Sulfonated copoly(norbornene)s bearing sultone pendant groups and application as proton exchange membranes candidates

Novel copolynorbornenes bearing pendant sultone groups (designated as P(BN/SulNBOH) and P(BN/SulNBOMe)) have been successfully synthesized via copolymerization of functionalized norbornenes bearing sultones (designated as SulNBOH and SulNBOMe) with 2-butoxymethylene norbornene (BN). The catalyst system showed high catalyst activity (10⁴ g_polymer/mol_Ni·h) and the obtained copolymers have high molecular weight and a narrow molecular weight distribution. Furthermore, the achieved copolymers P(BN/SulNBOH) and P(BN/SulNBOMe) were converted into sulfonated copolymers sP(BN/NBOH) and sP(BN/NBOMe). Both sP(BN/NBOH) and sP(BN/NBOMe) membranes displayed low water uptake, high thermal properties, good mechanical properties, and better proton exchange membranes properties. The proton conductivities measured in the hydrated state at 80?°C ranged from 10^?5 to 7.19?×?10^?3?S·cm^?1.

Optical Resolution Membranes from Polysulfones Bearing Alanine Derivatives as Chiral Selectors

Polysulfones bearing a derivative of alanyl residue employed as chiral selectors were prepared by polymer modification. The specific rotation ([α]_D) of the polysulfone with a derivative of D ‐alanyl residue (PSf‐Ac‐D ‐Ala) was determined to be 2.87 deg · cm² · g^?1 (c = 1.00 g · dL^?1 in DMF) and that with L ‐alanyl residue (PSf‐Ac‐L ‐Ala) to be ‐2.36 deg · cm² · g^?1 (c = 1.00 g · dL^?1 in DMF). The membrane from PSf‐Ac‐D ‐Ala preferentially adsorbed the D ‐isomer of Glu from racemic mixture of Glu and vice versa. Chiral separation ability was studied by applying a potential difference as a driving force for membrane transport. The permselectivity of PSf‐Ac‐D ‐Ala toward D ‐Glu (α_D/L) was determined to be 1.40, and that of PSf‐Ac‐L ‐Ala toward the L ‐isomer (α_L/D) to be 1.48 at 18.0 V, reflecting their adsorption selectivity.

     

Studies concerning the growth of cadmium dendrites. I. Morphology in alkaline media

The morphology of cadmium dendrites formed during potentiostatic electrodeposition onto nickel and cadmium substrates from cadmate solutions in alkaline supporting electrolyte has been investigated. The morphology is potential dependent for deposition under convective diffusion conditions to a nickel substrate. For 1.05×10^?4 mol dm^?3 Cd(OH) ₄ ^2? /30% KOH solutions, 2D- fern dendrites are observed at an overpotential of ?150mV, needle dendrites at ?200 mV, and large ‘filled-in’ fern dendrites at ?300 mV. Similar results were found at the higher concentration, 2.4×10^?4 mol dm^?3 Cd(OH) ₄ ^2? /50% KOH, but the time taken to grow an equivalent morphology and length were reduced in proportion. Crystalline aggregate dendrites were observed on a cadmium substrate in 1.05×10^?4 mol dm^?3 Cd(OH) ₄ ^2? /30% KOH, becoming more crystalline and well defined with increase in overpotential. A significant induction time of the order 8 h was observed for all deposition onto stationary nickel and cadmium wires. Under the well-defined diffusion conditions at a rotating nickel disc electrode only one morphology, namely small ferns, was observed over a wide range of overpotentials. The current-time behaviour is presented, and the current is shown to have a (time)² dependence, indicative of progressive nucleation of dendrites. The induction time, indicated approximately by the current minima, had decreased significantly.     

The effect of two β-alanine dosing strategies on 30-minute rowing performance: a randomized,controlled trial

Background

β-alanine (βA) supplementation has been shown to increase intramuscular carnosine content and subsequent high-intensity performance in events lasting <?4?minutes (min), which may be dependent on total, as opposed to daily, dose. The ergogenic effect of βA has also been demonstrated for 2000-m rowing performance prompting interest in whether βA may be beneficial for sustained aerobic exercise. This study therefore investigated the effect of two βA dosing strategies on 30-min rowing and subsequent sprint performance.

Methods

Following University Ethics approval, twenty-seven healthy, male rowers (age: 24?±?2?years; body-height: 1.81?±?0.02?m; body-mass: 82.3?±?2.5?kg; body-fat: 14.2?±?1.0%) were randomised in a double-blind manner to 4?weeks of: i) βA (2.4?g·d^??1, βA1); ii) matched total βA (4.8?g on alternate days, βA2); or iii) cornflour placebo (2.4?g·d^??1, PL). Participants completed a laboratory 30-min rowing time-trial, followed by 3x30-seconds (s) maximal sprint efforts at days 0, 14 and 28 (T1-T3). Total distance (m), average power (W), relative average power (W·kg^??1), cardio-respiratory measures and perceived exertion were assessed for each 10-min split. Blood lactate ([La-]_b mmol·L^??1) was monitored pre-post time-trial and following maximal sprint efforts. A 3-way repeated measures ANOVA was employed for main analyses, with Bonferonni post-hoc assessment (P?≤?0.05).

Results

Total 30-min time-trial distance significantly increased from T1-T3 within βA1 only (7397?±?195?m to 7580?±?171?m, P?=?0.002, ?p²?=?0.196), including absolute average power (194.8?±?18.3?W to 204.2?±?15.5?W, P?=?0.04, ?p²?=?0.115) and relative average power output (2.28?±?0.15?W·kg^??1 to 2.41?±?0.12?W·kg^??1, P?=?0.031, ?p²?=?0.122). These findings were potentially explained by within-group significance for the same variables for the first 10?min split (P?≤?0.01), and for distance covered (P?=?0.01) in the second 10-min split. However, no condition x time interactions were observed. No significant effects were found for sprint variables (P?>?0.05) with comparable values at T3 for mean distance (βA1: 163.9?±?3.8?m; βA2: 161.2?±?3.5?m; PL: 162.7?±?3.6?m), average power (βA1: 352.7?±?14.5?W; βA2: 342.2?±?13.5?W; PL: 348.2?±?13.9?W) and lactate (βA1: 10.0?±?0.9?mmol·L^??1; βA2: 9.2?±?1.1?mmol·L^??1; PL: 8.7?±?0.9?mmol·L^??1).

Conclusions

Whilst daily βA may confer individual benefits, these results demonstrate limited impact of βA (irrespective of dosing strategy) on 30-min rowing or subsequent sprint performance. Further investigation of βA dosage >?2.4?g·d^??1 and/or chronic intervention periods (>?4–8?weeks) may be warranted based on within-group observations.

     

Thermogravimetry and decomposition kinetics of British Kimmeridge Clay oil shale

The characteristics of volatile matter evolution and the kinetics of thermal decomposition of British Kimmeridge Clay oil shale have been examined by thermogravimetry. TG has provided an alternative to the Fischer assay for shale grade estimation. The following relation has been derived relating TG % volatiles yield to the shale gravimetric oil yield: oil yield (g kg^?1) = (TG volatiles, % × 5.82) ? 28.1 ± 14.5 g kg^?1. A relationship has also been established for volumetric oil yield estimation: oil yield (cm³ kg^?1) = (TG volatiles, % × 4.97) – 5.43. TG is considered to give a satisfactory estimation of shale oil yield except in certain circumstances. It is found to be less reliable for low yield shales producing <≈40 cm³ kg^?1 of oil (≈10 gal ton^?1) where oil content of the TG volatiles is low: volumetric yield estimation accuracy is affected by variations in shale oil specific gravity. First order rate constants, k = 4.82 × 10^?5s^?1 (346.3 cm³ kg^?1shale) and k = 6.78 × 10^?5s^?1 (44.6cm³ kg^?1shale) have been obtained for the devolatilization of two Kimmeridge oil shales at 280 °C using isothermal TG. Using published pre-exponential frequency factors, an activation energy of ≈57.9 kJ mol^?1 is calculated for the decomposition. Preliminary kinetic studies using temperature programmed TG suggest at least a two stage process in the thermal decomposition, with two maxima in the volatiles evolution rate at ≈450 and 325 °C being obtained for some samples. Use of published pre-exponential frequency factors gives activation energies of ≈212 and 43 kJ mol^?1 for these two stages in the decomposition.     

Kinetics and dissolution of intratracheally administered nickel oxide nanomaterials in rats

Background

The toxicokinetics of nanomaterials are an important factor in toxicity, which may be affected by slow clearance and/or distribution in the body.

Methods

Four types of nickel oxide (NiO) nanoparticles were single-administered intratracheally to male F344 rats at three doses of 0.67–6.0 mg/kg body weight. The rats were sacrificed under anesthesia and the lung, thoracic lymph nodes, bronchoalveolar lavage fluid, liver, and other organs were sampled for Ni burden measurement 3, 28, and 91 days post-administration; Ni excretion was measured 6 and 24 h after administration. Solubility of NiO nanoparticles was determined using artificial lysosomal fluid, artificial interstitial fluid, hydrogen peroxide solution, pure water, and saline. In addition, macrophage migration to trachea and phagosome-lysosome-fusion rate constants were estimated using pulmonary clearance and dissolution rate constants.

Results

The wire-like NiO nanoparticles were 100% dissolved by 24 h when mixed with artificial lysosomal fluid (dissolution rate coefficient: 0.18/h); spherical NiO nanoparticles were 12% and 35% dissolved after 216 h when mixed with artificial lysosomal fluid (1.4?×?10^?3 and 4.9?×?10^?3/h). The largest irregular-shaped NiO nanoparticles hardly dissolved in any solution, including artificial lysosomal fluid (7.8?×?10^?5/h). Pulmonary clearance rate constants, estimated using a one-compartment model, were much higher for the NiO nanoparticles with a wire-shape (0.069–0.078/day) than for the spherical and irregular-shaped NiO nanoparticles (0–0.012/day). Pulmonary clearance rate constants of the largest irregular-shaped NiO nanoparticles showed an inverse correlation with dose. Translocation of NiO from the lungs to the thoracic lymph nodes increased in a time- and dose-dependent manner for three spherical and irregular-shaped NiO nanoparticles, but not for the wire-like NiO nanoparticles. Thirty-five percent of the wire-like NiO nanoparticles were excreted in the first 24 h after administration; excretion was 0.33–3.6% in that time frame for the spherical and irregular-shaped NiO nanoparticles.

Conclusion

These findings suggest that nanomaterial solubility differences can result in variations in their pulmonary clearance. Nanoparticles with moderate lysosomal solubility may induce persistent pulmonary inflammation.

     

Level of dietary protein intake affects glucose turnover in endurance-trained men

Background

To examine the effects of higher-protein diets on endogenous glucose metabolism in healthy, physically active adults, glucose turnover was assessed in five endurance-trained men (age 21.3 ± 0.3 y, VO_2peak 70.6 ± 0.1 mL kg^-1 min^-1) who consumed dietary protein intakes spanning the current dietary reference intakes.

Findings

Using a randomized, crossover design, volunteers consumed 4 week eucaloric diets providing either a low (0.8 g kg^-1 d^-1; LP), moderate (1.8 g kg^-1 d^-1; MP), or high (3.6 g kg^-1 d^-1; HP) level of dietary protein. Glucose turnover (Ra, glucose rate of appearance; and Rd glucose rate of disappearance) was assessed under fasted, resting conditions using primed, constant infusions of [6,6-²H₂] glucose. Glucose Ra and Rd (mg kg^-1 min^-1) were higher for MP (2.8 ± 0.1 and 2.7 ± 0.1) compared to HP (2.4 ± 0.1 and 2.3 ± 0.2, P < 0.05) and LP (2.3 ± 0.1 and 2.2 ± 0.1, P < 0.01) diets. Glucose levels (mmol/L) were not different (P > 0.05) between LP (4.6 ± 0.1), MP (4.8 ± 0.1), and HP (4.7 ± 0.1) diets.

Conclusions

Level of protein consumption influenced resting glucose turnover in endurance athletes in a state of energy balance with a higher rate of turnover noted for a protein intake of 1.8 g kg^-1 d^-1. Findings suggest that consumption of protein in excess of the recommended dietary allowance but within the current acceptable macronutrient distribution range may contribute to the regulation of blood glucose when carbohydrate intake is reduced by serving as a gluconeogenic substrate in endurance-trained men.     

Dietary intake and stress fractures among elite male combat recruits

Background

We examined the effect of four weeks of ??-alanine supplementation on isometric endurance of the knee extensors at 45% maximal voluntary isometric contraction (MVIC).

Methods

Thirteen males (age 23?±?6 y; height 1.80?±?0.05?m; body mass 81.0?±?10.5?kg), matched for pre-supplementation isometric endurance, were allocated to either a placebo (n?=?6) or ??-alanine (n?=?7; 6.4?g·d^-1 over 4?weeks) supplementation group. Participants completed an isometric knee extension test (IKET) to fatigue, at an intensity of 45% MVIC, before and after supplementation. In addition, two habituation tests were completed in the week prior to the pre-supplementation test and a further practice test was completed in the week prior to the post-supplementation test. MVIC force, IKET hold-time, and impulse generated were recorded.

Results

IKET hold-time increased by 9.7?±?9.4?s (13.2%) and impulse by 3.7?±?1.3 kN·s^-1 (13.9%) following ??-alanine supplementation. These changes were significantly greater than those in the placebo group (IKET: t ₍₁₁₎?=?2.9, p ??0.05; impulse: t ₍₁₁₎?=?3.1, p????0.05). There were no significant changes in MVIC force in either group.

Conclusion

Four weeks of ??-alanine supplementation at 6.4?g·d^-1 improved endurance capacity of the knee extensors at 45% MVIC, which most likely results from improved pH regulation within the muscle cell as a result of elevated muscle carnosine levels.     

The specific surfaces of peat and wood

The specific surface areas of various particle size ranges of wood and peat were determined. The methods employed are mercury porosimetry, nitrogen adsorption, and solution isotherms. The results indicate that dye solution isotherms offer an accurate means of surface area measurement, however, the values obtained are dependent on (a) the chemical nature of the solute and adsorbent and (b) the molecular dimensions of the solute. Nitrogen isotherms indicate specific surfaces of (21 × 10³)?(27 × 10³) m² kg^?1 for wood depending on the particle size, while an area of 26.5 × 10³ m² kg^?1 was obtained for peat independent of particle size. Acid dye isotherms yield specific surfaces considerably lower than nitrogen isotherm values; for wood (7.3 × 10³)?(9.6 × 10³) m² kg^?1 and for peat, (5.2 × 10³)?(11.8 × 10³) m² kg^?1. Basic dye studies, using wood, indicate surface areas similar in magnitude to those obtained from nitrogen isotherms. For peat, however, very large apparent surface areas are obtained (～100 × 10³ m² kg^?1) and are attributed to chemical interaction between dye molecules and adsorbent and stacking of dye molecules.     

Aryl Halide Radical Clocks as Probes of Stannylene/Aryl Halide C–H Activation Rates

Using the radical cyclization induced by the reaction of (1) with 1-(but-3-en-1-yloxy)-2-iodobenzene, we have determined the rate of allylic and propargylic C–H activation to be 1.1 ± 0.2 × 10⁸ M^?1 s^?1. The rate of oxidative addition of aryl halide with 1 was estimated to be 10⁷–10⁸ M^?1 s^?1. The radical cyclization involving 1 and 1-(allyloxy)-2-iodobenzene proceeds quantitatively, indicating that the rate of cyclization (9.6 × 10⁹ s^?1) is faster than the rate of hydrocarbon/alkene/alkyne C–H abstraction.     

Mass Transfer Model of Chromium Reduction in a Fluidized Bed Electrochemical Reactor

Abstract

A batch recycling fluidized bed electrochemical reactor system was used to recover Cr(VI) from a very dilute solution containing 2.5 g Cr/L at pH 2. It was found that the electrowinning rate is controlled by mass transfer and that the reduction process of Cr(VI) is interrupted by the formation of Cr(H₂O)₃ ³⁺. The Cr₂O₇ ^2? and Cr(H₂O)₆ ³ concentration-time relationship can be predicted by a plug flow model. A finite difference method and a complex optimization technique were used to estimate the mass transfer coefficient. At Re_p between 10 and 30, the Cr₂O₇ ^2? and Cr(H₂O)₆ ³⁺ mass transfer coefficients lie between 1.52-3.20 × 10^?6 and 1.17-2.50 × 10^?6 cm/s, respectively, and increase with the Reynolds number based on the particulate cathode.     

Synthesis and characterization of novel polyhydrazides containing pendant amide-imide-pyridine moiety

Eight novel polyhydrazides (PH _a4?Ch3 ) were prepared from the reaction of two novel diacids, 5-(2-(6-methyl pyridine-2-yl)-1,3-dioxo isoindoline-6-carboxamido) isophthalic acid (3) and 5-(2-(4-methyl pyridine-2-yl)-1,3-dioxo isoindoline-6-carboxamido) isophthalic acid (4), with four dihydrazides by interfacial polycondensation. These polymers have moderate inherent viscosities (0.12?C0.17?dL/g) and are readily soluble in polar aprotic solvents. They start to decompose (T _10%) above 187?°C and display glass transition temperatures in the range of 130.3?C156.3?°C. All polymers could be thermally converted into the corresponding polyoxadiazole approximately in the region of 250?°C, as evidenced by the DSC thermograms. All of the above polymers were fully characterized by FT-IR and ¹HNMR spectroscopy, TGA, DSC, and inherent viscosity measurement.     

The influence of a CYP1A2 polymorphism on the ergogenic effects of caffeine

Background

Although caffeine supplementation improves performance, the ergogenic effect is variable. The cause(s) of this variability are unknown. A (C/A) single nucleotide polymorphism at intron 1 of the cytochrome P450 (CYP1A2) gene influences caffeine metabolism and clinical outcomes from caffeine ingestion. The purpose of this study was to determine if this polymorphism influences the ergogenic effect of caffeine supplementation.

Methods

Thirty-five trained male cyclists (age = 25.0 ± 7.3 yrs, height = 178.2 ± 8.8 cm, weight = 74.3 ± 8.8 kg, VO₂max = 59.35 ± 9.72 ml·kg^-1·min^-1) participated in two computer-simulated 40-kilometer time trials on a cycle ergometer. Each test was performed one hour following ingestion of 6 mg·kg^-1 of anhydrous caffeine or a placebo administered in double-blind fashion. DNA was obtained from whole blood samples and genotyped using restriction fragment length polymorphism-polymerase chain reaction. Participants were classified as AA homozygotes (N = 16) or C allele carriers (N = 19). The effects of treatment (caffeine, placebo) and the treatment × genotype interaction were assessed using Repeated Measures Analysis of Variance.

Results

Caffeine supplementation reduced 40 kilometer time by a greater (p < 0.05) magnitude in AA homozygotes (4.9%; caffeine = 72.4 ± 4.2 min, placebo = 76.1 ± 5.8 min) as compared to C allele carriers (1.8%; caffeine = 70.9 ± 4.3 min, placebo = 72.2 ± 4.2 min).

Conclusions

Results suggest that individuals homozygous for the A allele of this polymorphism may have a larger ergogenic effect following caffeine ingestion.     

No effect of creatine supplementation on oxidative stress and cardiovascular parameters in spontaneously hypertensive rats

Background

Exacerbated oxidative stress is thought to be a mediator of arterial hypertension. It has been postulated that creatine (Cr) could act as an antioxidant agent preventing increased oxidative stress. The aim of this study was to investigate the effects of nine weeks of Cr or placebo supplementation on oxidative stress and cardiovascular parameters in spontaneously hypertensive rats (SHR).

Findings

Lipid hydroperoxidation, one important oxidative stress marker, remained unchanged in the coronary artery (Cr: 12.6 ± 1.5 vs. Pl: 12.2 ± 1.7 nmol·mg^-1; p = 0.87), heart (Cr: 11.5 ± 1.8 vs. Pl: 14.6 ± 1.1 nmol·mg^-1; p = 0.15), plasma (Cr: 67.7 ± 9.1 vs. Pl: 56.0 ± 3.2 nmol·mg^-1; p = 0.19), plantaris (Cr: 10.0 ± 0.8 vs. Pl: 9.0 ± 0.8 nmol·mg^-1; p = 0.40), and EDL muscle (Cr: 14.9 ± 1.4 vs. Pl: 17.2 ± 1.5 nmol·mg^-1; p = 0.30). Additionally, Cr supplementation affected neither arterial blood pressure nor heart structure in SHR (p > 0.05).

Conclusions

Using a well-known experimental model of systemic arterial hypertension, this study did not confirm the possible therapeutic effects of Cr supplementation on oxidative stress and cardiovascular dysfunction associated with arterial hypertension.     

Electrochemical,spectroscopic and molecular docking studies of 4-methyl-5-((phenylimino)methyl)-3H- and 5-(4-fluorophenyl)-3H-1,2-dithiole-3-thione interacting with DNA

Cyclic voltammetry (CV) and UV–Visible spectroscopy (UV–Vis) techniques were used to calculate binding parameters of 4-methyl-5-((phenylimino)methyl)-3H-1,2-dithiole-3-thione (MPDT) and 5-(4-fluorophenyl)-3H-1,2-dithiole-3-thione (FPDT) with DNA. The results obtained from both techniques were confirmed by computational molecular docking using AutoDock molecular docking software. The anodic peak potential shift in CV indicated an intercalative mode of binding. The binding constants (M^?1) of the adducts MPDT-DNA and FPDT-DNA obtained from voltammetric measurements were found to be 8.0?×?10⁴ and 2.4?×?10⁴, respectively, with binding free energy being ?27.99 and ?25.01?KJ?mol^?1, respectively. These results are in good agreement with those obtained from UV–Visible spectroscopic studies. The diffusion coefficients of MPDT and FPDT (2.06?×?10^?10 and 2.42?×?10^?9, respectively) were found to be higher than those of DNA-bound compounds (1.27?×?10^?10 and 1.65?×?10^?9?cm²/s, respectively). The binding free energy of MPDT and FPDT to DNA was also calculated by molecular docking study. The docking study gave excellent approximation with experimental results, shedding light on the sites of binding.     

Microstructure characterization of one high-speed extrusion coating polyethylene resin fractionated by solvent gradient fractionation

One low density polyethylene (LDPE) resin with high-speed extrusion coating property is fractionated through solvent gradient fractionation (SGF) technique using 1,2,4-trimethylbenzene (TMB) and ethyl cellosolve (ECS) as good/poor solvent pair at 115 °C. The pristine sample and its fractions are characterized by high-temperature gel permeation chromatography (HT-GPC) coupled with triple detectors (refractive index RI, light scattering LS, viscometer VIS), ¹³C–nuclear magnetic resonance spectroscopy (¹³C–NMR), differential scanning calorimetry (DSC) and successive self-nucleation/annealing (SSA) thermal fractionation. By adjusting the ratio of good/poor solvent, the obtained fractions show their molecular weight from 1.58?×?10³ g/mol to 4.76?×?10⁵ g/mol. It is found that the fractions with high molecular weight (fractions 10–13) occupy about 55.85% in resin. Particularly, the molecular weight distribution (MWD) of most fractions is in the range of 1.1–1.2. Each fraction contains more short chain branch (SCB) and less long chain branch (LCB) simultaneously. With increasing the molecular weight, the branching content shows no regular change. The lowest SCB and total branch content regions correspond to molecular weight 1.97?×?10⁴ to 4.10?×?10⁴ g/mol. The melting and crystallization temperatures of fractions firstly increase and then decrease with the molecular weight. The crystallinity decreases gradually from 51.7% to 31.1%. In the SSA thermal fractionation, each fraction shows a broad range of endotherm with multiple melting peaks in DSC curve corresponding to the different methylene sequence length (MSL) (L _n and L _w ). The longest L _n (L _w ) region occurs in the molecular weight of 8.95?×?10³ to 3.14?×?10⁴ g/mol. The relationship between chain microstructure and properties is also discussed.

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Graphical Abstract One coating LDPE resin is effectively fractionated by solvent gradient fractionation using TMB/ECS as good/poor solvent pair according to molecular weight. The component with high molecular weight is more than that with low molecular weight. Higher molecular weight and LCB improve the melt strength synergetically, and suitable component with low molecular weight provides better flowability.

     

Synthesis and characterization of fluorescent PEG-polyurethane with free carboxyl groups

An innovative spherical poly(vinyl alcohol)(PVA)/peat/clay porous composite bead was prepared and shown to be suitable for use as an adsorbent. The mass transport process for the adsorption of metal ions onto this composite bead in an aqueous system was investigated. In the external mass transport process, the diffusion coefficient (D₁) of Cu⁺² and Zn⁺² ions increased with increasing initial metal ion concentration and the increasing effect was more pronounced in the initial metal ion concentrations range of 18?×?10^-3 to 22?×?10^-3?M. The diffusion rate of Zn⁺² ions was faster than that of Cu⁺² ions. In the intraparticle diffusion process, the diffusion coefficient (D₂) decreased with increasing initial metal ion concentration in the initial concentration range of 1?×?10^-3 to 4?×?10^-3?M, and the value of D₂ maintained an almost constant value in the initial concentration range of 8?×?10^-3 to 22?×?10^-3?M. The rate of ion diffusion within the adsorbent for Cu⁺² ions was faster than that for Zn⁺² ions. The adsorption mechanism was controlled by the intraparticle diffusion process. The adsorption followed the Langmuir adsorption isotherm model. The maximum amount of adsorbed metal ions for Cu⁺² and Zn⁺² ions were 22.57 and 13.62?mg/g composite bead, respectively.     

Improved stability in P3HT:PCBM photovoltaics by incorporation of well‐designed polythiophene/graphene compositions

Morphological and photovoltaic stabilities of poly(3‐hexylthiophene) (P3HT):phenyl‐C₆₁‐butyric acid methyl ester (PC₇₁BM) solar cells were investigated in pristine and modified states. To this end, four types of patterned/assembled nanostructures, namely reduced graphene oxide (rGO)‐g‐poly(3‐dodecylthiophene)/P3HT patched‐like pattern, rGO–polythiophene/P3HT/PC₇₁BM nanofiber, rGO‐g‐P3HT/P3HT cake‐like pattern and supra(polyaniline (PANI)‐g‐rGO/P3HT), were designed on the basis of rGO and various conjugated polymers. Intermediately covered rGO nanosheets by P3HT crystals (supra(PANI‐g‐rGO/P3HT)) performed better than sparsely (patched‐like pattern) and fully (cake‐like pattern) covered ones in P3HT:PC₇₁BM solar cell systems. Supra(PANI‐g‐rGO/P3HT) nanohybrids largely phase‐separated in active layers (root mean square = 0.88 nm) and also led to the highest performance (power conversion efficiency of 5.74%). The photovoltaic characteristics demonstrated decreasing trends during air aging for all devices, but with distinct slopes. The steepest decreasing plots were obtained for the unmodified P3HT:PC₇₁BM devices (from 1.77% to 0.28%). The two supramolecules with the most ordered structures, that is, cake‐like pattern (10.12 mA cm^?2, 51%, 0.58 V, 2.2 × 10^?6 cm² V^?1 s^?1, 4.3 × 10^?5 cm² V^?1 s^?1, 0.69 nm and 2.99%) and supra(PANI‐g‐rGO/P3HT) (12.51 mA cm^?2, 57%, 0.63 V, 1.2 × 10^?5 cm² V^?1 s^?1, 3.4 × 10^?4 cm² V^?1 s^?1, 0.82 nm and 4.49%), strongly retained morphological and photovoltaic stabilities in P3HT:PC₇₁BM devices after 1 month of air aging. According to the morphological, optical, photovoltaic and electrochemical results, the supra(PANI‐g‐rGO/P3HT) nanohybrid was the best candidate for stabilizing P3HT:PC₇₁BM solar cells. © 2020 Society of Chemical Industry     

Simple dilatometer for polymer density and thermal expansivity measurements

A dilatometer is described to study the temperature dependence of density (ρ) of solid and semiliquid polymers and the following linear relations have been established. Atactic poly(vinylisobutyl ether) (25–90°C): ρ = 0.9166 ? 7.15 × 10^?4 × T. Isotactic poly(vinylisobutyl ether) (25–70°C): ρ = 0.9184 ? 7.13 × 10^?4 × T. Poly(n-butyl methacrylate) (90–150°C): ρ = 1.0622 ? 8.41 × 10^?4 × T. Poly(dimethyl siloxane) (30–51°C, using Lipkins pycnometer): ρ = 0.9846 ? 8.81 × 10^?4 × T; where ρ is in g.cm^?3, temperature T is in Celsius, and the linearity correlation coefficient r is better than 0.9998. Their volume–temperature plots are also linear. As the plots of polyn-butyl methacrylate curved slightly near its glass transition (20°C), the quadratic equation ρ = 1.0402 ? 4.79 × 10^?4 × T ? 1.46 × 10^?6 × T² (standard deviation = 1.57 × 10^?3) has been suggested for the entire range of 30–150°C scrutinized in this study. The data have been utilized to derive thermal expansivity and some equation-of-state parameters of the polymers at the reference temperature (ca. 20°C).