Upper critical solution temperature—type cononsolvency of poly(N,N-dimethylacrylamide) in water—organic solvent mixtures

The behaviour of linear poly(N,N-dimethylacrylamide) (PDMAM) chains was studied by turbidimetry and viscometry in mixtures of water with the polar organic solvents methanol, dioxane and acetone. The swelling-deswelling behaviour of PDMAM gels in the same solvent mixtures was also investigated. Contrary to the behaviour in water-methanol mixtures, in water-dioxane and water-acetone mixtures a significant shrinkage of polymer chains and deswelling of polymer gels, followed by phase separation, was observed for high organic solvent fractions. Cononsolvency phenomena were found to be temperature-dependent, as demixing occurred upon decreasing temperature. This upper critical solution temperature (UCST) phase separation behaviour in mixed solvents was studied by turbidimetry and compared to the well-known lower critical solution temperature (LCST) behaviour of poly(N-isopropylacrylamide) (PNIPAM) in similar solvents mixtures.     

Synthesis, characterization and thermal properties of soluble aromatic poly(amide imide)s

Novel diamines such as N,N′-bis(aminoaryl)terephthalamido-2-carboxylic acids (BATCA), which contain primary amine, amide and carboxylic acid groups and are soluble in dilute aqueous NaOH solution, were synthesized by reacting aromatic diamines with trimellitic anhydride chloride in dimethylformamide. Poly(amide imide)s containing 3:1 ratio of amide:imide groups in the polymer chain were prepared by low temperature solution polymerization of BATCAs with isophthaloyl chloride or terephthaloyl chloride in dimethylformamide at 5-10 °C to form poly(amide amic acid)s, and followed by treating with a mixture of triethylamine and acetic anhydride. The PAIs were soluble in polar aprotic solvents like dimethylformamide, dimethylacetamide, dimethylsulphoxide and N-methylpyrrolidone, and have inherent viscosities in the range of 0.30-0.66 dL/g. The PAIs were characterized by IR, ¹H NMR and ¹³C NMR techniques. Thermogravimetric analysis (TGA) has shown that the initial decomposition temperatures of the polymers are in the range of 250-440 °C, depending upon the structures of diamine and diacid chloride. The glass transition temperatures of the PAIs are in the range of 128-320 °C. The IDT and T_g values of the polymers containing terephthaloyl unit are higher by about 20-40 °C than those of the polymers with isophthaloyl unit. BATCA could be utilized for the preparation of thin film composite membranes having PAA/PAI barrier layer on PES by in situ interfacial polymerization with IPC/TPC/TMC.     

CO2 absorption properties of Brønsted acid-base ionic liquid composed of N,N-dimethylformamide and bis(trifluoromethanesulfonyl)amide

The solubilities of CO₂ and the liquid densities in a Brønsted acid-base ionic liquid, [DMFH][Tf₂N], composed of N,N-dimethylformamide (DMF) and bis(trifluoromethanesulfonyl)amide (HTf₂N) have been investigated at high pressures and at different temperatures. The results were compared with those in DMF and a typical 1-butyl-3-methylimidazolium analogue with the same anion, [BMIM][Tf₂N]. The mole fraction scaled solubilities of CO₂ in the three liquids showed a slight increase in the following order, DMF < [DMFH][Tf₂N] < [BMIM][Tf₂N], whereas more remarkable difference was observed in the volume scaled concentrations of CO₂, [BMIM][Tf₂N] < [DMFH][Tf₂N] « DMF, mainly due to the bulkiness of liquid entities.     

Investigation of bulk hybrid heterojunction solar cells based on Cu(In,Ga)Se2 nanocrystals

This work presents the systematic studies of bulk hybrid heterojunction solar cells based on Cu(In, Ga)Se₂ (CIGS) nanocrystals (NCs) embedded in poly(3-hexylthiophene) matrix. The CIGS NCs of approximately 17 nm in diameter were homogeneously blended with P3HT layer to form an active layer of a photovoltaic device. The blend ratios of CIGS NCs to P3HT, solvent effects on thin film morphologies, interface between P3HT/CIGS NCs and post-production annealing of devices were investigated, and the best performance of photovoltaic devices was measured under AM 1.5 simulated solar illumination (100 mW/cm²).     

Spectroscopic studies of polymer electrolytes based on poly(N-ethylethylenimine) and poly(N-methylethylenimine)

Poly(ethylethylenimine), PEEI, was prepared from poly(ethylenimine) by reductive alkylation with acetaldehyde. Samples of PEEI and poly(methylenimine), PMEI, complexed with LiCF₃SO₃ were prepared and characterized using differential scanning calorimetry and FT-IR. Small differences in the room temperature spectra of the two complexes were noted; these differences were due to the presence of a CH₂ group in the side chain of PEEI. The predominant form of cation-anion interactions was a contact ion pair. As the samples were heated, a transition from ion pairs to “free” ions was observed, with most of the change occurring between 140 and 150 °C in both PEEI and PMEI complexes. Thermal cycling established that the transition was irreversible in the time frame of the cycling experiments. Two-dimensional correlation spectroscopy did not show any significant intensity or frequency changes in bands sensitive to cation-polymer interactions during any heating or cooling cycle.     

Thermo- and pH-sensitive dendrimer derivatives with a shell of poly(N,N-dimethylaminoethyl methacrylate) and study of their controlled drug release behavior

Novel dendrimer derivatives combining the temperature- and pH-sensitivities are synthesized. At first, polyamidoamine (PAMAM) dendrimers with generations 1-5 are synthesized by the reaction of ethylenediamine with methyl acrylate, and then the dendrimers are acylated by chloroacetyl chloride to obtain PAMAM-Cl, which can act as a macroinitiator for further synthesizing functional dendrimers. For fulfilling this goal, the polymers consisting of a dendritic PAMAM core and poly(N,N-dimethylaminoethyl methacrylate) (PDMA) shell are synthesized by atom transfer radical polymerization (ATRP). Their macromolecular structures are characterized by FTIR, ¹H NMR, DSC and particle size analyses, and their aqueous solutions are inspected by UV spectroscopy for understanding their thermo- and pH-sensitivities. The results show that novel dendrimer derivatives exhibit clearly thermo- and pH-respondings in accordance with the change of the environment. Using chlorambucil (CLB) as a model drug, the behaviors of the controlled drug release from polymers with different average graft length of PDMA are studied. The results indicate that the rate of the drug release can be effectively controlled by the pH value.     

Electroactive phases of poly(vinylidene fluoride): Determination,processing and applications

Poly(vinylidene fluoride), PVDF, and its copolymers are the family of polymers with the highest dielectric constant and electroactive response, including piezoelectric, pyroelectric and ferroelectric effects. The electroactive properties are increasingly important in a wide range of applications such as in biomedicine, energy generation and storage, monitoring and control, and include the development of sensors and actuators, separator and filtration membranes and smart scaffolds, among others. For many of these applications the polymer should be in one of its electroactive phases. This review presents the developments and summarizes the main characteristics of the electroactive phases of PVDF and copolymers, indicates the different processing strategies as well as the way in which the phase content is identified and quantified. Additionally, recent advances in the development of electroactive composites allowing novel effects, such as magnetoelectric responses, and opening new applications areas are presented. Finally, some of the more interesting potential applications and processing challenges are discussed.     

Effects of the Bradyrhizobium japonicum waaL (rfaL) Gene on Hydrophobicity,Motility, Stress Tolerance,and Symbiotic Relationship with Soybeans

We cloned and sequenced the waaL (rfaL) gene from Bradyrhizobium japonicum, which infects soybean and forms nitrogen-fixing nodules on soybean roots. waaL has been extensively studied in the lipopolysaccharide (LPS) biosynthesis of enteric bacteria, but little is known about its function in (brady)rhizobial LPS architecture. To characterize its role as O-antigen ligase in the LPS biosynthesis pathway, we constructed a waaL knock-out mutant and its complemented strain named JS015 and CS015, respectively. LPS analysis showed that an LPS structure of JS015 is deficient in O-antigen as compared to that of the wild type and complemented strain CS015, suggesting that WaaL ligates the O-antigen to lipid A-core oligosaccharide to form a complete LPS. JS015 also revealed increased cell surface hydrophobicity, but it showed decreased motility in soft agar plates. In addition to the alteration in cell surface properties, disruption of the waaL gene caused increased sensitivity of JS015 to hydrogen peroxide, osmotic pressure, and novobiocin. Specifically, plant tests revealed that JS015 failed to nodulate the host plant soybean, indicating that the rhizobial waaL gene is responsible for the establishment of a symbiotic relationship between soybean and B. japonicum.     

Mechanistic study on Sn(Oct)<Subscript>2</Subscript>-catalyzed,ring-opening polymerization of <Emphasis Type="Italic">p</Emphasis>-dioxanone by surface-initiated polymerization and x-ray photoelectron spectroscopy

Two mechanisms on Sn(Oct)₂-catalyzed, ring-opening polymerization of p-dioxanone (PDX) were mainly proposed: activated monomer mechanism and coordination-insertion mechanism. The activated monomer mechanism assumes that alcohol complexed with Sn(Oct)₂ reacts with monomer and forms a ternary complex. The initiation and chain growth then proceeds within the complex with liberation of the intact Sn(Oct) ₂. In contrast, the coordination-insertion mechanism hypothesizes that an actual initiator is the -Sn(OR) species and the polymerization proceeds on the -Sn-O-polymer. In this paper, to investigate the presence/absence of the Sn species in the PPDX chain, we used X-ray photoelectron spectroscopy (XPS) of poly(p-dioxanone) (PPDX) grown from a gold surface using the grafting-from approach, and the XPS data supports the coordination-insertion mechanism. After the polymerization of PPDX from the surface, the peaks from Sn were observed at 153, 486, and 495 eV in XPS spectrum, and the peaks disappeared after quenching with 1N HCl.     

Synthesis and characterization of pH-sensitivity semi-IPN hydrogel based on hydrogen bond between poly(N-vinylpyrrolidone) and poly(acrylic acid)

A novel spherically shaped semi-interpenetrating network (semi-IPN) hydrogel, which is based on hydrogen bond between chemical crosslinked poly(N-vinylpyrrolidone) (PVP) and linear poly(acrylic acid) (PAA), was prepared. The semi-IPN hydrogel was synthesized by three steps: (1) linear PAA with different molecular weights were obtained by a reaction of free radical polymerization used 2,2′-azo-bis-iso-butyronitrile (AIBN) as an initiator; (2) crosslinked PVP bead was obtained by a reaction of N-vinylpyrrolidone with AIBN used as an initiator and N,N′-methylene-bis-acrylamide (NNMBA) used as a crosslinker by the way of suspension polymerization; (3) complexation occurred between suitable amount of aqueous solution of PAA and the porous PVP bead and was stabilized by multiple frost-defrost, from this step the semi-IPN hydrogel was obtained. Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) proved the presence of the hydrogen bond in the hydrogel. The swelling behaviour of the hydrogel was studied in buffer solution with different pH and NaCl aqueous solution. The results showed that the semi-IPN hydrogel had excellent pH-sensitivity in the range of pH from 2.25 to 4.00 and the small molecule salt had little influence on the swelling behaviour of the semi-IPN hydrogel over the range of concentration of NaCl aqueous solution investigated. The results were confirmed further by scanning electron microscope (SEM). The mechanism of swelling and deswelling was discussed.     

H NMR study of temperature-induced phase transitions in D2O solutions of poly(N-isopropylmethacrylamide)/poly(N-isopropylacrylamide) mixtures and random copolymers

¹H NMR spectroscopy was used to investigate temperature-induced phase transitions in D₂O solutions of poly(N-isopropylmethacrylamide) (PIPMAm)/poly(N-isopropylacrylamide) (PIPAAm) mixtures and P(IPMAm/IPAAm) random copolymers of various composition on molecular level. While two phase transitions were detected for PIPMAm/PIPAAm mixtures, only single phase transition was found for P(IPMAm/IPAAm) copolymers. The phase transition temperatures of PIPAAm component (appears at lower temperatures) are not affected by the presence of PIPMAm in the mixtures; on the other hand, the temperatures of the phase transition of PIPMAm component (appears at higher temperatures) are affected by the phase separation of the PIPAAm component and depend on concentration of the solution. For P(IPMAm/IPAAm) random copolymers, a departure from the linear dependence of the transition temperatures on the copolymer composition was found for a sample with 75 mol% of IPMAm monomeric units.     

Aluminium (III)-selective PVC membrane sensor based on a Schiff base complex of N,N′-bis (salicylidene)-1, 2-cyclohexanediamine

A potentiometric aluminium sensor, based on the use N,N′-bis(salicylidene)-1,2-cyclohexanediamine (NBSC) as a neutral carrier, in poly(vinyl chloride) (PVC) matrix, is reported. Effect of various plasticizers; 2-nitrophenyloctylether (o-NPOE), tri-n-butyl phosphates (TBP), dioctylpththalate (DOP) & chloronapthalen (CN), and anion excluder, sodium tetraphenylborate (NaTPB) was studied. The best performance was obtained with a membrane composition of PVC: o-NPOE: NBSC: NaTPB ratio (w/w; mg) of 150:150:5:5. The sensor exhibits significantly enhanced selectivity toward Al³⁺ ions over the concentration range 1.0 × 10⁻⁸-1.0 × 10⁻¹ M with a lower detection limit of 5.0 × 10⁻⁹ M and a Nernstian slope of 20.3 ± 0.1 mV decade⁻¹ of activity. Influence of the membrane composition and possible interfering ions was investigated on the response properties of the electrode. Fast and stable response, good reproducibility and long-term stability are demonstrated. The sensor shows response time of <5 s and can be used for about 3 months without any considerable divergence in their potential response. Selectivity coefficients determined by matched potential method (MPM) indicate high selectivity for aluminium (III) ion. The proposed electrode shows fairly good discrimination of aluminium (III) from many metal ions. It was successfully applied for direct determination of aluminium (III) in biological, industrial and environmental samples. The electrode can be used in the pH range of 2.0-9.0 and mixtures containing up to 20% (v/v) non-aqueous content. It was used as an indicator electrode in potentiometric titration of aluminium ion vs. EDTA.     

Effect of Pt addition on the isomerization properties of MoO2 − x(OH)y deposited on TiO2

Isomerization of n-hexane and n-pentane were studied using equivalent 5 monolayers of MoO₃ deposited on TiO₂. Addition of 2.5% Pt by weight of MoO₃ on the Mo catalyst resulted in an increase in the catalytic activity of the system in favor of hydrocracking products. Surface characterization by XPS-UPS and ISS reveal that the sample surface contains Oxygen, Molybdenum, Platinum and Titanium. Apparently, the metallic properties of the deposited Pt favors the hydrocracking reactions and becomes dominant at reaction temperatures higher than 623 K. Balanced metal-acid functions in MoO_2 − x(OH)_y phase seems to be in optimized condition toward the hydroisomerization process. The contribution of Platinum addition to this catalytic reaction is not obvious. Combination of surface XPS-UPS, ISS and catalytic reactions carried out at similar experimental conditions enabled us to have better insight concerning the catalytic activities of the different chemical species present on the sample surface.     

Pulse and pulse reverse plating—Conceptual, advantages and applications

A review on pulse and pulse reverse techniques for electrodeposition have been attempted. Pulse electrodeposition (PED) of some metals and alloys are reported. The effects of mass, transport, electrical double layer pulse parameters and current distribution on surface roughness and morphology are presented. Applications, advantages and disadvantages of PC and PRC techniques are discussed along with theoretical aspects and mechanism.     

Novel conductive magnetic nanocomposite based on poly (indole-co-thiophene) as a hemoglobin diagnostic biosensor: Synthesis,characterization and physical properties

The novel conductive nanocomposite has been successfully prepared by emulsion polymerization. First, magnetite nanoparticles were synthesized via coprecipitation reaction. Then, poly (indole-co-thiophene)@Fe₃O₄ nanocomposite was prepared via emulsion copolymerization of indole and thiophene monomers using sodium dodecyl sulfate as an emulsifier and ammonium persulfate as an oxidant in the presence of Fe₃O₄ nanoparticles. Characterization of the synthesized copolymer, Poly (In-co-T), and its magnetic nanocomposite were studied by Fourier transform infrared spectra, X-ray diffraction, scanning electron microscopy, thermal gravimetric analysis, differential scanning calorimetric, UV-vis spectrophotometer, and vibrating sample magnetometer. Also, the electrical conductivity of copolymer and nanocomposite were determined by four-probe instrument. Results showed a synergic effect in thermal stability by good interaction between polymer chain and magnetic nanoparticles. The conductivity of the nanocomposite was higher than bare copolymer, and increase of nanoparticles content caused an increment in the conductivity of the nanocomposites. The applicable properties of proposed conductive nanocomposite as a base at electrochemical biosensing have been investigated.     

Self-assembled nano-arrays of single-walled carbon nanotube-octa(hydroxyethylthio)phthalocyaninatoiron(II) on gold surfaces: Impacts of SWCNT and solution pH on electron transfer kinetics

The construction by sequential self-assembly process of reproducible, highly stable and pH-responsive redox-active nanostructured arrays of single-walled carbon nanotubes (SWCNTs) integrated with octa(hydroxyethylthio)phthalocyaninatoiron(II) (FeOHETPc) via ester bonds on a gold surface (Au-Cys-SWCNT-FeOHETPc) is investigated and discussed. The successful construction of this electrode is confirmed using atomic force microscopy and X-ray photoelectron spectroscopy as well as from the distinct cyclic voltammetric and electrochemical impedance spectroscopic profiles. The Au-Cys-SWCNT-FeOHETPc electrode exhibited strong dependence on the reaction of the head groups and the pH of the working electrolytes, the surface pK_a is estimated as 7.3. The high electron transfer capability of the Au-Cys-SWCNT-FeOHETPc electrode over other electrodes (Au-Cys-SWCNT or the Au-Cys-FeOHETPc or the Au-FeOHETPc) suggests that SWCNT greatly improves the electronic communication between FeOHETPc and the bare gold electrode. The electron transfer rate constant (k_app) of Au-Cys-SWCNT-FeOHETPc in pH 4.8 conditions (∼1.7 × 10⁻² cm⁻² s⁻¹) over that of the electrode obtained from SWCNT integrated with tetraaminophthalocyninatocobalt(II) (Au-Cys-SWCNT-CoTAPc) (5.1 × 10⁻³ cm⁻² s⁻¹) is attributed to the possible effect of the central metal on the phthalocyanine core and substituents on the peripheral positions of the phthalocyanine rings. We also prove that aligned SWCNT arrays exhibit much faster electron transfer kinetics to redox-active species in solutions compared to the randomly dispersed (drop-dried) SWCNTs.     

Identification,Functional Study,and Promoter Analysis of HbMFT1, a Homolog of MFT from Rubber Tree (Hevea brasiliensis)

A homolog of MOTHER OF FT AND TFL1 (MFT) was isolated from Heveabrasiliensis and its biological function was investigated. Protein multiple sequence alignment and phylogenetic analysis revealed that HbMFT1 conserved critical amino acid residues to distinguish MFT, FLOWERING LOCUS T (FT) and TERMINAL FLOWER1 (TFL1)-like proteins and showed a closer genetic relationship to the MFT-like group. The accumulation of HbMFT1 was generally detected in various tissues except pericarps, with the highest expression in embryos and relatively higher expression in roots and stems of seedlings, flowering inflorescences, and male and female flowers. HbMFT1 putative promoter analysis showed that tissue-specific, environmental change responsive and hormone-signaling responsive elements were generally present. HbMFT1 was strongly induced under a short-day condition at 28 °C, with the highest expression after the onset of a day. Overexpression of HbMFT1 inhibited seed germination, seedling growth, and flowering in transgenic Arabidopsis. The qRT-PCR further confirmed that APETALA1 (AP1) and FRUITFULL (FUL) were drastically down-regulated in 35S::HbMFT1 plants. A histochemical β-glucuronidase (GUS) assay showed that HbMFT1::GUS activity was mainly detected in stamens and mature seeds coinciding with its original expression and notably induced in rosette leaves and seedlings of transgenic Arabidopsis by exogenous abscisic acid (ABA) due to the presence of ABA cis-elements in HbMFT1 promoter. These results suggested that HbMFT1 was mainly involved in maintenance of seed maturation and stamen development, but negatively controlled germination, growth and development of seedlings and flowering. In addition, the HbMFT1 promoter can be utilized in controlling transgene expression in stamens and seeds of rubber tree or other plant species.     

Homogeneous Nature of Malaysian Marine Fish Epinephelus fuscoguttatus (Perciformes; Serranidae): Evidence Based on Molecular Markers,Morphology and Fourier Transform Infrared Analysis

Taxonomic confusion exists within the genus Epinephelus due to the lack of morphological specializations and the overwhelming number of species reported in several studies. The homogenous nature of the morphology has created confusion in the Malaysian Marine fish species Epinephelus fuscoguttatus and Epinephelus hexagonatus. In this study, the partial DNA sequence of the 16S gene and mitochondrial nucleotide sequences of two gene regions, Cytochrome Oxidase Subunit I and III were used to investigate the phylogenetic relationship between them. In the phylogenetic trees, E. fuscoguttatus was monophyletic with E. hexagonatus species and morphology examination shows that no significant differences were found in the morphometric features between these two taxa. This suggests that E. fuscoguttatus is not distinguishable from E. hexagonatus species, and that E. fuscoguttatus have been identified to be E. hexagonatus species is likely attributed to differences in environment and ability to camouflage themselves under certain conditions. Interestingly, this finding was also supported by Principal Component Analysis on Attenuated Total Reflectance–Fourier-transform Infrared (ATR-FTIR) data analysis. Molecular, morphological and meristic characteristics were combined with ATR-FTIR analysis used in this study offer new perspectives in fish species identification. To our knowledge, this is the first report of an extensive genetic population study of E. fuscoguttatus in Malaysia and this understanding will play an important role in informing genetic stock-specific strategies for the management and conservation of this highly valued fish.     

Influence of A-site Ba substitution on microwave dielectric properties of (BaxMg1−x)(A0.05Ti0.95)O3 (A=Zr,Sn) ceramics

The microwave dielectric properties of (Ba_xMg_1−x)(A_0.05Ti_0.95)TiO₃ (A=Zr, Sn) ceramics were investigated with regard to substitution of Ba for Mg of A-site. The microwave dielectric properties were correlated with the Ba content. With an increase in Ba content from 0.01 to 0.1, the dielectric constant and the τ_f value increased, but the Q×f value decreased. The sintered (Ba_xMg_1−x)(Zr_0.05Ti_0.95)TiO₃ (called B_xMZT) ceramics had a permittivity in the range of 19.1−20.6, quality factor from 180,000 to 25,000 GHz, and variation in temperature coefficient of resonant frequency from −35 to −39 ppm/°C with increasing composition x. For sintered (Ba_xMg_1−x)(Sn_0.05Ti_0.95)TiO₃ (called B_xMST) ceramics, the dielectric constant increased from 19 to 20.5, Q×f value increased from 120,000 to 37,000 (GHz), and the τ_f value increased from −50 to −3.3 ppm/°C as the x increased from 0.01 to 0.1. When A=Sn and x=0.1, (Ba_0.1Mg_0.9)(Sn_0.05Ti_0.95)TiO₃ ceramics exhibited dielectric constant of 20.5, Q×f value of 37,000 (GHz), and a near-zero τ_f value of −3.3 ppm/°C sintered at 1210 °C for 4 h.