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.     

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]     

活性炭吸附及离子交换富集分离-分光光度法测定水中痕量银

建立了用活性炭对水中痕量银进行预富集的新方法。结果表明,pH=1.0时,活性炭能对水中被抗坏血酸还原后的痕量银进行吸附富集,而Cu(Ⅱ)、Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)、Pb(Ⅱ)、Zn(Ⅱ)、Mn(Ⅱ)、Al(Ⅲ)、Bi(Ⅲ)和Sb(Ⅲ)等常见阳离子不被吸附,用K2S2O8将吸附在活性炭上的单质银氧化解脱后,用Mg(NO3)2辅助置换洗脱,可用分光光度法测定。该法在8～50μg/L银(Ⅰ)范围内加标回收率为93.2～97.1%。同时还研究了活性炭对银的吸附行为,提出了活性炭表面上被氧化的Ag(Ⅰ)和Mg(Ⅱ)有离子交换作用。应用该法测定自来水中痕量银,结果令人满意。     

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.     

Solvent-dependent interconversions between Rh(I), Rh(II), and Rh(III) complexes of an aryl-monophosphine ligand

Reaction of the aryl-monophosphine ligand alpha(2)-(diisopropylphosphino)isodurene (1) with the Rh(I) precursor [Rh(coe)(2)(acetone)(2)]BF(4) (coe=cyclooctene) in different solvents yielded complexes of all three common oxidation states of rhodium, depending on the solvent used. When the reaction was carried out in methanol a cyclometalated, solvent-stabilized Rh(III) alkyl-hydride complex (2) was obtained. However, when the reaction was carried out in acetone or dichloromethane a dinuclear eta(6)-arene Rh(II) complex (5) was obtained in the absence of added redox reagents. Moreover, when acetonitrile was added to a solution of either the Rh(II) or Rh(III) complexes, a new solvent-stabilized, noncyclometalated Rh(I) complex (6) was obtained. In this report we describe the different complexes, which were fully characterized, and probe the processes behind the remarkable solvent effect observed.     

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.     

Determination of coenzyme Q10 in human breast milk by high-performance liquid chromatography

An isocratic HPLC method was developed for the determination of coenzyme Q(10) (CoQ(10)) in human breast milk. After a single-step liquid-liquid extraction, the milk extract was injected directly into the HPLC system. The analytical method is based on pre-column inline treatment of CoQ(10). Chromatographic separation of CoQ(10) and coenzyme Q(9) (CoQ(9)) internal standard was achieved using a reversed-phase Microsorb-MV C(18) analytical column. CoQ(10) and CoQ(9) were monitored by an electrochemical detector (ECD). An excellent linearity (r = 0.999) was observed for CoQ(10) in the concentration range 0.06-2.5 micromol L(-1) in breast milk. The limit of quantitation (LOQ) was 60 nmol L(-1). Coefficients of variations (CVs) for intra-day and inter-day assay precisions were less than 5%. A total of 194 breast milk samples were analyzed for the CoQ(10) concentration; the mean value was 0.32 +/- 0.21 micromol L(-1).     

The effect of covalent immobilization of sialic acid on the removal of lipopolysaccharide and reactive oxygen species for polyethylene terephthalate

Polyethylene terephthalate (PET) was aminolyzed with 1,6‐diaminohexane (DAH) and then sialic acid (NANA) was immobilized via amidation onto the surface. The surface concentration of NANA was determined by 2‐thiobarbituric acid (TBA) test. The hemocompatibility of the resulting PET fabrics was evaluated based on complete blood count (CBC), coagulating times, and protein adsorption. The ability to remove lipopolysaccharide (LPS) was also determined. In addition, the effect of contacting NANA‐immobilizing PET on the suppression of reactive oxygen species (ROS) production was measured by the chemiluminescence (CL) method. The results show that by immobilizing NANA onto PET, the adhesion of platelet (PLt) was reduced, and oxidative stress was suppressed. The level of LPS was also greatly reduced. Copyright © 2010 John Wiley & Sons, Ltd.     

掺硼纳米TiO2对农药毒死蜱的光催化降解作用

采用溶胶-凝胶法制备了掺杂硼的纳米TiO2,并用X射线衍射、红外光谱表征了产物的组成和结构.用制备好的掺硼纳米TiO2作为光催化剂对农药毒死蜱进行了光催化降解研究.结果表明:通过掺硼可以显著提高TiO2对毒死蜱的光催化效率.在硼掺杂量为3%,催化剂煅烧温度为500℃,煅烧时间为1 h,催化剂用量为15%时,毒死蜱的降解率最高.     

A cleaner and simple spectrophotometric micro-fluidic procedure for copper determination using nitroso-R salt as chromogenic agent

A cleaner and simple spectrophotometric method using microflow analysis (muFA) was performed. It consisted of a T-junction with microcoil on a polymethyl methacrylate (PMMA) chip which was fabricated by laser ablation and a molded polydimethylsiloxane (PDMS) as top plate. The fabricated PMMA chip was integrated with light emitting diode (LED) as light source and spectrometer as detector. The proposed device was applied to determining copper in water samples using nitroso-R salt as chromogenic reagent at 495nm. It was found that the proposed muFA system was with less reagents and samples consumption with tiny waste generation. The relative standard deviation (R.S.D.) was less than 2% (n=11) with the percentage recovery of 98.0+/-1.7% (n=7). The linear range for determination of copper in water samples was over the range of 0.05-3.0mugmL(-1) with a correlation coefficient (r(2)) of 0.999. The limit of detection (3sigma) was 47ngmL(-1) with a sample throughput of 30h(-1).     

高效液相色谱梯度洗脱同时测定化妆品中防腐剂、抗氧化剂和杀菌剂

建立了一种灵敏、快速的高效液相色谱梯度洗脱同时测定化妆品中防腐剂、抗氧化剂和杀菌剂的方法。采用C8柱,以甲醇和水为流动相梯度洗脱。在检测波长273nm用二极管阵列检测器,17min内可将4种防腐剂、2种抗氧化剂和2种杀菌剂分离测定。方法快速准确,用于实际样品的测定。     

温度对掺杂球形Ni(OH)_2质子扩散的影响

应用微电极恒电位阶跃法研究了在Ni(OH) 2 电极的阳极及阴极过程反应中 ,温度对球形Ni(OH) 2 的质子扩散系数和表观扩散活化能的影响 .研究表明 ,于Ni(OH) 2 中掺杂Co和Co +Zn后可降低其阳极和阴极过程的表观扩散活化能 ,增大质子扩散系数 ,掺Co的效果更加明显 ,而掺Zn则增大表观扩散活化能 ,降低了扩散系数 .这说明前者的掺入其作用是降低了质子扩散阻力使电极的反应活性增加、而后者的掺入则是增大了质子的扩散阻力而使电极反应活性降低 .     

新型抑菌聚砜超滤膜的制备及性能

将辣素功能结构单体N-(4-羟基-3-甲氧基苯甲基)丙烯酰胺(HMBA)和甲基丙烯酸甲酯(MMA)通过自由基引发合成出抑菌型共聚物P(H-co-M), 通过红外吸收光谱和热重分析证实了共聚物的结构. 采用共混法将共聚物引入聚砜(PSF)铸膜液中, 通过浸没沉淀相转化法制备了新型抑菌超滤膜. 考察了P(H-co-M)含量对超滤膜分离性能及抑菌性能的影响. 结果表明, 当P(H-co-M)质量分数为0.5%时, 超滤膜分离性能最佳, 对5 mg/L腐殖酸溶液的稳定水通量为122.2 L/(m2·h), 截留率为84.4%, 与未添加P(H-co-M)的超滤膜相比, 分别提高了19.2%和9.2%. 改性超滤膜具有较强的抑菌性能, 当P(H-co-M)含量为1.0%时, 抑菌率最大(约80.7%).     

Chiral capillary electrophoresis-mass spectrometry of tetrahydroisoquinoline-derived neurotoxins: observation of complex stereoisomerism

Previous studies have shown that certain 1,2,3,4-tetrahydroisoquinoline derivatives (TIQs) are neurotoxins inducing Parkinsonism. Further, individual enantiomers of these toxins such as (R/S)-N-methylsalsolinol ((R/S)-NMSal) possess distinct neurotoxicological properties. In this work, a chiral capillary electrophoresis (CE) method with electrospray ionization-tandem mass spectrometric (ESI-MS/MS) detection was developed for the quantification of TIQ enantiomers. Enantioseparation was achieved with sulfated β-cyclodextrin (sulfated β-CD) as chiral selector. To avoid any potential contamination of MS ionization source by the non-volatile chiral selector, partial filling technique was deployed in the CE separation. TIQ derivatives, including (R/S)-6,7-dihydroxy-1-methy-TIQ (salsolinol, Sal), (R/S)-1-benzyl-TIQ (BTIQ), and (R/S)-NMSal, were base-line resolved with resolution values (R) ranging from 3 (for Sal) to 4.5 (for BTIQ), which were much better than those reported previously by HPLC methods. ESI-MS/MS detection of the resolved TIQ enantiomers was specific and sensitive (LOD=1.2 μM for Sal enantiomers). The proposed chiral CE-MS/MS method was used to study in vitro formation of (R/S)-NMSal. It was found that NMSal was formed from the incubation of epinine (a dopamine metabolite) with acetaldehyde (a metabolite of alcohol). More interestingly, four isomers of NMSal were separated and detected in the incubation solution. They were identified as (R)-e.e-NMSal, (R)-e.a-NMSal, (S)-e.e-NMSal, and (S)-e.a-NMSal. This was the first lab evidence that this Parkinsonian neurotoxin exists in multiple isomeric forms.     

Graphene oxide assisted facile hydrothermal synthesis of LiMn0.6Fe0.4PO4 nanoparticles as cathode material for lithium ion battery

Assisted by graphene oxide（GO）,nano-sized LiMn0.6Fe0.4PO4 with excellent electrochemical performance was prepared by a facile hydrothermal method as cathode material for lithium ion battery.SEM and TEM images indicate that the particle size of LiMn0.6Fe0.4PO4（S2）was about 80 nm in diameter.The discharge capacity of LiMn0.6Fe0.4PO4 nanoparticles was 140.3 mAh-g^1 in the first cycle.It showed that graphene oxide was able to restrict the growth of LiMn0.6Fe0.4PO4 and it in situ reduction of GO could improve the electrical conductivity of LiMn0.6Fe0.4PO4 material.     

四(3,4-二甲基苯基)卟啉钴的合成及其光学性质

采用“两步法”,以吡咯和3,4-二甲基苯甲醛为原料,合成了四(3,4-二甲基苯基)卟啉(TDMPP, 1); 1与四水醋酸钴经络合反应合成四(3,4-二甲基苯基)卟啉钴(TDMPPCo, 2),其结构经¹H NMR, IR和荧光光谱确证。考察了金属盐的预处理、反应物浓度、浓缩比和投料比对合成2的收率影响。实验结果表明：在最佳反应条件［γ=n(1)：n(四水乙酸钴)=1 ：7, c（1）为22.95 mmol·L^-1,回流（150 ℃）反应4 h,浓缩比η为75%］下,收率可达82%。     

Separation of strontium ions from a simulated highly active liquid waste using a composite of silica-crown ether in a polymer

To partition Sr(II) from highly active liquid waste (HLW), a macroporous silica-based 4,4',(5')-di(t-butylcyclohexano)-18-crown-6 (DtBuCH18C6)-tri-n-butyl phosphate (TBP) polymeric composite, (DtBuCH18C6+TBP)/SiO(2)-P, was synthesized. It was done by impregnation and immobilization of DtBuCH18C6 and TBP into the pores of the SiO(2)-P particles, where DtBuCH18C6 was modified with TBP. The sorption of Sr(II) and some co-existent elements contained in a simulated HLW onto (DtBuCH18C6+TBP)/SiO(2)-P was investigated at 323 K. It was found that in 2.0 M HNO(3), Sr(II) exhibited strong sorption ability and high selectivity over all the tested metals except Ba(II). Chromatographic partitioning of Sr(II) from 2.0 M HNO(3) containing 5 mM of the tested elements was performed by (DtBuCH18C6+TBP)/SiO(2)-P packed column. La(III), Y(III), Na(I), K(I), Cs(I), Ru(III), Mo(VI), and Pd(II) had almost no sorption and flowed into effluent along with 2.0 M HNO(3). Sr(II) adsorbed strongly by (DtBuCH18C6+TBP)/SiO(2)-P was then eluted effectively by water, while Ba(II) flowed into effluent along with Sr(II) due to the similar chemical properties. In addition, the bleeding of total organic carbon in aqueous phase was evaluated. The results demonstrated that in 2.0 M HNO(3), application of the macroporous silica-based DtBuCH18C6 polymeric composite in chromatographic partitioning of Sr(II) from the simulated HLW is feasible.     

对苯乙烯磺酸在水滑石层间的柱撑及聚合

对苯乙烯磺酸在水滑石层间的柱撑及聚合;水滑石;对苯乙烯磺酸;柱撑;聚合     

耐超高温SiC(Al)纤维先驱体——聚铝碳硅烷纤维的研究

以聚硅碳硅烷(PSCS)与乙酰丙酮铝(Al(AcAc)3)为原料,在常压高温条件下反应制备出聚铝碳硅烷(PACS),经过熔融纺丝制备了PACS纤维.应用GPC、IR、XPS、29Si-NMR、27Al-NMR、TG、SEM、元素分析和增重等一系列分析,分别对PACS纤维的微观组成、结构以及性能进行了分析.研究结果表明,以原料质量配比为6∶100(Al(AcAc)3∶PSCS)合成的PACS化学式为SiC2.0H7.5O0.13Al0.018,数均分子量为1700左右,最适宜制备PACS纤维;PACS纤维中主要存在SiC4、SiC3H等结构,同时存在Si—O—Al键;在氮气气氛中,PACS纤维的陶瓷产率达到52%左右;预氧化处理,PACS纤维中Si—H键与空气中的氧反应形成Si—O—Si交联结构,较聚碳硅烷(PCS)纤维易于氧化,经过预氧化的PACS纤维陶瓷产率达到80%左右,是制备耐超高温SiC(Al)陶瓷纤维的合适纤维;用预氧化PACS纤维制备的SiC(OAl)纤维和SiC(Al)纤维抗拉强度高,耐高温性能好.     

梨小食心虫性信息素的新法合成

梨小食心虫 (Grapholia molesta)是一种世界性果树害虫 ,主要危害梨、桃和苹果等果树 . 1 96 5年Geroge等 [1] 从该雌蛾腹部分离得到其性信息素 . 1 96 9年 Roelofs等 [2 ] 鉴定其结构为 8(Z/E) -十二碳烯 - 1 -醇乙酸酯 (6 ) .国内外对其生物活性进行了大面积田间试验 ,并用于