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.

Intramolecular Charge Transfer Dual Fluorescence pH Sensing using p-Dibutylaminobenzoic Acid-β-cyclodextrin Inclusion Complex

The intramolecular charge transfer dual fluorescence of p-dibutylaminobenzoic acid-b-cyclodextrin inclusion complex showed a substantially higher sensitivity toward aqueous solution pH variation when compared with that of p-dibutylaminobenzoic acid alone, which established a new principle for direct CT fluorescence sensing in aqueous solution by using the CT fluorophore-cyclodextrin inclusion complex.

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.

Fabrication of Semiconductor Polymer Membranes Combined with a Colored Charge Transfer Complexes Used in the Manufacture of Solar Cells as a Source of Alternative Energy

The main task of this article was to prepared of new pigment model in situ solar cells accordance to charge-transfer complexes of rhodamine C(RhC) donor as dye laser gain media with iodine(σ-acceptor) and chloranilic acid, CLA(π-acceptor). The synthesis stoichiometry of these complexes were of 1∶2(donor∶acceptor) with general formulas [(RhC)]I·I3 and [(RhC)(CLA)2]. The discussed data of elemental analysis, conductivity measurements, FT-IR, UV-Vis spectroscopy and photometric titration data visualized the stoichiometry, formula and complexity of the complexes. The physicochemical and spectroscopic analyses obtained suggested that the electron transfer occurred through nitrogen atom in a tertiary amine —N(C2H5)2 of RhC donor with acceptor. The synthesized solid complexes were under go to thermogravimetric analyses to investigate their thermal stability and decomposition steps. The molar conductance measurements revealed that RhC complexes have an electrolytic statement. The thermal stability of rhodamine C complexes was enhanced in comparable with RhC itself. The polymer membranes of poly-methyl methacrylate)(PMMA) combined with the RhC charge(transfer complexes in chloroform solvent have been prepared and characterized by(infrared & electronic) spectroscopy and scanning electron microscopy(SEM) morphological examination. The photo-stability properties of the RhC complexes have been investigated.

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.

Estimation of Metformin Drug for the Diabetes Patients by Simple,Quick and Cheap Techniques within the Formation of Colored Charge Transfer Complexes

Metformin(Met)is a drug developed for the treatment of patients with typeⅡ diabetes.Recently,Met estimation in pharmaceutical formulations and human fluids has gained a growing interest.To extend requisite data that can be used to assessment of Met quantitatively based on charge-transfer(CT)complexation,the present study describes the synthesis and characterization of CT complexes that formed between drug Met and the organicπ-acceptors picric acid(PA),chloranilic acid(CLA),chloranil(CHL),7,7',8,8'-tetracyanoquinodimethane(TCNQ),and dichlorodicyanobenzoquinone(DDQ).The properties of the formed CT complexes were investigated by elemental,spectral(UV-visible,IR,and Raman spectroscopies),thermal(TG)and morphological(SEM)studies.IR results indicated that the complexation of Met with either PA or CLA acceptors occurs through proton transfer interaction,whereas its complexation with CHL,TCNQ,or DDQ acceptors occurs through n→π*interaction.

Charge transfer complex enabled photoreduction of ether phosphonium salts for the selective oxyalkylation of enamides

A charge transfer complex(CTC)-enabled photoreduction of ether phosphonium salts for the generation of oxyalkyl radicals was described.The photoreduction provides a convenient method to achieve selective oxyalkylation of enamides with broad substrate scope.The method features operational simplicity,mild and inherent green conditions.

Spectroscopic Analysis and Study of Charge Transport Properties for Pinacyanol Chloride-Organic Acceptor Complex as Potential Optoelectronics Material

Organic photoconductor, pinacyanol chloride, has been studied with infrared spectroscopy because of its thermal activation energy (Ea) and band gap (Eg = 2Ea) lying in the infrared range. Particularly, pinacyanol chloride and its charge transfer (CT) complexes with chloranil, DDQ, TCNQ and TCNE as organic acceptors are studied in details. The CT complexes are having neither two absorption edges like ternary complex having one donor and two acceptors nor binary type with Lorentzian or Gaussian envelopes. The forbidden gap is direct band gap except chloranil complex due to increase in molecular distance and CT interaction. There is imperfect nesting and partial screening determining the mid-IR envelope, which is qualitatively different from the envelopes in binary systems. There is inverted parabola in some range below this envelope. It is explained how infrared absorption is related with the applications of such organic photoconductors in optoelectronic devices.

Doping-induced charge transfer in conductive polymers

Molecular doping has become a widely used method to modulate the electric performance of organic semiconductors(OSC).Highly effective charge transfer during molecular doping is desired to achieve ideal electrical conductivity.Two types of charge transfer mechanisms are widely accepted in molecular doping process:integer charge transfer(ICT)and charge transfer complex(CTC).In this review,fundamental principles of two mechanisms are revisited and the characterization methods are depicted.The key points for the formation of two mechanisms are highlighted from aspects of molecular structure and process engineering.Then,the strategies to improve the proportion of ICT are discussed.Finally,the challenges and perspectives for future developments in the molecular doping of polymer semiconductors are provided.

Gaussian wave formalism model for propagation of charged-particle beam through a first-order optical systems

An elliptical Gaussian wave formalism model of a charged-particle beam is proposed by analogy with an elliptical Gaussian light beam. In the paraxial approximation, the charged-particle beam can be described as a whole by a complex radius of curvature in the real space domains. Therefore, the propagation and transform of charged-particle beam passing through a first-order optical system is represented by the ABCD-like law. As an example of the application of this model, the relation between the beam waist and the minimum beam spot at a fixed target is discussed. The result, well matches that from conventional phase space model, and proves that the Gaussian wave formalism model is highly effective and reasonable.

Spectrophotometric study of the charge transfer complexes of 4′-nitrobenzo-15-crown-5 and benzo-15-crown-5 with iodine in nonaqueous solvents

The formation of charge transfer complex between iodine with 4＇-nitrobenzo-15-crown-5（NB15C5） and benzo-15-crown-5 （B15C5） is investigated spectrophotometrically in chloroform and dichloromethane（DCM） solutions at 25℃.The pseudo-first-order rate constants for the transformation process were evaluated from the absorbance-time data and found to vary in the order of DCM CHCl_3.The values of the formation constant,K_f,for each complex are evaluated from Benesi-Hilebrand equation. Stability of the resulting complex in two solvents was also found to vary in the order of DCM CHCl_3.

Spectrophotometric Determination of Albendazole Drug in Tablets： Spectroscopic Characterization of the Chargetransfer Solid Complexes

Simple, rapid and reliable method for the determination of albendazole （ABZ） was described. This includes the utility of some π-acceptors such as 2,3-dichloro-5,6-dicyano-p-benzoquinone （DDQ） and 3,6-dichloro-2,5-dihydroxy-p-benzoquinone （p-CLA） for estimation of ABZ drug （act as donor）. The experimental conditions were optimized and the system obeys Beer＇s law for 7.50-80 and 10.00-85.00 ug·mL-1 of ABZ using DDQ and p-CLA, respectively. The molar absorptivity and Sandell sensitivity were calculated to be 1.83× 10^3 and 1.12× 10^3 L·mol ·cm -1 and 2.60 and 3.40 ng·cm -2 using DDQ and p-CLA, respectively. The limits of detection and quantification were calculated to be （7.42 and 6.73） and （9.94 and 4.13） ug·mL-1 using DDQ and p-CLA, respectively. The proposed methods were successfully applied to the determination of ABZ in commercially available dosage forms. The reliability of the assays was established by parallel determination by the official method and recovery studies. The chemical structures of the solid charge-transfer （CT） complexes formed via reaction between ABZ under study and π-acceptors, have been elucidated using elemental analyses （C, H and N）, IR, 1H NMR and mass spectra.

配体-金属电子转移强化类芬顿技术的破络特性与机制

为有效分解近中性废水中典型难降解强络合物Ni-EDTA,构建配体-金属电子转移强化类芬顿技术(LFGR),基于Ni(Ⅱ)去除效能等系统分析其在近中性条件下对Ni-EDTA的破络特性,重点探究Fe(Ⅲ)与H2O2投加量、pH值、浊度、常见有机酸与常规无机盐对LFGR破络特性的影响。结合H2O2消耗观测、自由基淬灭实验、自由基信号检测与降解产物分析等科学识别LFGR体系中主要活性氧物种,并进一步剖析Ni-EDTA的破络过程与主导机制。定量比较分析LFGR与其他UV活化氧化技术去除多种重金属EDTA络合物(M-EDTA)的特性,并进一步阐明LFGR的运行成本优势。对于络合物浓度为1.0 mmol/L的近中性模拟废水,LFGR的优化反应条件为:Fe(Ⅲ)投加量为0.1 mmol/L,H2O2投加量为50 mmol/L,UV光照时间为20 min。该条件下,EDTA可完全转化,且经碱沉淀后Ni(Ⅱ)去除率可高达99.40%;LFGR对水中常见有机酸与常规无机盐呈现出良好的抗干扰性;H_(2)O_(2)主要通过与配体-金属电子转移产生的Fe(Ⅱ)发生类芬顿反应消耗;LFGR的主要作用过程是Fe(Ⅲ)置换Ni(Ⅱ)并激发配体-金属电子转移反应从而促进EDTA光解,UV进一步驱动Fe(Ⅲ)还原并加快Fe物种循环,进而强化类芬顿技术活性氧自由基(主要为·OH和·O_(2)^(-))的催化作用。LFGR可在近中性条件下实现多种M-EDTA的良好破络效果,水处理费用合计为4.21元/t,具有良好技术经济性。

亚硫酸氢钠协同催化对苯醌加氢性能

利用亚硫酸氢钠与对苯醌加成反应形成的水溶性α-羟基亚硫酸钠衍生物可抑制醌氢醌的生成特点,考察了亚硫酸氢钠用量对醌氢醌的抑制效果,确定了对苯醌加氢反应的最优条件,并对亚硫酸氢钠的抑制机理进行了研究。实验结果表明,最佳的反应条件为氢气压力1.0 MPa、反应温度90℃、亚硫酸氢钠添加量为对苯醌量的25%(x)。添加亚硫酸氢钠可抑制对苯醌和对苯二酚的相互作用,在水相中,亚硫酸氢钠与对苯醌发生加成反应,阻断了对苯醌与对苯二酚之间氢键的形成,同时将对苯醌以水溶性α-羟基磺酸钠衍生物的形式存储,加氢时再调用,能有效抑制醌氢醌的形成,促进加氢反应进行。

Engineering intermolecular charge transfer in chiral organometallic crystals by rational doping for high-contrast CPL switches

The development of circularly polarized luminescence(CPL)switches is of great importance but challenging.Herein,a charge donor/acceptor pair comprising two chiral gold(I)-isocyanide complexes was designed to construct light-harvesting system via intermolecular charge-transfer(CT)interactions.By doping nonemissive S-Au I into blue-emitting S-AuCN,(S-Au CN)_(1-x)(S-AuI)_(x)(0≤x≤3.4%)with tunable emission from blue to red was achieved.This large red-shifted emission was realized based on the remarkable change of the electronic properties between the S-Au CN dimer and red-emitting(S-A CN)-(S-AuI)CT pair,and the resulting energy-transfer(En T)process between them.Importantly,the En T process can be switched off/on by external stimuli of grinding and CH_(2)Cl_(2)fuming,giving rise to high-contrast(blue versus red)CPL switching properties.This study opens a novel avenue for developing CPL switches by constructing light-harvesting CT-doped systems based on chiral organometallic complexes.

Phosphorescent Cationic Iridium（Ⅲ） Complexes with 1,3,4-Oxadiazole Cyclometalating Ligands： Solvent-Dependent Excited-State Dynamics

To elucidate the nature of low-lying triplet states and the effect of ligand modifica- tions on the excited-state properties of functional cationic iridium complexes, the solvent- dependent excited-state dynamics of two phosphorescent cationic iridium（Ⅲ） complexes, namely [Ir（dph-oxd）2（bpy）]PF6 （1） and [Ir（dph-oxd）2（pzpy）]Pf6 （2）, were investigated by femtosecond and nanosecond transient absorption spectroscopy. Upon photoexcitation to the metal-to-ligand charge-transfer （MLCT） states, the excited-state dynamics shows a rapid process （τ-=0.7-3 ps） for the formation of solvent stabilized 3MLCT states, which significantly depends on the solvent polarity for both 1 and 2. Sequentially, a relatively slow process assigned to the vibrational cooling/geometrical relaxation and a long-lived phospho- rescent emissive state is identified. Due to the different excited-state electronic structures regulated by ancillary ligands, the solvation-induced stabilization of the 3MLCT state in 1 is faster than that in 2. The present results provide a better sight of excited-state relaxation dynamics of ligand-related iridium（Ⅲ） complexes and solvation effects on triplet manifolds.

Luminescent Properties of A Novel Terbium Complex Tb(o-BBA)_3(phen)

A novel rare earth complex of terbium ion with 2-benzoylbenzoic acid and 1, 10-phenathroline （Tb（o-BBA）3 （phen）, o-BBA-2-benzoylbenzoic acid, phen = 1, 10-phenathroline） was used as an electroluminescent material for the first time. The Tb complex was blended with poly（N-vinylcarbazole） （PVK） in different weight ratios and spinn to coated into films （noted as PVK ：Tb films）. The photoluminescence （PL） properties of films were investigated and the optimum weight ratio between PVK and Tb（o-BBA）3（phen） was found to be 3：1. Monolayer devices with the structure ITO/PVK： Tb/AI were fabricated and emitted green light, which was characteristic of Tb^3＋ emission. The results show that mecha- nisms for PL and EL are different. The PL is considered to be caused because of energy transfer and direct excitation to the Tb（o-BBA）3（phen） molecule, while EL is mainly on charging trapping.

Spectrophotometric Study on the Interaction of Water with Chloranilic Acid and its Analytical Application

The reaction between chloranilic acid and water in alcohol was studied spectrophotometrically. The conditions of reaction were investigated in detail. The stable purple complex with an absorption wavelength at 530 nm was produced from the reaction between chloranilic acid and water. As a method for determination of H2O, Beer’s law was obeyed in range of 0-6.0 % or 0-8.0 % (V/V) with the detection limit of 0.13 %. The relative standard deviation (RSD) was less than 2 %. The proposed method has been applied to determination of trace amount of water in ethanol, flour and food flavoring, respectively. The recoveries of water in samples were 97～102 %.

Building up 1-D, 2-D, and 3-D Polyiodide Frameworks by Finely Tuning the Size of Aryls on Ar-S-TTF in the Charge-Transfer （CT） Complexes of Ar-S-TTFs and Iodine

The arylthio-substituted tetrathiafuivalenes （Ar-S-TTFs） are electron donors having three reversible states, neutral, cation radical, and dica- tion. The charge-transfer （CT） between Ar-S-TTFs （TTF1--TTF3） and iodine （12） is reported herein. TTF1--TTF3 show the CT with 12 in the CH2C12 solution, but they are not completely converted into cation radical state. In CT complexes of TTF1--TTF3 with 12, the charged states of Ar-S-TTFs are distinct from those in solution. TTF1 is at cation radical state, and TTF2--TTF3 are oxidized to dication. The iodine components in complexes show various structures including 1-D chain of V-shaped （Is）-, and 2-D and 3-D iodine networks composed of 12 and （13）^- .

Study of Spectrophotometric Characteristics of the Charge Transfer Reaction of Aminomethylbenzoic Acid with 7,7,8, 8-Tetracyanoq u inodimethane

A new spectrophotometric method was developed for the determination of aminomethylbenzoic acid （PAMBA） using 7,7,8,8-tetracyanoquinodimethane （TCNQ）. The method was based on the formation of charge transfer （CT） complex of this drug as n-electron donor with the n-acceptor TCNQ. TCNQ was found to react with PAMBA to produce a kind of yellow complex. The CT reaction proceeded quantitatively in pH 8.5 buffer solution. Different variables affecting the reaction were carefully studied and optimized. Under optimal reaction conditions, the stoichiometric ratio of the reaction, maximum absorption wavelength and the value of molar absorptivity were measured to be 1 ： 1, 425 nm, and 1.9 × 10^4 L.mol ^-1.cm^-1, respectively. Beer＇s law was obeyed in the range of 1- 9 μgomL-1 of PAMBA. The data have been filled to a linear regression equation A= -0.2612＋0.1123c （μgomL^-1）, with a correlation coefficient of 0.9996. The detection limit was 0.4 μg·mL^-1, R,S.D. was less than 1.9%, and average recovery was over 97.6%. The formation of the CT complex was also confirmed by both infrared and 1H NMR measurements. The thermodynamic property, kinetic property and reaction mechanism have also been discussed. The method developed was applied successfully to the determination of the subject drug in its pharmaceutical dosage forms with good precision and accuracy compared to official method revealed by t- and F-tests.