Several attempts were made by compounding prevulcanised ENR 50 at various sulphur levels ranging from 0.5 to 3.0 pphr. Using suitable coagulant dipping systems, ENR 50 film could be formed despite the high contents of non-ionic surfactant. It was found that the tensile strength of prevulcanised ENR 50 film decreased with the increase in the sulphur level. The results show that as level of sulphur increased, M300 also increased to an optimum value of 1.5 pphr of sulphur. For the postvulcanised ENR 50 film, however, the tensile strength increased and then decreased with the increasing sulphur level. Meanwhile M300 increased with the increasing postvulcanization time and sulphur level. The postvulcanisation of ENR 50 film seems to be a more effective way of increasing tensile properties than by prevulcanisation of ENR 50.
The study presents the synthesis of polypyrrole-coated palladium platinum/nitrogen-doped reduced graphene oxide nanocomposites (PdPt-PPy/N-rGO NC) via direct the reduction of Pd(II) and Pt(II) in the presence of pyrrole monomer, N-rGO and L-cysteine as the reducing agent. X-ray diffraction confirmed the presence of metallic Pd and Pt from the reduction of Pd and Pt cations. Transmission electron microscopy images revealed the presence of Pd, Pt and PPy deposition on N-rGO. Impedance spectroscopy results gave a decreased charge transfer resistance due to the presence of N-rGO. The nanocomposites were synthesized with different Pd/Pt ratios (2:1, 1:1 and 1:2). A glassy carbon electrode (GCE) modified with the nanocomposite showed enhanced electrochemical sensing capability for formaldehyde in 0.1 M sulfuric acid solution. Cyclic voltammetry showed an increase in the formaldehyde oxidation peak current at the GCE modified with Pd2Pt1 PPy N-rGO. At a typical potential of 0.45 V (vs. SCE), the sensitivity in the linear segment was 345.8 μA.mM -1. cm-2. The voltammetric response was linear between 0.01 and 0.9 mM formaldehyde concentration range, with a 27 µM detection limit (at S/N = 3). Graphical abstract Schematic presentation of formaldehyde detection by Pd2Pt1-PPy/nitrogen-doped reduced Graphene Oxide Nanocomposite (Pd2Pt1-PPy /N-Gr NC). The decrease of charge transfer resistance and the agglomeration of deposited metals in the presence of N-rGO enhance the current response of the electrochemical sensor.
A flexible solid polymer electrolyte (SPE) system based on poly(ε-caprolactone) (PCL), a FDA approved non-toxic and biodegradable material in the effort to lower environmental impact was prepared. Ammonium thiocyanate (NH4SCN) and ethylene carbonate (EC) were incorporated as the source of charge carriers and plasticizing agent, respectively. When 50wt.% of ethylene carbonate (EC) was added to PCL-NH4SCN system, the conductivity increased by two orders from of 3.94×10(-7)Scm(-1) to 3.82×10(-5)Scm(-1). Molecular vibrational analysis via infrared spectroscopy had been carried out to study the interaction between EC, PCL and NH4SCN. The relative percentage of free ions, ion pairs and ion aggregates was calculated quantitatively by deconvoluting the SCN(-) stretching mode (2030-2090cm(-1)). This study provides fundamental insight on how EC influences the free ion dissociation rate and ion mobility. The findings are also in good agreement to conductivity, differential scanning calorimetry and X-ray diffraction results. High dielectric constant value (89.8) of EC had made it an effective ion dissociation agent to dissociate both ion pairs and ion aggregates, thus contributing to higher number density of free ions. The incorporation of EC had made the polymer chains more flexible in expanding amorphous domain. This will facilitate the coupling synergy between ionic motion and polymer segmental motion. Possible new pathway through EC-NH4(+) complex sites for ions to migrate with shorter distance has been anticipated. This implies an easier ion migration route from one complex site to another.
The valorization of lignin to replace phenol is significant in the production of phenolic resins. However, a great challenge is to produce lignin-based resin (LR) with a suitable viscosity and high substitution rate of lignin to phenol. In this study, LRs were produced using hardwood technical lignin derived from the pulping industry. Structural analysis of the LRs indicated that the unsubstituted para and ortho carbon atoms of the aromatic ring influenced the curing temperature and activation energy of the resins. The curing kinetics and thermal decomposition study implied that urea and methylene groups in cured LRs were significant factors that affected the thermal stability negatively. The prepared LRs showed desirable features if used as adhesives to make plywood. This is the first approach in which a substitution rate of up to 65 % is achieved for low-reactive-site hardwood lignin, which provides a solution to the challenge of the simultaneous realization of the high addition of lignin and the adaptive viscosity of resins.
Thermally assisted hydrolysis and methylation-gas chromatography (THM-GC) in the presence of an organic alkali was validated for the compositional analysis of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(3HB-co-3HHx)] accumulated in whole bacterial cells. Recombinant Cupriavidus necator Re2058/pCB113 was grown in a batch fermentation with different concentration of palm oil and fructose in order to control the molar fraction of 3HHx in P(3HB-co-3HHx) produced in the cells. Trace amounts (30μg) of freeze-dried cells were directly subjected to THM-GC in the presence of tetramethylammonium hydroxide (TMAH) at 400°C. The obtained chromatograms clearly showed nine characteristic peaks, attributed to the THM products from 3HB and 3HHx units in the polymer chains, without any appreciable interference by the bacterial matrix components. Based on these peak intensities, the copolymer compositions were determined rapidly without using any cumbersome and lengthy sample pretreatment as in conventional GC method. Moreover, the compositions thus obtained were strongly correlated with those by NMR and conventional GC involving solvent extraction.
Vaginal infection is widespread and > 80% of females encounter such infections during their lives. Topical treatment and prevention of vaginal infection allows direct therapeutic action, reduced drug doses and adverse effects, convenient administration and improved compliance. The advent of nanotechnology results in the use of nanoparticulate vehicle to control drug release, to enhance dosage form mucoadhesive properties and vaginal retention, and to promote mucus and epithelium permeation for both extracellular and intracellular drug delivery.
The application of pultruded glass fiber-reinforced polymer composites (PGFRPCs) as a replacement for conventional wooden cross-arms in transmission towers is relatively new. Although numerous studies have conducted creep tests on coupon-scale PGFRPC cross-arms, none had performed creep analyses on full-scale PGFRPC cross-arms under actual working load conditions. Thus, this work proposed to study the influence of an additional bracing system on the creep responses of PGFRPC cross-arms in a 132 kV transmission tower. The creep behaviors and responses of the main members in current and braced PGFRPC cross-arm designs were compared and evaluated in a transmission tower under actual working conditions. These PGFRPC cross-arms were subjected to actual working loads mimicking the actual weight of electrical cables and insulators for a duration of 1000 h. The cross-arms were installed on a custom test rig in an open area to simulate the actual environment of tropical climate conditions. Further creep analysis was performed by using Findley and Burger models on the basis of experimental data to link instantaneous and extended (transient and viscoelastic) creep strains. The addition of braced arms to the structure reduced the total strain of a cross-arm's main member beams and improved elastic and viscous moduli. The addition of bracing arms improved the structural integrity and stiffness of the cross-arm structure. The findings of this study suggested that the use of a bracing system in cross-arm structures could prolong the structures' service life and subsequently reduce maintenance effort and cost for long-term applications in transmission towers.
Binary blends of palm olein (PO) with sunflower oil (SFO), canola oil (CNO), and cottonseed oil (CSO) were formulated to assess their stability under continuous frying conditions. The results were then compared with those obtained in PO. The oil blends studied were: (1) 60:40 for PO + SFO; (2) 70:30 for PO + CNO; and (3) 50:50 for PO + CSO. The PO and its blends were used to fry potato chips at 180°C for a total of 56 h of operation. The evolution of analytical parameters such as tocols, induction period, color, p-anisidine value, free fatty acid, smoke point, polar compounds, and polymer compounds were evaluated over the frying time. Blending PO with unsaturated oils was generally proved to keep most qualitative parameters comparable to those demonstrated in PO. Indeed, none of the oils surpassed the legislative limits for used frying. Overall, it was noted that oil containing PO and SFO showed higher resistance toward oxidative and hydrolytic behaviors as compared to the other oil blends.
A novel layer-by-layer (LBL) based electrode material for supercapacitor consists of polypyrrole/graphene oxide and polypyrrole/manganese oxide (PPy/GO|PPy/MnO2) has prepared by electrochemical deposition. The formation of LBL assembled nanocomposite is confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy and X-ray diffraction. The field emission scanning electron microscopy images clearly showed that PPy/MnO2 was uniformly coated on PPy/GO. The PPy/GO|PPy/MnO2 symmetrical supercapacitor has revealed outstanding supercapacitive performance with a high specific capacitance of 786.6 F/g, an exceptionally high specific energy of 52.3 Wh/kg at a specific power of 1392.9 W/kg and preserve a good cycling stability over 1000 cycles. It is certain that PPy/GO|PPy/MnO2 has an extraordinary perspective as an electrode for future supercapacitor developments. This finding contributes to a significant impact on the evolution of electrochemical supercapacitor.
Pseudomonas putida Bet001 and Delftia tsuruhatensis Bet002, isolated from palm oil mill effluent, accumulated poly(3-hydroxyalkanoates) (PHAs) when grown on aliphatic fatty acids, sugars, and glycerol. The substrates were supplied at 20:1 C/N mole ratio. Among C-even n-alkanoic acids, myristic acid gave the highest PHA content 26 and 28 wt% in P. putida and D. tsuruhatensis, respectively. Among C-odd n-alkanoic acids, undecanoic gave the highest PHA content at 40 wt% in P. putida and 46 wt% in D. tsuruhatensis on pentadecanoic acid. Sugar and glycerol gave <10 wt% of PHA content for both bacteria. Interestingly, D. tsuruhatensis accumulated both short- and medium-chain length PHA when supplied with n-alkanoic acids ranging from octanoic to lauric, sucrose, and glycerol with 3-hydroxybutyrate as the major monomer unit. In P. putida, the major hydroxyalkanoates unit was 3-hydroxyoctanoate and 3-hydroxydecanoate when grown on C-even acids. Conversely, 3-hydroxyheptanoate, 3-hydrxoynonanoate, and 3-hydroxyundecanoate were accumulated with C-odd acids. Weight-averaged molecular weight (Mw ) was in the range of 53-81 kDa and 107-415 kDa for P. putida and D. tsuruhatensis, respectively. Calorimetric analyses indicated that both bacteria synthesized semicrystalline polymer with good thermal stability with degradation temperature (Td ) ranging from 178 to 282 °C.
Stent designs with ultrathin struts may further increase the procedural success of challenging lesion subsets. The objective of this study was to assess the safety and efficacy of ultrathin strut, polymer-free sirolimus eluting stent (PF-SES) implantations in a large scale, unselected patient population.Adult patients underwent percutaneous coronary interventions (PCI) with a thin-strut PF-SES. Data from two all-comers observational studies having the same protocol (ClinicalTrials.gov Identifiers: NCT02629575 and NCT02905214) were pooled. The accumulated target lesion revascularization (TLR) rate at 9-12 months was the primary endpoint. All dual antiplatelet therapy strategies according to the applicable guidelines were permissible.In total, 7243 patients were prospectively enrolled for PCI with PF-SES in stable coronary artery disease or acute coronary syndrome (ACS). Major risk factors in the overall cohort were diabetes (37.3%), ST elevation myocardial infarction (18.1%) and non-ST myocardial infarction (24.6%). The follow-up rate was 88.6% in the overall population. The TLR rate in the overall cohort was 2.2% whereas definite/probable stent thrombosis (ST) occurred in 0.7%. In patients with in-stent restenosis lesions, the major adverse cardiac events rate was 6.4% whereas the corresponding rate for isolated left main coronary artery (LMCA) disease was highest with 6.7% followed by patients with culprit lesions in vein bypasses (VB, 7.1%). The mortality rate in patients treated in VB lesions was highest with 5.4%, followed by the isolated LMCA subgroup (3.4%) and ACS (2.6%).PCI with PF-SES in an unselected patient population, is associated with low clinical event and ST rates. Furthermore, PF-SES angioplasty in niche indications demonstrated favorable safety and efficacy outcomes with high procedural success rates.