Fast ethylamine gas sensing based on intermolecular charge-transfer complexation

We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride（CDBF） loaded poly（acrylonitrile） nanofiber based on an intermolecular charge-transfer complexation.Reversible response and recovery were achieved using alternating gas exposure.This system shows a fast ethylamine gas sensing within 0.4 s.

Sensitive Spectrofluorimetric Method for Determination of Fluoroquinolones through Charge-Transfer Complex Formation

A sensitive spectrofluorimetric method was developed for determination of ciprofloxacin (CPFX), levofloxacin (LEV), gatifloxacin (GAT) and moxifloxacin (MOX) in pure, commercial formulations, human urine and plasma. The method is based on charge-transfer (CT) complex with chloranilic acid. Fluorescence intensity of the complexes was measured at emission wavelength ranging from 445-492 nm with excitation wavelengths from 285-330 nm. At optimum experimental conditions, a linear calibration plot was obtained in the concentration range of 20-1000 ng·mL-1, 60-320 ng·mL-1, 20-800 ng·mL-1 and 20 -00 ng·mL-1 for CPFX, LEV, MOX and GAT, respectively with good correlation coefficient in the range of 0.9929-1.0 in methanolic medium. The limit of detection and limit of quantification were found to be 5 ng·mL-1 and 18 ng·mL-1 for CPFX, 12 ng·mL-1 and 40 ng·mL-1 for LEV, 8 ng·mL-1 and 19 ng·mL-1 for MOX, 6 ng·mL-1 and 19 ng·mL-1 for GAT, respectively. The method was found free of interferences from excipients used as additive in pharmaceutical preparations, some common cations and compounds present in urine and plasma as well as co-administered analgesic, vitamins and other drugs. The method was successfully applied for quantification of selected fluoroquinolones in commercial formulations and also in spiked human urine and plasma samples with percent recoveries of 100.0 ± 1.56 and 100.2 ± 1.29 respectively.

Highly efficient H-bonding charge-transfer complex for microsupercapacitors under extreme conditions of low temperatures

Owing to sluggish ionic mobility at low temperatures, supercapacitors, as well as other energy-storage devices, always suffer from severe capacity decay and even failure under extreme low-temperature circumstances. Solar-thermal-enabled self-heating promises an attractive approach to overcome this issue.Here, we report a unique H-bonding charge-transfer complex with a high photothermal conversion efficiency of 79.5% at 405 nm based on chloranilic acid and albendazole. Integrated with a microsupercapacitor, the chloranilic acid-albendazole complex(CAC) film prompts an apparent temperature increase of 22.7 °C under 1 sun illumination at-32.6 °C, effectively elevating the working temperature of devices.As a result, the rate capability of the microsupercapacitor has been significantly improved with a 17-fold increase in capacitance at a current density of 60 μA cm^(-2), leading to outstanding low-temperature performances. Importantly, the integrated device is capable of working at a low temperature of-30 °C in the open air, which demonstrates the potential of CAC in practical applications for low-temperature ultracapacitive energy-storage devices.

SPECTROPHOTOMETRIC STUDY OF DDQ CHARGE-TRANSFER COMPLEXES WITH 1,10-PHENANTHROLINE AND ITS DERIVATIVES

1,10-phenanthroline and its derivatives can form charge-transfer complexes with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone(DDQ).The absorption spectra and conditions of complex formation,such as the reaction time,the quantity of DDQ, and the solvents, have been studied.After the HMO calculation of phenanthrolines,the molar absorptivities were found to depend on the substituents on the phenanthroline rings.

REACTIVITY RATIOS FOR COPOLYMERIZATION WITH THE PARTICIPATION OF A CHARGE-TRANSFER COMPLEX

The complexation between styrene (St) and N-phenylmaleimide (PMI) was investigated by H-1-NMR spectroscopy, and the existence of a complex was proved. The equilibrium constant of St/PMI in chloroform at 50 degrees C was determined to be 0.27. New elementary propagation reactions were proposed. On the basis of the propagation elementary reactions for copolymerization with the participation of a charge-transfer complex (CTC), a method for measuring the reactivity ratios is presented. Four reactivity ratios and relative reactivities of free monomer and CTC were obtained. They are r(12) = 0.034, r(21) = 0.012, r(1C) = 0.0030, r(2C) = 0.0034, and k(1C)/k(12) = 11.34, k(2C)/k(21) = 3.42.

Study on Alternating LB Films of Charge-Transfer Complex of Octadecyl-TCNQ and Copper Phthalocyanine Derivative

Infrared spectra of alternating LB films of octadecyl-TCNQ/CuPc are studied. Charge-transfer complexes are formed in LB films and conductance increases about three orders than that of pure CuPc LB films.

Preparation and Crystal Structure of a Charge-transfer Complex between an Organic Substrate and Molybdosilicic Acid [(CH_3)_2NH(CH_2)C_6H_5]_4SiMo_(12)O_(40)·2CH_3CN·H_2O

The charge transfer complex N,N-dimethylbenzylamine which is between the molybdosilicic acid and organic substrate has been prepared. Yellow crystals of the title compound ([(CH3)2NH(CH2)C6H5]4SiMo12O402CH3CNH2O) were synthesized from the mixture of water and acetonitrile. The single-crystal X-ray analysis reveals that the crystal crystallizes in triclinic system, space group P1 with a = 13.313(2), b = 14.673(2), c = 19.736(3) ? a = 86.22(1), b = 88.76(1), g = 66.97(1), V = 3540.2(9) 3 and Z = 2. The anion has the Keggin structure. The MoO bond distances range from 1.675(3) to 1.691(3) ?for the terminal oxygen atoms, 1.798(3) to 2.045(3) ?for the bridging ones, and 2.328(3) to 2.361(3) ?for those in the SiO4 tetrahedron. The SiO bond distances fall in the range of 1.623(3)～1.630(3) ?

Pyrrole and Pyrimidine Derivatives as Possible Electron Donors for Colored Charge-Transfer Complexes with a Weakly Electrophilic Energetic Material,FOX-7:A Theoretical Study

A number of electron-rich heterocycles are studied as potential reagents for visual colorimetric detection of FOX-7 due to colored charge-transfer complexes formation.The obtained results suggest that pyrrole and pyrimidine derivatives can form such complexes playing the role of electron donors despite a low electrophilicity of FOX-7.Density functional theory calculations,as well as quantum theory of atoms in molecules analysis,suggest stacking binding mode as the most preferable one with the binding energy of about 21-36 kJ/mol.All the complexes demonstrate a clear single charge-transfer absorption band in the visible region and the expected colors of the complexes are varying from violet and blue to red and orange.The calculations of the crystalline state of the studied complexes indicate high lattice energies,which are higher than that of pure FOX-7 and are close to the recently reported hydrogen-bonded complex of FOX-7 with 1,10-phenanthroline.Additional analysis of the studied charge-transfer complexes using properties based on density difference grids clearly suggests the acceptor role of FOX-7 in the complexes.This analysis can be effectively applied to identify the nature of other possible complexes of FOX-7,in which its role is unclear because of the specific reactivity,namely,both weak electrophilic and nucleophilic properties at the same time.

Synthesis and Characterization of Charge-transfer Complexes of Aminoethylphosphono-and Dimethylaminoethylphosphono-heteropolytungstic Acids of Keggin Type Structure

Two charge-transfer complexes of 2a and 2b of Keggin type were synthesized and characterized by elemental analysis, IR spectra, UV spectra, XRD, TG-DSC; and were compared with Hquin-PW12. The primary structure of the heteropolyanions had not been changed after the formation of the charge transfer complexes.

Cu(Ⅱ),Ni(Ⅱ)Complexation with Acid Alizarine Blue B in the Presence of Cetyltrimethylammonium Bromide

The coordination reactions of Cu（Ⅱ） and Ni（Ⅱ） with acid alizarine blue B （AABB） in the presence of cetyltrimethylammonium bromide （CTAB） micelle were investigated using the microsurface adsorptionspectral correction technique （MSASC）. The aggregation of AABB on CTAB followed the Langmuir isothermal adsorption law. The enrichment of AABB on CTAB sensitized the complexation between Cu（Ⅱ） or Ni（Ⅱ）and AABB. The binding ratio of AABB to CTAB was 1：2.5, and monomeric aggregate, AABB2CTAB5, was formed with an adsorption constant of 5.95×10^5 at 20 ℃ or 2.48×10^5 at 40 ℃. In the ternary complexation, the ratio of AABB：Cu and AABB：Ni were 1：1 and 1：2.5, respectively. Two types of aggregates, Cu2.AABB2·CTAB80 and Ni5.AABB2.CTAB80, were formed.

Species distribution of polymeric aluminium ferrum——timed complexation colorimetric analysis method of Al-Fe-Ferron

The effects of the calorimetric buffer solutions were investigated while the two colorimetric reactions of AI-ferron complex and Fe-ferron complex occurred individually, and the effects of the testing wavelength and the pH of the solutions were also investigated. A timed complexatian colorimetric analysis method of Al-Fe-ferron in view of the total concentration of {AI + Fe} was then established to determine the species distribution of polymeric Al-Fe. The testing wavelength was recommended at 362 net and the testing pH value was 5. With a comparison of the ratios of n(Al)/n(Fe), the standard adsorption curves of the polymeric Al-Fe solutions were derived from the experimental results. Furthermore, the solutions' composition were carious in both the molar n(Al)/n(Fe) ratios, i.e. 0/0, 5/5, 9/1 and 0/10, and the concentrations associated with the total ( Al + Fe which ranged from 10(-5) to 10(-4) mol/L..

Recent developments of surface complexation models applied to environmental aquatic chemistry

Based on numerous latest references, the current developments in surface complexation, surface precipitation and the corresponding models (SCMs and SPMs), were reviewed. The contents involved comparison on surface charge composition and layer-structure of solid-solution interface for the classical 1-pK and 2-pK models. In addition, the fundamental concept and relations of the new models, i. e., multi-site complexation (MUSIC) and charge- distribution (CD) MUSIC models were described as well. To avoid misuse or abuse, it must be emphasized that the applicability and limitation for each model should be considered carefully when selecting the concerned model(s). In addition, some new powerful techniques for surface characterization and analysis applied to model establishment and modification were also briefly introduced.

Inclusion complexes of cefuroxime axetil with β-cyclodextrin:Physicochemical characterization, molecular modeling and effect of Larginine on complexation

The inclusion complexes of poorly water-soluble cephalosporin, cefuroxime axetil(CFA), were prepared with β-cyclodextrin(βCD) with or without addition of L-arginine(ARG) to improve its physicochemical properties. We also investigated the effect of ARG on complexation efficiency(CE) of βCD towards CFA in an aqueous medium through phase solubility behaviour according to Higuchi and Connors. Although phase solubility studies showed AL(linear) type of solubility curve in presence and absence of ARG, the CE and association constant(Ks) of βCD towards CFA were significantly promoted in presence of ARG,justifying its use as a ternary component. The solid systems of CFA with βCD were obtained by spray drying technique with or without incorporation of ARG and characterized by differential scanning calorimetry(DSC), X-ray powder diffractometry(XRPD), scanning electron microscopy(SEM), and saturation solubility and dissolution studies. The molecular modeling studies provided a better insight into geometry and inclusion mode of CFA inside βCD cavity. The solubility and dissolution rate of CFA were significantly improved upon complexation with βCD as compared to CFA alone. However, ternary system incorporated with ARG performed better than binary system in physicochemical evaluation. In conclusion, ARG could be exploited as a ternary component to improve the physicochemical properties of CFA via βCD complexation.

Quantitative analysis of cefixime via complexation with palladium(Ⅱ) in pharmaceutical formulations by spectrophotometry

An optimized and validated spectrophotometric method has been developed for the determination of cefixime in pharmaceutical formulations. The method is based on the complexa- tion reaction between cefixime and palladium ion in the presence of acidic buffer solution （pH 3） in ethanol-distilled water medium at room temperature. The complex absorbed maximally at 352 nm. Beer＇s law is obeyed in the working concentration range of 2.5-35 μg/mL with apparent molar absorptivity of 1.015×104 L/mol cm and Sandell＇s sensitivity of 0.001 μg/cm2/0.001 absorbance unit. The limits of detection and quantitation for the proposed method are 0.175 and 0.583μg/mL, respectively. The effect of common excipients used as additives has been studied in the determination of cefixime. The proposed method has been successfully applied for the determina- tion of cefixime in pharmaceutical formulations. The results obtained by the proposed method were statistically compared with the reference method using t and F values and found no significant difference between the two methods.

Complexation separation for vanadium and chromium by dithiocarbamate and its application in treatment of chromium-vanadium-bearing slag

A novel method for the separation and reclamation of vanadium and chromium from acidic solution was proposed. The principle for the separation is based on selective complexation. In specific, V(V) can be complexated by dithiocarbamate to form VO(R1R2NCS2)3 precipitate, leaving Cr(Ⅲ) remained in the acidic solution. Then the reclamation of V and Cr from VO(R1R2NCS2)3 precipitate and Cr(Ⅲ)-bearing solution can be reached by decomplexation and neutralization, respectively. The kinetics of the complexation reaction was studied. In addition, the precipitation ratio of vanadium reached 97% and the loss of chromium was less than 4% after process optimization. The complexing agent could be regenerated with a high ratio of 99.5%. The method was successfully applied to treating chromium-vanadium-bearing slag produced in conventional vanadium production industry. Vanadium and chromium could be extracted from the slag in the form of calcium vanadate and Cr2O3 product with a purity of over 98%.

Effects of Anions and Cations on π-Complexation Between Olefin and Metal Halide

An ab initio molecular orbital study was performed to determine the effects of anions and cations on the π-complexation of C_2H_4 on MX(M=Ag, Cu; X=F, Cl). The calculated results show the following order of adsorption strength: F ->Cl - for anions; Cu +>Ag + for cations. The results can be explained by the detailed analysis of atomic charge, orbital energy and orbital population by using the natural bond orbital(NBO) theory: (1) anions with stronger electronegativity can attract more electrons from the s orbital of M, while at the same time it does not obviously weaken the d orbital occupation of M, thus the nearly vacant s orbital and the sufficiently filled d orbitals of M help with forming σ-donation and d-π * backdonation with the π orbital and the π * orbital of olefin, respectively; (2) a smaller energy gap of symmetry-adapted orbitals between olefin and a cation can favor the electron transfer, that is why Cu + forms stronger adsorption with olefin than Ag + does.

Enhancement of norfloxacin solubility via inclusion complexation with β-cyclodextrin and its derivative hydroxypropyl-β-cyclodextrin

The objectives of the study were to investigate the effects of β-cyclodextrin(βCD) and hydroxypropyl-β-cyclodextrin(HPβCD) on the solubility and dissolution rate of norfloxacin prepared using three different methods, at drug to cyclodextrin weight ratios of 1:1, 1:2, 1:4 and 1:8. All the methods increased the solubility and dissolution rate of norfloxacin via inclusion complexation with βCD and HPβCD. Norfloxacin was converted from crystalline to amorphous form through inclusion complexation. Solvent evaporation method was the most effective method in terms of norfloxacin solubilisation, while inclusion complex of HPβCD has higher solubility than βCD complex when prepared using the same procedure.

Determination of complexation capacity of trace metal-organic in natural water

The complexation capacity for heavy metals (Cu, Cd, Pb) were determined by anodic stripping voltammetry in South China Sea, Hulun Lake and Wuliang Suhai. The conditional stability constants and complexation capacity index were calculated. The data showed that the complexation capacity of the Hulun Lake was greater than that of seawater and Wuliang Suhai. The sequence of complexation capacity is C (CuL)> C (CdL)> C (PbL), the values are in concord with results of analysis on dissolved organic carbon. The conditional stability constants were in an opposite sequence: K (CuL)< K (CdL)< K (PbL). When log K are similar, the greater the complexation capacity, the greater the complexation capacity index.

Self-Assembled Film of Tb^(3+) and Poly(3- Thiophene Acetic Acid) via Layer-by-Layer Complexation Technique and Its Photoluminescence

The layer by layer complexation technique of polymer and metal ion was successfully utilized to fabricate the ultrathin multilayer film of poly(3 thiophene acetic acid (PTAA) and Tb 3+ ion by dipping the substrates alternatively in polymer and Tb 3+ ion aqueous solutions. UV-vis measurement revealed that the absorbance has linearity with the bilayer number from layer to layer and the X ray photoelectron spectrum (XPS) confirmed the existence of Tb 3+ ion. The pH of both the polymer and TbCl 3 solutions influence the thickness dramatically while the concentration of the solutions is not so sensitive. The luminescent spectrum of the complex film shows the characteristic emission of Tb 3+ ion as well as the ligand indicating the formation of the complex.

Adsorption，Oxidation and Complexation of Water－So－Inble Organic Snbstances in Soils

A greater part of water-solnble organic substances, accounting for 6070To of the total, could be adsorbedby soils, which included strongly and weekly reducing substances, positively and negatively charged substancesand substances containing amido. There existed a tendency of decrease in adsorption of the negativelycharged organic substances by the soil from South China to North China, with expression as Coulombianadsorption. A simultaneous reduction of iron and manganese appeared with clear voltammetric behavioursupon oxidation of water-soluble organic substances. Complexation of organic ligands with ferrons iron andmanganous manganese was proved by differential pulse voltammetric method, with disappearance of oxidationpeaks of ferrous iron and manganous manganese at 0.00 V and 0.35 V and occurrence of Fe`+-complex andMn￣2+ -complex at 0.75 V and 1.2 V respectively, whose peak potentials shifted backward.