Influence of structure of poly(<Emphasis Type="Italic">o</Emphasis>-phenylenediamine) on the doping ability and conducting property

Poly(o-phenylenediamine) with ladder-type structure was formed in aqueous hydrochloric acid medium below pH 1, while open ring-type amine derivative, i.e., ?NH₂ functional group substitution of polyaniline structure, was obtained in 1:1 aqueous sulfuric acid medium from the chemical synthesis of the monomer o-phenylenediamine. However, poly(o-phenylenediamine) having structure like polyaniline derivative with free =NH functional groups was obtained by chemical synthesis in dimethyl sulfoxide medium. The ladder-type polymer was almost insoluble but the other two types of synthesized polymers having polar functional group substitutions were well soluble in polar organic solvent like dimethyl sulfoxide, N,N-dimethyl formamide, and tetrahydrofuran. The freestanding films were cast from dimethyl sulfoxide solution of both the soluble functional polymers. The polymers having different structures were doped with inorganic acid by solution doping technique and the doped polymers were characterized by various standard characterizations. In order to explore the electronic uses of the polymers like sensor and actuators, the influences of their structure on the doping ability as well as ionic properties of the sulfuric acid-doped polymers were compared.     

Swelling Behavior of Physically Cross-Linked Gelatin Gels in Varied Salt Solutions

A series of physically cross-linked gelatin networks were prepared and the effects of salt concentration and chemical valence of the salt ions on the swelling properties of the gelatin gels were studied in detail. It was found that the swelling behaviors as polyelectrolytic or polyampholytic gels depended on the charge distribution on the gelatin chains. The swelling capacity of polyelectrolytic gels with excess positive charges decreased with an increase in salt concentrations. However, the swelling capacity of polyelectrolytic gels with excess negative charges showed a nonmonotonic change with salt concentration. For polyampholytic gels, the equilibrium swelling ratio increased monotonously with the concentration of NaCl and CaCl₂ solutions_. On the other hand, the swelling capacities of the polymer networks increased first and were then followed by a decrease with an increase in the concentration of AlCl₃ solution. Moreover, the swelling kinetics of the gelatin gels in varied salt solutions with different concentrations was also investigated.     

Viscometric Study of the Gelatin Solutions Ranging from Dilute to Extremely Dilute Concentrations

The viscosity of gelatin solutions with concentrations between 10^?4 and 10^?5 g/cm³, covering the extremely dilute zones, was studied via a photoelectric viscometer, and the effects of the electrolyte, pH, surfactant, urea, and temperature were discussed. The results showed that the reduced viscosity (η_sp/C) of gelatin exhibited a drastic increase with dilution in the extremely dilute aqueous solutions, this being a typical polyelectrolyte effect. The reduced viscosity of gelatin underwent several oscillations with varying pH; the minimum value of the viscosity was at pH = 5.0, corresponding to its isoelectric point, where gelatin exhibited antipolyelectrolyte behavior. The reduced viscosity of gelatin decreased with increasing temperature, which was due to the helix–coil transition in the gelatin solution. The temperature of the helix–coil transition was 30.0°C in gelatin aqueous solution; however the temperature of helix–coil transition decreased to 20.0°C in urea. Upon cooling, the gelatin molecules in aqueous solution underwent a coil–helix transition. Hydrophobic interactions caused chain folding in the presence of the surfactant sodium dodecylsulphate.     

Modeling of CN-functionalized silica as vehicle for delivery of the chemotherapeutic agent: cisplatin

The adsorption of cisplatin and its complexes, cis-[PtCl(NH₃)₂]⁺ and cis-[Pt(NH₃)₂]²⁺, on a CN-functionalized SiO₂(111) surface has been studied by the atom superposition and electron delocalization method. The adiabatic energy curves for the adsorption of the drug and its complexes on the delivery system were considered. Electronic structure and bonding analyses were also performed. The molecules are adsorbed on the functionalized surface resulting in a major absorption of the cis-[Pt(NH₃)₂]²⁺ complex. The molecule?Csurface interactions are strengthened due to the incorporation of the CN silane group. The most important bonds occur through Pt?CC, Pt?CN and Pt?CSi interactions. Despite the new interactions, the functionalized carrier maintains its matrix properties after adsorption. The remarkable properties may be attributed to the small electronic structure changes in the Si?CCN groups caused by the interaction with neighboring cisplatin molecules and the enhancement in Pt-bonding interactions due to the surface incorporation of the CN silane groups.     

Gelation,Network Structure and Properties of Physically Crosslinked Gelatin Gels: Effect of Salt Cation Valence

A series of physically cross-linked gelatin networks with and without salts (NaCl, CaCl₂ and CrCl₃) were prepared. The effect of the valence of the cations at the same concentration on the gelation of the gelatin was investigated by a rheometer. It was found that both the gelation temperature and the distance between crosslinks of the networks increased with an increase in valence of the cations. However, the opposite trend was observed for the storage modulus of the gels. Moreover, the influences of the valence and concentration of cations on the swelling and thermal behaviors of the gelatin composite films were studied in detail. It was generally observed that the equilibrium swelling ratio (ESR) decreased with salt concentration for all three cations following the trend ESR for Cr³⁺ <Ca²⁺ <Na⁺. However, the glass transition temperature (T_g) showed an opposite dependence on the valence and concentration of the cations. The relationships between the network structure and the properties of the gelatin composite films are discussed based on two effects (shielding and crosslinking effect), caused by the introduction of the salts.     

Fabrication of In-rich AgInS<Subscript>2</Subscript> nanoplates and nanotubes by a facile low-temperature co-precipitation strategy and their excellent visible-light photocatalytic mineralization performance

Visible-light-driven In-rich AgInS₂ nanoplates and nanotubes were successfully prepared by a convenient co-precipitation strategy at low temperature. The effect of different In/Ag molar ratio in the raw materials on the physicochemical properties and photocatalytic activity of AgInS₂ was investigated. The In/Ag molar ratio has an obvious effect on the morphology of AgInS₂, and the physicochemical properties and photocatalytic activity of AgInS₂ are also dependent on the In/Ag molar ratio. When the molar ratio of In/Ag is 9, the photoluminescence intensity of AgInS₂ reaches a minimum value, while its photocurrent density is maximum (0.011 mA/cm²), indicating the most efficient separation of electron-hole pairs. The AgInS₂ with the In/Ag molar ratio of 9 exhibits the highest visible-light photocatalytic activities with almost complete degradation of 2-nitrophenol, which is attributed to the narrowest band gap and the most efficient separation of electron-hole pairs. Moreover, In-rich AgInS₂ exhibits excellent regeneration ability.     

Structure and magnetic properties of nanocrystalline cobalt ferrite powders synthesized using organic acid precursor method

Nanocrystalline octahedra of cobalt ferrite CoFe₂O₄ powders were synthesized using the organic acid precursor route. The effect of the calcination temperature, Fe³⁺/Co²⁺ molar ratio, calcination time and type of organic acid (oxalic, benzoic and tartaric acids) on the formation, crystallite size, microstructure and magnetic properties was studied systematically. The Fe³⁺/Co²⁺ molar ratio was varied from 2 to 1.739 while the annealing temperature was controlled from 400 to 1000 °C for various periods from 0.5 to 2 h. The resulting powders were investigated using X-ray diffraction (XRD) analysis, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). XRD results indicate that a well crystallized, single spinel cobalt ferrite phase was formed for the precursors annealed at 600-800 °C for 2 h, using oxalic and tartaric acids as precursors for Fe³⁺/Co²⁺ molar ratio 1.818. The crystallite size of as-formed powders was in the range of 38.0-92.6 nm at different operating conditions. The calcination temperature and Fe³⁺/Co²⁺ molar ratio have a significant effect on the microstructure of the produced cobalt ferrite. The microstructure of the produced powders was found to be octahedra-shaped. The crystalline, pure cobalt ferrite powders with magnetic properties having a maximum saturation magnetization (76.1 emu/g) was achieved for the single phase at Fe³⁺/Co²⁺ molar ratio 1.818 and annealing temperature of 600 °C for 2 h using tartaric acid precursor.     

Molten salt synthesis of LaF<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> nanoplates with tunable size and their luminescence properties

A molten salt route to LaF₃:Eu³⁺ nanoplate with tunable size was developed and the products were characterized by the X-ray diffraction (XRD), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM) and high-resolution TEM (HR-TEM). It is found that the nanoplates with different sizes (ca. 46, 20, and 12 nm) could be obtained when the molar ratio of the reagents NH₄F and La(NO₃)₃ · 6H₂O was adjusted. The possible formation process of reaction was discussed, and the reasonable mechanism of size controlling was also proposed. Furthermore, the luminescent properties of all the samples with different sizes and doping levels were investigated at room temperature.     

Preparation of activated carbon from cherry stones by chemical activation with ZnCl2

Cherry stones (CS), an industrial product generated abundantly in the Valle del Jerte (Cáceres province, Spain), were used as precursor in the preparation of activated carbon by chemical activation with ZnCl₂. The influence of process variables such as the carbonisation temperature and the ZnCl₂:CS ratio (impregnation ratio) on textural and chemical-surface properties of the products obtained was studied. Such products were characterised texturally by adsorption of N₂ at −196 °C, mercury porosimetry and density measurements. Information on the surface functional groups and structures of the carbons was provided by FT-IR spectroscopy. Activated carbon with a high development of surface area and porosity is prepared. When using the 4:1 impregnation ratio, the specific surface area (BET) of the resultant carbon is as high as 1971 m² g⁻¹. The effect of the increase in the impregnation ratio on the porous structure of activated carbon is stronger than that of the rise in the carbonisation temperature, whereas the opposite applies to the effect on the surface functional groups and structures.     

Proton-conducting biopolymer electrolytes based on pectin doped with NH4X (X=Cl,Br)

Research has been undertaken to develop polymer electrolytes based on biodegradable natural polymers such as cellulose acetate, starch, gelatin, and chitosan, which are being used as polymer hosts for obtaining new polymer electrolytes for their applications in various electrochemical devices such as batteries, sensors, and electrochromic windows. Pectin is a naturally available material which is extracted from the skin of citrus fruits. Pectins, also known as pectic polysaccharides, are rich in galacturonic acid. The present study focuses on the proton-conducting polymer electrolytes based on the biopolymer pectin doped with ammonium chloride (NH₄Cl) and ammonium bromide (NH₄Br) prepared by solution casting technique. The prepared membranes are characterized using XRD, FTIR, and AC impedance techniques to study their complexation behavior, amorphous nature, and electrical properties. The conductivity of pure pectin membrane has been found to be 9.41 × 10⁻⁷ S cm⁻¹. The polymer systems with 30 mol% NH₄Cl-doped pectin and 40 mol% NH₄Br-doped pectin have been found to have maximum ionic conductivity of 4.52 × 10⁻⁴ and 1.07 × 10⁻³ S cm⁻¹, respectively. The conductivity value has increased by three orders of magnitude compared to pure pectin membrane. The dielectric behavior of both the systems has been explained using dielectric permittivity and electric modulus spectra.

     

Synthesis of Hydrophobic Cationic Chitosan Flocculant and Its Sludge Dewatering Property

The hydrophobic cationic chitosan (HTCC) flocculant was synthesized by reacting chitosan with epoxy propyl trimethyl ammonium chloride (EPTAC) and (2,3-epoxy propyl) dodecyl dimethyl ammonium chloride (EDC), to improve its waste sludge dewaterability. By FTIR and ¹H NMR analysis, EPTAC and EDC were confirmed to be grafted onto the molecular chains of chitosan (CTS) successfully. With the increase of EDC content, G′ of HTCC aqueous solution with 1:1.5:1.5 mole ratio of CTS:EPTAC:EDC consistently showed higher values than G″ over the entire frequency range explored, indicating the formation of a physically cross-linked network. The crystallization ability of HTCC decreased compared with pristine CTS. The long alkyl chains on the EDC molecules enhanced the hydrophobicity of HTCC, and better dewaterability of the waste sludge was achieved through the promoted bridging action of HTCC.     

［Mg(NH2)2］n(n=1—5)团簇的密度泛函理论研究

用密度泛函理论的杂化密度泛函B3LYP方法在6-31G^*基组水平上对［Mg(NH₂)₂］_n(n=1—5)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.对最稳定结构的振动特性、成键特性、电荷特性等进行了理论研究.结果表明：团簇易形成链状结构,Mg—N键长为0.190—0.234 nm,N—H键长为0.101—0.103 nm,H—N—H键角为100.2°—107.5°;团簇中M 关键词： 2)₂］_n(n=1—5)团簇')" href="#">［Mg(NH₂)₂］_n(n=1—5)团簇 密度泛函理论 结构与性质 储氢材料     

The structure and the analytical potential energy function of NH2 （X^2B1）

This paper reports that the equilibrium structure of NH2 has been optimized at the QCISD/6-311＋＋G （3df, 3pd） level. The ground-state NH2 has a bent （C2v, X^2B1） structure with an angle of 103.0582°. The geometrical structure is in good agreement with the other calculational and experimental results. The harmonic frequencies and the force constants have also been calculated. Based on the group theory and the principle of microscopic reversibility, the dissociation limits of NH2（C2v, X^2B1） have been derived. The potential energy surface of NH2（X^2B1） is reasonable. The contour lines are constructed, the structure and energy of NH2 reappear on the potential energy surface.     

Controlling the stability and the electronic structure of transition metal dichalcogenide single layer under chemical doping

By means of ab initio calculation based on density-functional theory (DFT), we have investigated the electronic and optical properties of single layer MoSe₂ under chemical doping by various groups, such as ?H, ?OH, ?NH₂ and ?CH₃. This work is generalized for all polymorph 1H, 1T, 1T′ and the new investigated phase 1T″. We found that all those functional groups (FG) bonded covalently to the chalcogen atom (Se). The evaluation of adsorption energy shows that the hydrogen atom binds more strongly than other functional groups in particular with the T phase. Furthermore, the attachment of functional groups to T-MoSe₂ leads to dramatic changes to the structure stability and the optoelectronic properties of the material by tuning its band gap from metallic to a semiconductor. Also, we found that the band gap is strongly depending on the type and the densities of dopants.     

Surface‐enhanced Raman evidence for Rhodamine 6 G and its derivative with different adsorption geometry to colloidal silver nanoparticle

Some high‐affinity functional groups or resonant molecules were often used as probe molecules adsorbed on silver nanoparticles for Surface‐enhanced Raman scattering (SERS). However, it is still unclear how the attached molecules interact with the silver nanoparticles' surface, and how the anchoring groups affect the optical and electronic properties of molecules. Here, we report that surface‐enhanced Raman studies of two organic compounds; rhodamine 6G (R6G) and its aminated derivative (R‐NH₂) have very different functional groups for surface binding but nearly identical SERS spectroscopic properties at pH = 7 and UV–vis at pH = 3, respectively. A surprise was found that under the same experimental conditions, the SERS signal intensity for R6G is nearly 50‐fold higher than that of R‐NH₂. Furthermore, the pH‐dependent study reveals that the structure of R6G is irreversibly stabilized or ‘locked’ in its form and no longer responsive to pH changes. In contrast, R‐NH₂ is still sensitive to pH, and can be switched between its open‐ring and closed‐ring structures. Copyright © 2013 John Wiley & Sons, Ltd.     

Spectral Studies On Some 2-Quinolones

Spectral properties of some 2-Quinolones were investigate-ed. IR and ¹H NMR were applied to characterize the ligands. The hydrogen bond property is of important parameter for controlling the behaviour of the compounds. The N[sbnd]H, O[sbnd]H, C[dbnd]O, C[sbnd]H, and C[sbnd]N fundamental functional groups are characterized. The electronic transitions are assigned. The data are explained on the basis of molecular structure and substituents effects. The acid-base equilibria and the phenomena of tautomerism for these compounds are explained and discussed. The acid exponents (pK_OH, and pK_NH) are evaluated.     

Properties of Polyamide-6 Composites Reinforced with Hydroxyapatite Nanospheres

Hydroxyapatite nanospheres (nHA) were first synthesized from (NH₄)₂HPO₄ and CaCl₂ precursors in the presence of poly(vinyl alcohol) templates. The structure and morphology of as-synthesized products were examined by materials characterization techniques. X-ray diffraction patterns and Fourier transform infrared spectra showed that the nHA (50–70 nm) exhibit the crystalline structure and vibration bands of HA. The Ca/P molar ratio of nHA approached the stoichiometric value of 1.67. The nHA were then melt blended with polyamide-6 (PA6), followed by injection molding. Tensile and flexural measurements showed that the tensile and bending strengths of injection molded PA6–10 wt% nHA composite were close to those of human cortical bone. A simulated body fluid immersion test revealed that apatite crystals can be readily deposited on the PA6–10 wt% nHA composite surface after immersion for 30 days.     

Plasma-based introduction of monosort functional groups of different type and density onto polymer surfaces. Part 1: Behaviour of polymers exposed to oxygen plasma

Several approaches were investigated to produce monosort functionalized polymer surfaces with a high density and homogeneity of functional groups: (i) Plasma oxidation followed by wet-chemical reduction, (ii) formation of radicals and grafting on of functional group carrying molecules, (iii) plasma bromination followed by (iv) Williamson or Gabriel-like synthesis of spacer molecules, and (v) a pulsed plasma polymerization of functional groups bearing monomers or (vi) their copolymerisation with other comonomers. The formation of hydroxyl (OH), primary amino (NH₂), and carboxyl (COOH) groups was studied in detail. The oxygen plasma treatment (i) in a low-pressure non-isothermal glow discharge results in the formation of a wide variety of O functional groups, polymer degradation and crosslinking. Low power densities and short exposure times (0.1 to 2 s) are required to functionalize a surface while preserving the original polymer structure. Carbonate, ester, and aromatic groups are rapidly degraded by an oxygen plasma treatment leading to scissions of polymer backbones and loss in molecular weight. Also the formation of macrocycles and C=C bonds was observed in a region of around 4 nm in depth. The investigated polymers could be classified by their degradation behaviour on exposure to the oxygen plasma. In order to maximize the process selectivity for OH groups, the variety of oxygen functionalities formed by the oxygen plasma was wet-chemically reduced by diborane, vitride? (Na complex), and LiAlH₄. Typical yields were 9 to 14 OH groups per 100 carbon atoms. Plasma bromination (iii) (40 Br per 100 C atoms) of polymers, followed by grafting of spacer molecules (iv), has been proved to be a highly selective reaction. Another way to produce high densities of monosort functionalities was the pulsed plasma polymerization of functional group bearing monomers such as allylamine, allylalcohol or acrylic acid (v). The retention of chemical structure and functional groups during plasma polymerization was achieved by using low power densities and the pulsed plasma technique. The maximum yields were 30 OH, 18 NH₂, and 24 COOH groups per 100 C atoms. To vary the density of functional groups a chemical copolymerization with 'chain-extending' comonomers such as butadiene and ethylene was initiated in the pulsed plasma (vi). Additionally, the often-observed post-plasma oxidations of such layers initiated by reaction of trapped radicals with oxygen from the air were successfully suppressed by using NO gas as radical quencher.     

Surface modification of indium tin oxide films by amino ion implantation for the attachment of multi-wall carbon nanotubes

Amino ion implantation was carried out at the energy of 80 keV with fluence of 5 × 10¹⁵ ions cm⁻² for indium tin oxide film (ITO) coated glass, and the existence of amino group on the ITO surface was verified by X-ray photoelectron spectroscopy analysis and Fourier transform infrared spectra. Scanning electron microscopy images show that multi-wall carbon nanotubes (MWCNTs) directly attached to the amino ion implanted ITO (NH₂/ITO) surface homogeneously and stably. The resulting MWCNTs-attached NH₂/ITO (MWCNTs/NH₂/ITO) substrate can be used as electrode material. Cyclic voltammetry results indicate that the MWCNTs/NH₂/ITO electrode shows excellent electrochemical properties and obvious electrocatalytic activity towards uric acid, thus this material is expected to have potential in electrochemical analysis and biosensors.     

NH3在Ni/Pt(111)和Ni/WC(001)表面上分解的第一性原理研究

采用密度泛函理论和slab模型,研究NH₃在Ni单原子层覆盖的Pt（111）和WC（001）表面上的物理与化学行为,计算了Ni单原子覆盖表面的电子结构以及NH₃的吸附与分解.表面覆盖的单原子层中,Ni原子的性质与Ni（111）面上的Ni原子明显不同.与Ni（111）相比,Ni/Pt（111）和Ni/WC（001）表面上Ni原子dz²轨道上的电子更多地转移到了其它位置,该轨道上电荷密度降低有利于NH₃吸附.在Ni/Pt（111）和Ni/WC（001）面上NH₃吸附能均大于Ni（111）,NH₃分子第一个N-H键断裂的活化能则明显比Ni（111）面上低,有利于NH₃的分解,吸附能增大使NH₃在Ni/Pt（111）和Ni/WC（001）面上更倾向于分解,而不是脱附.N₂分子的生成是NH₃分解的速控步骤,该反应能垒较高,说明N₂分子只有在较高温度下才能生成.WC与Pt性质相似,但Ni/Pt（111）和Ni/WC（001）的电子结构还是有差异的,与Ni（111）表面相比,NH₃在Ni/Pt（111）表面上分解速控步骤的能垒降低,而在Ni/WC（001）上却升高.要获得活性好且便宜的催化剂,需要对Ni/WC（001）表面做进一步改进,降低N₂分子生成步骤的活化能.