Structural Characterization and Toxicity Prediction of Some Organic Compounds

A new molecular structural characterization(MSC)method called molecular vertexes correlative index(MVCI)was constructed in this paper.The index was used to describe the structures of 45 compounds and a quantitative structure-activity relationship(QSAR)model of toxicity(–lgEC50)was obtained through multiple linear regression(MLR)and stepwise multiple regression(SMR).The correlation coefficient(R)of the model was 0.912,and the standard deviation(SD)of the model was 0.525.The estimation stability and prediction ability of the model were strictly analyzed by both internal and external validations.The Leave-One-Out(LOO)Cross-Validation(CV)correlation coefficient(RCV)was 0.816 and the standard deviation(SDCV)was 0.739,respectively.For the external validation,the correlation coefficient(Rtest)was 0.905 and the standard deviation(SDtest)was 0.520,respectively.The results showed that the index was superior in molecular structural representation.The stability and predictability of the model were good.     

Evaluation of luminol-H(2)O(2)-KIO(4) chemiluminescence system and its application to hydrogen peroxide, glucose and ascorbic acid assays

A novel chemiluminescence (CL) system was evaluated for the determination of hydrogen peroxide, glucose and ascorbic acid based on hydrogen peroxide, which has a catalytic-cooxidative effect on the oxidation of luminol by KIO(4). Hydrogen peroxide can be directly determined by luminol-KIO(4)-H(2)O(2) CL system. The detection limit was 3.0x10(-8) mol l(-1) and the calibration graph was linear over the range of 2.0x10(-7)-6.0x10(-4) mol l(-1). The relative standard deviation of H(2)O(2) was 1.1% for 2.0x10(-6) mol l(-1) (N=11). Glucose was indirectly determined through measuring the H(2)O(2) generated by the oxidation of glucose in the presence of glucose oxidase at pH 7.6. The present method provides a source for H(2)O(2), which, in turn, coupled with the luminol-KIO(4)-H(2)O(2) CL reaction system. The CL was linearly correlated with glucose concentration of 0.6-110 mug ml(-1). The relative standard deviation was 2.1% for 10 mug ml(-1) (N=11). Detection limit of glucose was 0.08 mug ml(-1). Ascorbic acid was also indirectly determined by the suppression of luminol-KIO(4)-H(2)O(2) CL system. The calibration curve was linear over the range of 1.0x10(-7)-1.0x10(-5) mol l(-1) of ascorbic acid. The relative standard deviation was 1.0% for 8.0x10(-7) mol l(-1) (N=11). Detection limit of ascorbic acid was 6.0x10(-8) mol l(-1). These proposed methods have been applied to determine glucose, ascorbic acid in tablets and injection.     

Selective transport of yttrium(III) in the presence of iron(III) through liquid-membrane impregnating acidic organophosphonate mobile carrier

The extraction and stripping behavior of yttrium(III) and iron(III) with 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (EHPA) was investigated and applied to liquid-membrane transport for their mutual separation. The extractability of yttrium(III) with EHPA was less than that of iron(III) at equilibrium, but the rates of extraction and stripping of iron(III) were slow. The carrier-mediated transport of yttrium(III) in the presence of iron(III) was investigated through a supported liquid membrane (SLM), impregnated with EHPA as a mobile carrier. Yttrium(III) with fast kinetics was selectively transported across an SLM from a dilute-acid solution into a sulfuric-acid stripping solution, while iron(III) with slow kinetics was hardly transported and was retained in the feed solution. Yttrium(III) was separated from iron(III) through the SLM and quantitative recovery was realized.     

Synthesis of a putative antigenic heptapeptide from Escherichia coli K88 ab protein fimbriae

The heptapeptide Tyr-Arg-Glu-Asp-Met-Glu-Tyr-OMe, spanning region 213-219 of Escherichia coli K88 ab protein fimbriae, was synthesized with an overall yield of 37% using dicyclohexylcarbodiimide (DCC) and 1-hydroxybenzotriazole (HOBt) preactivation in all condensation reactions. The C-terminal was protected as the methyl ester. The protection scheme of N alpha-tert-butyloxycarbonyl-(Boc) and benzyl-(Bzl) or benzyloxycarbonyl (Z) groups for side chain protection was found to be orthogonal when a mixture of trifluoroacetic acid (TFA), phenol (PhOH) and p-cresol (CrOH) was used for repetitive deprotection. The final deprotection of Boc-Tyr(Bzl)-Arg(Z2)-Glu(Bzl)-Asp(Bzl)-Met-Glu(Bzl+ ++)-Tyr(Bzl)-OMe (17) was accomplished in 80% yield by prolonged treatment with hydrogen fluoride, dimethyl sulfide, p-cresol and p-thiocresol. The BSA-linked synthetic peptide was used in immunisation experiments on rabbits.     

High-resolution time-of-flight spectra obtained using the MULTUM II multi-turn type time-of-flight mass spectrometer with an electron ionization ion source

This paper describes experiments demonstrating the high mass-resolving power of the MULTUM II multi-turn type time-of-flight (ToF) mass spectrometer with a 1.308-meter circuit controlled by four toroidal electric sector fields(1) and an electron ionization (EI) ion source. A mass resolution of 250,000 [full-width at half maximum: (FWHM)] was obtained for N(2)(+) after a flight time of 9.0 ms (flight cycles: 1,200, flight length: 1,500 M). A doublet of (12)C(5)H(5)(14)N and (13)C(12)C(5)H(6) (m/Deltam = 9,746; Deltam: mass difference of doublet, m: mass of lighter ion of doublet) was separated and a mass resolution of 91,000 (FWHM) was obtained. A doublet of CDCl(2) and CH(2)Cl(2) (m/Deltam = 54,162) was also separated. A mass resolution of 115,000 (FWHM) was then achieved. When one peak of these doublets was used as a calibrant, the mass of the other peak was determined within a few ppm by mass difference. The ToF depending on the square of m/z was significantly larger than the systematic errors in the ToF, so that good mass accuracy was obtained by one-point mass determination.     

Kinetic parameters of urease immobilized on modified acrylonitrile copolymer membranes in the presence and absence of Cu(II) ions

Poly(acrylonitrile-methylmethacrylate-sodium vinylsulfonate) membranes were subjected to seven different chemical modifications and the amount of the newly formed groups was measured for each membrane. Urease was then covalently immobilized onto the modified membranes and the amount of bound protein was determined. The kinetic parameters V(max) and K(m) of the immobilized urease were studied under static and dynamic conditions. Results showed that the rate of the enzyme reaction was higher for the membranes modified with NH(2)OH . H(2)SO(4), NH(2)NH(2) . H(2)SO(4), NaOH + EDA and NaOH + GA + EDA. It was confirmed that the reaction rate, measured under dynamic conditions, was higher than that one determined under static conditions. The influence of Cu(II) ions, as inhibitors, on the enzyme reaction kinetics (V(i) and K(i)) was also investigated. It turned out that the most sensitive membranes towards Cu(II) were those modified with NH(2)NH(2) . H(2)SO(4), NaOH + EDA and H(2)O(2). The results initiated further investigations on the influence of other heavy metal ions (Cd(II), Zn(II), Ni(II) and Pb(II)) over urease bound to a NH(2)OH . H(2)SO(4)-modified membrane. It was found that the inhibition effect of the heavy metal ions over immobilized urease decreases in the order: Cu(II) > Cd(II) > Zn(II) > Ni(II) > Pb(II). [Diagram: see text]     

Extraction behaviour of copper(II) and silver(I) with a thiacrown ether carboxylic acid, 2-(3,6,10,13-tetrathiacyclotetradec-1-oxy)hexanoic acid

The extraction behaviour of copper(II) and silver(I) with 2-(3,6,10,13-tetrathiacyclotetradec-1-oxy)hexanoic acid (TTCTOHA) was investigated at 25+/-0.1 degrees C and ionic strength of 0.1. The value of the logarithmic distribution coefficient, logK(DR) of TTCTOHA between octan-1-ol and aqueous phases was determined to be 4.13. Copper(II) was extracted with TTCTOHA into octan-1-ol as CuL(2), where L represents the anionic species of TTCTOHA. The logarithmic extraction constant, logK(ex(10)), was determined at -7.42. Silver(I) was extracted with TTCTOHA into octan-1-ol as AgL and Ag(2)L(2). The logarithmic distribution constant, logK(DC), of AgL was estimated to be 0.49. On the other hand, silver(I) was extracted into 1,2-dichloroethane as AgL and the logarithmic extraction constant, logK(ex(10)), was determined to be -2.24.     

Microwave-assisted derivatization and single-drop microextraction for gas chromatographic determination of chromium(III) in water

A rapid and efficient sample preparation method combining microwave-assisted derivatization (MAD) and single-drop microextraction (SDME) for the gas chromatographic (GC) determination of trace Cr(III) in water was developed. Aqueous Cr(III) was first converted to the volatile chromium trifluoroacetylacetonate (Cr(tfa)3) by reaction with 1,1,1-trifluoroacetylacetone (Htfa) under the irradiation of microwave. Derivatization of Cr(III) at ng ml(-1) level could be completed in less than 1 min. The formed Cr(tfa)3 was then extracted into a small droplet (2 microl) of toluene suspended at the tip of a microsyringe needle. The optimal extraction time was 30 min. The solvent drop was directly injected into a GC equipped with a flame photometric detector (FPD) for analysis. The two Cr(tfa)3 isomers extracted could be efficiently separated in 2 min. Linearity (r>0.99) over the concentration range 2-300 ng ml(-1) Cr was obtained and the limit of detection was 0.5 ng ml(-1) Cr. The relative standard deviation was 7.8% at 20 ng ml(-1) Cr (n=5). Applicability of this method to water analysis was examined by analyzing the chromium content in a reference standard water sample and an industrial effluent.     

Di(2-ethyl hexyl) butyramide and di(2-ethyl hexyl)isobutyramide as extractants for uranium(VI) and plutonium(IV)

The extraction of uranium(VI) and plutonium(IV) from nitric acid into n-dodecane was studied using two isomeric branched alkyl amides, di(2-ethyl hexyl) butyramide (DEHBA) and di(2-ethyl hexyl) isobutyramide (DEHIBA). The extraction ratios of Pu(IV) at relatively high acidities were higher than the corresponding values for U(VI) in the case of DEHBA. However, with DEHIBA the values for Pu(IV) were negligibly small. Pu(IV) was found to be extracted as trisolvate by DEHBA and as disolvate by DEHIBA. U(VI) was extracted by both the amides. From the study of the extraction reactions at different temperatures, it was shown that all the reactions in the present investigation were enthalpy favoured and entropy disfavoured. Separation of Pu(IV) from bulk of U(VI) was feasible. However, the purity of the separated plutonium was not satisfactory in batch extraction studies.     

Exhaustive chlorination of [B12H12]2- without chlorine gas and the use of [B12Cl12]2- as a Supporting anion in catalytic hydrodefluorination of aliphatic C-F bonds

The fully chlorinated closo-dodecaborate salt Cs(2)[B(12)Cl(12)] was prepared in high yield from Cs(2)[B(12)H(12)] and SO(2)Cl(2) in acetonitrile at refluxing temperature. [Ph(3)C](2)[B(12)Cl(12)] was obtained by simple metathesis reactions. Catalytic hydrodefluorination of benzotrifluoride sp(3) C-F bonds was accomplished using [Ph(3)C](2)[B(12)Cl(12)] as a precatalyst and Et(3)SiH as a stoichiometric reagent. Full consumption of the sp(3) C-F bonds in p-FC(6)H(4)CF(3) and C(6)F(5)CF(3) with a turnover number up to 2000 was achieved.     

Remote substituent effects on bond dissociation energies of para-substituted aromatic silanes

UB3LYP/6-31G(d) and ROMP2/6-311++G(d,2p) methods were used to calculate the Si-X bond dissociation energies (BDEs) of a number of para-substituted aromatic silanes (4-Y-C(6)H(4)-SiH(2)X, where X = H, F, Cl, or Li). It was found that the substituent effect on the Si-H BDE of 4-Y-C(6)H(4)-SiH(3) was small, as the slope (rho(+)()) of the BDE- regression was only 0.09 kJ/mol. In comparison, the substituent effect on the Si-F BDE of 4-Y-C(6)H(4)-SiH(2)F was much stronger, whose rho(+ )()value was -2.34 kJ/mol. The substituent effect on the Si-Cl BDE of 4-Y-C(6)H(4)-SiH(2)Cl was also found to be strong with a rho(+)() value of -1.70 kJ/mol. However, the substituent effect on the Si-Li BDE of 4-Y-C(6)H(4)-SiH(2)Li was found to have a large and positive slope (+9.12 kJ/mol) against. The origin of the above remarkably different substituent effects on the Si-X BDEs was found to be associated with the ability of the substituent to stabilize or destabilize the starting material (4-Y-C(6)H(4)-SiH(2)X) as well as the product (4-Y-C(6)H(4)-SiH(2)* radical) of the homolysis. Therefore, the direction and magnitude of the effects of Y-substituents on the Z-X BDEs in compounds such as 4-YC(6)H(4)Z-X should have some important dependence on the polarity of the Z-X bond undergoing homolysis. This conclusion was in agreement with that from earlier studies (for example, J. Am. Chem. Soc. 1991, 113, 9363). However, it indicated that the proposal from a recent work (J. Am. Chem. Soc. 2001, 123, 5518) was unfortunately not justified.     

NH3/NH4Cl中镍(Ⅱ)-丁二肟体系在悬汞电极上电化学还原机理的研究

The behaviour of the Nickel(Ⅱ) ion in the presence of dimethyl-glyoxime (DMG) on the hanging mercury drop electrode in NH_3/NH_4Cl media was investigated with different electrochemical techniques. It was found that: (1) the reactant was Ni(Ⅱ) complex with DMG, Ni(Ⅱ)A_2, adsorbed on the electrode surface; (2) the intermediate was Ni(Ⅰ)A_2 and (3) the product was metal amalgam Ni(0)(Hg). Two electrons were transferred in the overall reaction and the transfer coefficient was 1.8 which was measured experimentally. From experimental results, it was obvious that the reaction orders with respect to Ni(Ⅱ), DMG and H~+ were 1,2, and 1, respectively. A new compound, X, was detected. The reaction scheme could be written as followsNi(Ⅱ)A_2+Hg<=>Ni(Ⅱ)A_2(ads)(Hg)Ni(Ⅱ)A_2(ads)(Hg)+e~-<=>Ni(Ⅰ)A_2(ads)(Hg)Ni(Ⅰ)A_2(ads)(Hg)+H~++e~-→Ni(0)(Hg)+HA(des)+A~-(des)→X+Hg     

Nonstoichiometric La(2 - x)GeO(5 - delta) monoclinic oxide as a new fast oxide ion conductor.

Oxide ion conductivity in La(2)GeO(5)-based oxide was investigated and it was found that La-deficient La(2)GeO(5) exhibits oxide ion conductivity over a wide range of oxygen partial pressure. The crystal structure of La(2)GeO(5) was estimated to be monoclinic with P2(1)/c space group. Conductivity increased with increasing the amount of La deficiency and the maximum value was attained at x = 0.39 in La(2 - x)GeO(5 - delta). The oxide ion transport number in La(2)GeO(5)-based oxide was estimated to be unity by the electromotive force measurement in H(2)-O(2) and N(2)-O(2) gas concentration cells. At a temperature higher than 1000 K, the oxide ion conductivity of La(1.61)GeO(5 - delta) was almost the same as that of La(0.9)Sr(0.1)Ga(0.8)Mg(0.2)O(3 - delta) or Ce(0.85)Gd(0.15)O(2 - delta), which are well-known fast oxide ion conductors. On the other hand, a change in the activation energy for oxide ion conductivity was observed at 973 K, and at intermediate temperature, the oxide ion conductivity of La(1.61)GeO(5 - delta) became much smaller than that of these well-known fast oxide ion conductors. The change in the activation energy of the oxide ion conductivity seems to be caused by a change in the local oxygen vacancy structure. However, doping a small amount of Sr for La in La(2)GeO(5) was effective to stabilize the high-temperature crystal structure to low temperature. Consequently, doping a small amount of Sr increases the oxide ion conductivity of La(2)GeO(5)-based oxide at low temperature.     

腈氧化物的研究(Ⅱ)——合成新诺明(SMZ)的新路线

利用腈氧化物的1,3-偶极加成反应,合成新诺明(SMZ),以1,2,3-三氯代丁醛肟(Ⅰ_a),经转化为α,β-二氯代丁腈氧化物(Ⅱ_a)后,与对乙酰氨基苯磺酰胺加成,继而就地进行环合、消除反应,浮5-甲基-3-(对乙酰氨基苯磺酰氨基)异噁唑(Ⅲ_a),(Ⅲ_a)水解即得SMZ(Ⅳ_a)。同时依法制得5-苯基-3-(对氨基苯磺酰氨基)异噁唑(Ⅳ_b)。     

Synthesis of a novel fluorescent probe based on acridine skeleton used for sensitive determination of DNA

In this study, a novel fluorescent probe of acridine derivative N-((N-(2-dimethylamino)ethyl)acridine-4-carboxamide)-alpha-alanine (N-(ACR-4-CA)-alpha-ALA) was synthesized. The structure of the new compound was characterized by (1)H NMR, MS, elemental analysis, fluorescent and ultraviolet spectra. It was found that DNA had the ability to quench the fluorescence of N-(ACR-4-CA)-alpha-ALA, and the quenched intensity of fluorescence was proportional to the concentration of DNA. A method for DNA determination based on the quenching fluorescence (lambda(ex) = 260 nm, lambda(em) = 451 nm) of N-(ACR-4-CA)-alpha-ALA was established. Under optimal conditions, the linear range is 0.05-2.0 microg mL(-1) for both fish semen (fsDNA) and calf thymus DNA (ctDNA). The corresponding determination limits are 9.1 ng mL(-1) for fsDNA and 8.7 ng mL(-1) for ctDNA, respectively. The results suggested that the interaction mode between N-(ACR-4-CA)-alpha-ALA and DNA was intercalative binding. The intrinsic binding constant was determined and the result showed a large binding constant of N-(ACR-4-CA)-alpha-ALA with DNA.     

Kinetics of ClONO(2) reactive uptake on ice surfaces at temperatures of the upper troposphere

The reactive uptake kinetics of ClONO(2) on pure and doped water-ice surfaces have been studied using a coated wall flow tube reactor coupled to an electron impact mass spectrometer. Experiments have been conducted on frozen film ice surfaces in the temperature range 208-228 K with P((ClONO)(2)) < or = 10(-6) Torr. The uptake coefficient (gamma) of ClONO(2) on pure ice was time dependent with a maximum value of gamma(max) approximately 0.1. On HNO(3)-doped ice at 218 K the gamma(max) was 0.02. HOCl formation was detected in both experiments. On HCl-doped ice, uptake was gas-phase diffusion limited (gamma > 0.1) and gas-phase Cl(2) was formed. The uptake of HCl on ice continuously doped with HNO(3) was reversible such that there was no net uptake of HCl once the equilibrium surface coverage was established. The data were well described by a single site 2-species competitive Langmuir adsorption isotherm. The surface coverage of HCl on HNO(3)-doped ice was an order of magnitude lower than on bare ice for a given temperature and P(HCl). ClONO(2) uptake on this HCl/HNO(3)-doped ice was studied as a function of P(HCl). gamma(max) was no longer gas-phase diffusion limited and was found to be linearly dependent on the surface concentration of HCl. Under conditions of low HCl surface concentration, hydrolysis of ClONO(2) and reaction with HCl were competing such that both Cl(2) and HOCl were formed. A numerical model was used to simulate the experimental results and to aid in the parametrization of ClONO(2) reactivity on cirrus ice clouds in the upper troposphere.     

Determination of chromium(III) in water by solid-phase microextraction with a polyimide-coated fiber and gas chromatography-flame photometric detection

A method for the determination of trace Cr(III) in aqueous solution by solid-phase microextraction (SPME) coupled with gas chromatography (GC)-flame photometric detection (FPD) was developed. Aqueous Cr(III) was first converted to the volatile chromium trifluoroacetylacetonate (Cr(tfa)3) by derivatization with 1,1,1-trifluoroacetylacetone (Htfa), followed by SPME extraction using a polyimide-coated silica fiber. The distribution constants (K) of derivatized cis- and trans-Cr(tfa)3 between the polyimide phase and aqueous phase were 2012 and 2214, respectively. The two Cr(tfa)3 isomers extracted can be efficiently separated by a DB-210 GC column within 9 min. Selective detection of Cr was performed by a FPD equipped with a 385-nm long-pass filter. Linearity (r> 0.99) over the concentration range 5-300 ng ml(-1) Cr was obtained and the limit of detection was 2 ng ml(-1) Cr. The relative standard deviation was 7% at 10 ng ml(-1) Cr (n = 5). Applicability of this method to water analysis was tested by analyzing the chromium content in a reference standard water sample and an industrial effluent.     

Chemometric study of selected polychlorinated biphenyls in ambient air of Madrid (Spain)

The formation of Fe(III) and Fe(II) chelates with pyridylazo and thiazolylazo reagents was examined. Optimum conditions for the formation of Fe(III) and Fe(II) chelates with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) were in detail evaluated. The LC method for simultaneous separation of Fe(III) and Fe(II) ions as 5-Br-PADAP chelates was evaluated using the PEEK column with C18 e.c. stationary phase and acetonitrile+water (90:10, v/v) eluent containing the 1x10(-3) mol l(-1) C(12)H(25)SO(3)Na, the ion-pairing reagent, pH 3.4-3.6. The simultaneous determination of 20-500 mug l(-1) Fe(II) ions (detection at 555 nm) and 20-500 mug l(-1) Fe(III) ions (detection at 585 nm) as 5-Br-PADAP chelates (for both ions, detection limit, 18 mug l(-1) for 20 mul loop) was established. The chromatographic method was applied to the water analysis. Although the present method is able to determine both Fe(III) and Fe(II) ions, the Fe(III) ion was not detected in all water samples. The Fe(II) was detected only in fresh gathered oligocene water at the level of 135 mug l(-1). The present method was used to the investigation of the distribution of Fe(III)/Fe(II) ions in aqueous and micellar solutions after action of external, ultrasonic field.     

Chromatographic separation of carrier free 90Y from 90Sr using a diglycolamide based resin for possible pharmaceutical applications

N,N,N',N'-tetraoctyl diglycolamide (TODGA) has been used as the stationary phase in an extraction chromatography resin (XCR) material prepared for evaluating the uptake and the separation behaviour of (90)Y and (90)Sr from acidic feeds. Chromosorb-W was used as the solid support material while the feed solution was usually 4M HNO(3). The batch uptake studies have suggested almost no Sr(II) uptake while Y(III) uptake increased with acidity up to 4M HNO(3) beyond which a decrease in the K(d,w) values were observed. Column studies were carried out and breakthrough profiles were obtained for both Y(III) and Sr(II). No breakthrough of Y(III) was noticed even when >50 column volumes of the feed (carrier free (90)Y at 4 M HNO(3)) was passed through the column while about 20 column volumes were required for the breakthrough of Y(III) when the feed contained 1 g/L Y in 4 M HNO(3) spiked with (90)Y tracer. The reusability of the column was also studied which indicated in the deterioration of the column performance as shown by the sharp fall in the breakthrough volumes and was attributed to the probable leaching of the reagent from the support material. The role of absorbed dose was also investigated for Y(III) uptake. Separation of carrier free (90)Y tracer was carried out by loading the column with (90)Sr and eluting with 0.01M solutions of HNO(3) as well as EDTA. The purity of the product was ascertained by half-life method.     

Microfluidic chip for high efficiency DNA extraction

A high efficiency DNA extraction microchip was designed to extract DNA from lysed cells using immobilized beads and the solution flowing back and forth. This chip was able to increase the extraction efficiency by 2-fold when there was no serum. When serum existed in the solution, the extraction efficiency of immobilized beads was 88-fold higher than that of free beads. The extraction efficiency of the microchip was tested under different conditions and numbers of E. coli cells. When the number of E. coli cells was between 10(6) and 10(8) in 25 microl of whole blood, the extraction efficiency using immobilized beads was only slightly higher than that using free beads (10(0) to 10(1) fold). When the number of E. coli cells was in the range 10(4) to 10(6) in 25 microl of whole blood, the extraction efficiency of immobilized beads was greater than that of the free beads (10(1) to 10(2) fold). When the number of E. coli cells was lower, in the range 10(3) to 10(4) in 25 microl of whole blood, the extraction efficiency of immobilized beads was much higher than that of the free beads (10(2) to 10(3) fold). This study indicated that DNA could be efficiently extracted even when the number of bacterial cells was smaller (10(5) to 10(3)). This microfluidic extraction chip could find potential applications in rare sample genomic study.