A new composite polymer electrolyte based on poly(ethyleneoxide)/ polysiloxane/BMImTFSI/organomontmorillonite

Composite polymer electrolytes based on poly(ethylene oxide)-polysiloxane/l-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide/organomontmorillonite(PEO-PDMS/1L/OMMT) were prepared and characterized.Addition of both an ionic liquid and OMMT to the polymer base of PEO-PDMS resulted in an increase in ionic conductivity.At room temperature,the ionic conductivity of sample PPB100-OMMT4 was 2.19×10~3 S/cm.The composite polymer electrolyte also exhibited high thermal and electrochemical stability and may potentially be applied in lithium batteries.     

Preparation of new hybrid organic/inorganic polymeric chiral stationary phases for ligand-exchange chromatography

Three new hybrid organic/inorganic polymeric ligand-exchange chiral stationary phases were developed by radical chain transfer reaction and surface grafting on silica gel,and successfully used for the enantioseparations of DL-amino acids and DL-hydroxyl acids.The resolutions were achieved by using water containing 2.0×10~(-4) mol/L of CuAc_2 as a mobile phase,column temperature of 40℃,flow rate of 1.0mL/min and detection at UV 254 nm.The elution order of D-isomer before L-isomer was observed for all DL-amino acids resolved except DL-Pro.     

Glucose biosensor based on new carbon nanotube-gold-titania nano-composites modified glassy carbon electrode

In this paper, a novel biosensor was prepared by immobilizing glucose oxidase （GOx） on carbon nanotube-gold-titania nanocomposites （CNT/Au/TiO2） modified glassy carbon electrode （GCE）. SEM was initially used to investigate the surface morphology of CNT/Au/TiO2 nanocomposites modified GCE, indicating the formation of the nano-porous structure which could readily facilitate the attachment of GOx on the electrode surface. Cyclic voltammogram （CV） and electrochemical impedance spectrum （EIS） were further utilized to explore relevant electrochemical activity on CNT]Au/TiO2 nanocomposites modified GCE. The observations demonstrated that the immobilized GOx could efficiently execute its bioelectrocatalytic activity for the oxidation of glucose. The biosensor exhibited a wider linearity range from 0.1 mmol L-1 to 8 mmol L^-1 glucose with a detection limit of 0.077 mmol L^- 1.     

Gas permeation properties of poly(lactic acid)

The need for the development of polymeric materials based on renewable resources has led to the development of poly(lactic acid) (PLA) which is being produced from a feedstock of corn rather than petroleum. The present study examines the permeation of nitrogen, oxygen, carbon dioxide, and methane in amorphous films of PLA cast from solution. The properties of PLA are compared to other commodity plastics and it is shown that PLA permeation closely resembles that of polystyrene. At 30°C, N₂ permeation in PLA is 1.3 (10⁻¹⁰ cm³ (STP) cm/cm² s cmHg) and the activation energy is 11.2 kJ/mol. For oxygen the corresponding values are 3.3 (10⁻¹⁰ cm³(STP) cm/cm² s cm Hg) and 11.1 kJ/mol. The values for carbon dioxide permeation are 1.2 (10⁻¹⁰ cm³ (STP) cm/cm² s cmHg) and 6.1 kJ/mol. For methane values of 1.0 (10⁻¹⁰ cm³ (STP) cm/cm² s cmHg) and an activation energy of 13.0 kJ/mol are found. Studies with pure gases show that polymer chain branching and small changes in l:d stereochemical content have no effect on permeation properties. Crystallinity is found to dominate permeation properties in a biaxially oriented film. The separation factor for a CO₂/CH₄ mixed gas system is measured between 0 and 50°C and does not deviate significantly from the calculated ideal separation factor; at 0°C the separation factor is 16, a value that suggests continued studies of PLA as a separation medium are warranted.     

Far-infrared studies on Nafion and perfluoroimide acid (PFIA) and their alkali salts

The terahertz/far-infrared spectra (<300 cm⁻¹) of perfluorinated sulfonic acid (Nafion NR211 polymer) and perfluoroimide acid (PFIA polymer) and their alkali (M⁺) salts have been analyzed and the results are presented. Pronounced features in the spectra of these ionomers that correlate systematically with the corresponding cation mass are reported and from their spectral position the force constants are derived. The average vibrational force constants for Nafion/M⁺ and PFIA/M⁺ are found to be 54 ± 7 and 39 ± 4 N/m, respectively. Such terahertz/far-infrared signatures probe the detailed structure of the Nafion/M⁺ and PFIA/M⁺ ionic clusters and, in turn, provide benchmarks for elucidating the ionomer “water channels” or water molecules located in the ionomer–water interface upon hydration. Qualitative trends in the vibrational energies of Nafion and PFIA can be explained by consideration of electronic and/or structural (ionic domain-size) effects.     

Preparation of porous polymer electrolyte by a microwave assisted effervescent disintegrable reaction

Porous polymer membranes with sub-micrometer pores were successfully prepared by a novel microwave assisted effervescent disintegrable reaction. The fine connected porous structure was obtained by promoting effervescent disintegrable reaction between citric acid and sodium bicarbonate due to the assistance of microwave. The ionic conductivity of the prepared gelled polymer electrolyte is up to 1.17 × 10^?3 S cm^?1 and electrochemical window 4.5 V. This method provides a convenient route to prepare porous polymer electrolyte, which will greatly promote the practical application of porous polymer electrolytes.     

Dye-sensitized solar cells employing amphiphilic poly(ethylene glycol) electrolytes

Poly(ethylene glycol) (PEG) was modified with a long alkyl acid to produce a self-organized amphiphilic polymer (amPEG). FT-IR and NMR spectroscopies confirmed the amPEG synthesis. This polymer was complexed with lithium iodide (LiI) and 1-methyl-3-propylimidazolium iodide (MPII) to prepare polymer electrolytes to be applied to dye-sensitized solar cells (DSSC). FT-IR studies showed that upon the addition of litium salt the free ether and ester carbonyl bands shifted towards lower wavenumbers, indicating the complexation of Li ions with oxygens on the amPEG. Alkylation and salt introduction reduced PEG crystallinity, as characterized by wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC). The ionic conductivities of the polymer electrolytes increased with increasing salt concentrations, and the energy conversion efficiency of DSSC reached 2.6% at 100 mW cm^?2 for amPEG/MPII system which is higher than amPEG/LiI. This may be due to the higher mobility of MPII ion than the lithium ion in the polymer electrolyte. The interfacial properties between electrolytes and electrodes were investigated using field-emission scanning electron microscopy (FE-SEM) and electrochemical impedance spectroscopy (EIS).     

Ionogels encompassing ionic liquid with liquid like performance preferable for fast solid state electrochromic devices

Novel ionogels encompassing an ionic liquid encaged in an inorganic matrix were synthesized by sol–gel chemistry. The ability of these highly conducting ionogels (∼10⁻² S cm⁻¹ at 25 °C) to act as liquid electrolytes in spite of their solid form has been exploited in inorganic electrochromic devices based on tungsten oxide and Prussian blue electrodes. These devices exhibit extremely fast switching kinetics and make it the best and only candidate for the realization of fast all solid state electrochromic devices.     

Synthesis and properties of polyfluorene copolymers bearing thiophene and porphyrin

To search for more wider absorption and higher charge carriers mobilities materials of polymer solar cell, a series of soluble alternating polyfluorene copolymers were synthesized by palladium-catalyzed Suzuki coupling reaction. Their structures were determined by 1H NMR, IR and UV-vis. And their UV-vis absorption spectra indicated that they had strong absorption over 600 nm spectral range and nearly cover 400-700 nm visible region. The band gaps of copolymers calculated according to cyclic voltammetry （CV） were between 1.96 and 2.03 eV. Polymer：TiO2 bulk-heterojunction films were made from mixtures of polymer and titanium isopropoxide, a precursor for TiO2, via hydrolysis in air overnight. The photoluminescence at 380-800 nm of the blend film of PT-TPP20 （5 mg/mL）：Ti（OC3H7）4 （80 μL/mL） （20% volume fraction） was significantly quenched in the 50% Ti（OC3H7）4 blend film, indicating that rapid and efficient separation of photoinduced electron-hole pairs.     

Sulfur doped reduced graphene oxide as metal-free catalyst for the oxygen reduction reaction in anion and proton exchange fuel cells

Sulfur doped reduced graphene oxide (S-rGO) is investigated for catalytic activity towards the oxygen reduction reaction (ORR) in acidic and alkaline electrolytes. X-ray photoelectron spectroscopy shows that sulfur in S-rGO is predominantly integrated as thiophene motifs within graphene sheets. The overall sulfur content is determined to be approximately 2.2 at.% (elemental analysis). The catalytic activity of S-rGO towards the ORR is investigated by both rotating disc electrode (RDE) and polymer electrolyte fuel cell (PEFC) measurements. RDE measurements reveal onset potentials of 0.3 V and 0.74 V (vs. RHE) in acidic and alkaline electrolyte, respectively. In a solid electrolyte fuel cell with S-rGO as cathode material, this is reflected in an open circuit voltage of 0.37 V and 0.78 V and a maximum power density of 1.19 mW/cm² and 2.38 mW/cm² in acidic and alkaline polymer electrolyte, respectively. This is the first report investigating the catalytic activity of a sulfur doped carbon material in both acidic and alkaline liquid electrolyte, as well as in both proton and anion exchange polymer electrolyte fuel cells.     

Potentiometric determination of diclofenac in pharmaceutical formulation by membrane electrode based on ion associate with base dye

The characteristics,performance and application of membrane electrode based on ion associate of diclofenac with base dye Safranine T are described.The electrode response to diclofenac has the sensitivity of 47±1.0 mV decade~(-1)over the range of 5×10~(-5)to 5×10~(-2)mol/L at pH 6-12,and the detection limit of 3.2×10~(-5)mol/L.The electrode is easy assembled at a relatively low cost has fast response time(2-4 s)and can be used for a period up to 3.5 months without any considerable divergence in potential.The proposed sensor displayed good selectivity for diclofenac in the presence of different substances.It was used to determine diclofenac in pharmaceuticals by means of the standard addition method.     

Polymer gel electrolytes based on oligomeric polyether/cross-linked PMMA blends prepared via in situ polymerization

Very-low-vapor-pressure oligomeric polyether electrolytes blended with and dimensionally stabilized by cross-linked poly(methyl methacrylate) (PMMA) are prepared via in situ polymerization. The synthesized polymer gel electrolytes (PGEs) are freestanding films with excellent dimensional stability, mechanical integrity and strength. They exhibit high ionic conductivity at room temperature reaching 4.3 × 10⁻⁴ S/cm for the highest conducting sample and exceptional thermal stability. The oligomeric polyether and PMMA appear to have molecular level interaction in the blends and the PGEs remain a single phase from at least −50 to 200 °C, potentially enabling their application in advanced batteries in wide temperature ranges. The novel in situ polymerization process allows precise control of the composition of the PGEs and can enable in situ fabrication of advanced cells.     

Investigation of laser-induced breakdown spectroscopy and multivariate analysis for differentiating inorganic and organic C in a variety of soils

Laser-induced breakdown spectroscopy (LIBS) along with multivariate analysis was used to differentiate between the total carbon (C), inorganic C, and organic C in a set of 58 different soils from 5 soil orders. A 532 nm laser with 45 mJ of laser power was used to excite the 58 samples of soil and the emission of all the elements present in the soil samples was recorded in a single spectrum with a wide wavelength range of 200–800 nm. The results were compared to the laboratory standard technique, e.g., combustion on a LECO-CN analyzer, to determine the true values for total C, inorganic C, and organic C concentrations. Our objectives were: 1) to determine the characteristic spectra of soils containing different amounts of organic and inorganic C, and 2) to examine the viability of this technique for differentiating between soils that contain predominantly organic and/or inorganic C content for a range of diverse soils. Previous work has shown that LIBS is an accurate and reliable approach to measuring total carbon content of soils, but it remains uncertain whether inorganic and organic forms of carbon can be separated using this approach. Total C and inorganic C exhibited correlation with rock-forming elements such as Al, Si, Fe, Ti, Ca, and Sr, while organic C exhibited minor correlation with these elements and a major correlation with Mg. We calculated a figure of merit (Mg/Ca) based on our results to enable differentiation between inorganic versus organic C. We obtained the LIBS validation prediction for total, inorganic, and organic C to have a coefficient of regression, r² = 0.91, 0.87, and 0.91 respectively. These examples demonstrate an advance in LIBS-based techniques to distinguish between organic and inorganic C using the full wavelength spectra.     

Vapour pressure osmometry determination of water activity of binary and ternary aqueous (polymer + polymer) solutions

Precise water activity measurements at T = 308.15 K were carried out on several binary (water + polymer) and ternary {water + polymer (1) + polymer (2)} systems using the vapour pressure osmometry (VPO) technique. Polymers were polyethylene glycol 400 (PEG400), polyethylene glycol 6000 (PEG6000), polypropylene glycol 400 (PPG400), polyvinylpyrrolidone (PVP) and dextran (DEX). The water activity results obtained were used to calculate the vapour pressure of solutions as a function of concentration and the segment-based local composition models, NRTL and Wilson, were used to correlate the experimental water activity values. It was found that, for the polymer concentration range studied here, the values of the water activity obtained for the binary (water + polymer) solutions decrease in the order DEX > PVP > PEG6000 > PPG400 > PEG400. Furthermore, water activities of solutions of each polymer in the aqueous solutions of (5, 10, 15 and 20)% (w/w) other polymers investigated were also measured at T = 308.15 K. The ability of polymer (1) in decreasing the water activity of binary {water + polymer (2)} solutions was discussed on the basis of the (polymer + water) and {polymer (1) + polymer (2)} interactions.     

Amperometric glucose sensor based on glucose oxidase immobilized on gelatin-multiwalled carbon nanotube modified glassy carbon electrode

We investigated the direct electrochemistry of glucose oxidase (GOx) at gelatin-multiwalled carbon nanotube (GCNT) modified glassy carbon electrode (GCE). GOx was covalently immobilized onto GCNT modified GCE through the well known glutaraldehyde (GAD) chemistry. The immobilized GOx showed a pair of well-defined reversible redox peaks with a formal potential (E⁰′) of ? 0.40 V and a peak to peak separation (ΔE_p) of 47 mV. The surface coverage concentration (Г) of GOx in GCNT/GOx/GAD composite film modified GCE was 3.88 × 10^? 9 mol cm^? 2 which indicates the high enzyme loading. The electron transfer rate constant (k_s) of GOx immobilized onto GCNT was 1.08 s^? 1 which validates a rapid electron transfer processes. The composite film shows linear response towards 6.30 to 20.09 mM glucose. We observed a good sensitivity of 2.47 μA mM^?1 cm^? 2 for glucose at the composite film. The fabricated biosensor displayed two weeks stability. Moreover, it shows no response to 0.5 mM of ascorbic acid (AA), uric acid (UA), acetaminophen (AP), pyruvate (PA) and lactate (LA) which shows its potential application in the determination of glucose from human serum samples. The composite film exhibits excellent recovery for glucose in human serum at physiological pH with good practical applicability.     

‘‘Soggy sand＇＇ polymer composite nanofber membrane electrolytes for lithium ion batteries

A kind of octanol-modifded silica nanoparticle was fabricated and employed as a framework to form‘‘soggy sand’’electrolyte along with 1-butyl-3-methylimidazolium tetrafluoroborate.‘‘Soggy sand’’and poly（vinylidene fluoride-hexafluoropropylene）composite electrolyte membranes were electrospun for the frst time.The properties of this membrane electrolyte have been evaluated by the mechanical test and electrochemical test.The Young’s modulus increased by 275%from 6.8 MPa to 25.5 MPa and the electrical conductivity increased to 7.6 10à5S/cm at 290.15 K when compared to pristine P（VdF-HFP）membrane electrolyte.The conductivity is 3.1 10à4S/cm at 323.15 K.     

Flow injection-chemical vapor generation atomic fluorescence spectrometry hyphenated system for organic mercury determination: A step forward

Monomethylmercury and ethylmercury were determined on line using flow injection-chemical vapor generation atomic fluorescence spectrometry without neither requiring a pre-treatment with chemical oxidants, nor UV/MW additional post column interface, nor organic solvents, nor complexing agents, such as cysteine. Inorganic mercury, monomethylmercury and ethylmercury were detected by atomic fluorescence spectrometry in an Ar/H₂ miniaturized flame after sodium borohydride reduction to Hg⁰, monomethylmercury hydride and ethylmercury hydride, respectively. The effect of mercury complexing agent such as cysteine, ethylendiaminotetracetic acid and HCl with respect to water and Ar/H₂ microflame was investigated.The behavior of inorganic mercury, monomethylmercury and ethylmercury and their cysteine-complexes was also studied by continuous flow-chemical vapor generation atomic fluorescence spectrometry in order to characterize the reduction reaction with tetrahydroborate. When complexed with cysteine, inorganic mercury, monomethylmercury and ethylmercury cannot be separately quantified varying tetrahydroborate concentration due to a lack of selectivity, and their speciation requires a pre-separation stage (e.g. a chromatographic separation). If not complexed with cysteine, monomethylmercury and ethylmercury cannot be separated, as well, but their sum can be quantified separately with respect to inorganic mercury choosing a suitable concentration of tetrahydroborate (e.g. 10^? 5 mol L^? 1), thus allowing the organic/inorganic mercury speciation.The detection limits of the flow injection-chemical vapor generation atomic fluorescence spectrometry method were about 45 nmol L^? 1 (as mercury) for all the species considered, a relative standard deviation ranging between 1.8 and 2.9% and a linear dynamic range between 0.1 and 5 μmol L^? 1 were obtained. Recoveries of monomethylmercury and ethylmercury with respect to inorganic mercury were never less than 91%. Flow injection-chemical vapor generation atomic fluorescence spectrometry method was validated by analyzing the TORT-1 certificate reference material, which contains only monomethylmercury, and obtaining 83 ± 5% of monomethylmercury recovered, respectively. This method was also applied to the determination of monomethylmercury in saliva samples.     

A novel method for Co(Ⅱ) and Cu(Ⅱ) analysis by capillary electrophoresis with chemiluminescence detection

Based on the fact that some metal ions can catalyze the chemiluminescence(CL)reaction of luminol with K_3Fe(CN)_6,a novel capillary electrophoresis CL method was developed for the determination of Co(Ⅱ)and Cu(Ⅱ).The separation was carried out with a 10 mmol/L sodium acetate solution containing 0.8 mmol/L luminol and 2.0 mmol/Lα-HIBA(adjusted to pH 4.8 by HAc solution).The post-capillary reagent was 2.0 mmol/L K_3Fe(CN)_6 which was adjusted to pH 13.0 by NaOH solution.Under the optimum conditions,the detection limits(S/N=3)for Co(Ⅱ)and Cu(Ⅱ)were 7.5×10~(-11)mol/L and 7.5×10~(-9)mol/L,with the linear range of 7.5×10~(-9)mol/L to 1.0×10~(-6)mol/L and 7.5×10~(-8)mol/L to 5.0×10~(-5)mol/L, respectively.     

Laser Raman and ac impedance spectroscopic studies of PVA: NH4NO3 polymer electrolyte

Ion conducting polymer electrolyte PVA:NH₄NO₃ has been prepared by solution casting technique and characterized using XRD, Raman and ac impedance spectroscopic analyses. The amorphous nature of the polymer films has been confirmed by XRD and Raman spectroscopy. An insight into the deconvoluted Raman peaks of υ₁ vibration of NO₃^? anion for the polymer electrolyte reveals the dominancy of ion aggregates at higher NH₄NO₃ concentration. From the ac impedance studies, the highest ion conductivity at 303 K has been found to be 7.5 × 10^?3 S cm^?1 for 80PVA:20NH₄NO₃. The conductivity of the polymer electrolytes has been found to depend on the degree of dissociation of the salt in the host polymer matrix. The combination of the above-mentioned analyses has proven worth while and in fact necessary in order to achieve better understanding of these complex systems.