基于吹气分离富集的异烟酸-巴比妥酸分光光度法测定水中痕量氰化物

鉴于氰化物转化成氯化氰是HJ 484-2009中异烟酸-巴比妥酸分光光度法测定氰化物的独立中间环节,利用氯化氰沸点低(14℃)、稳定性好的特性,提出了基于吹气分离富集的异烟酸-巴比妥酸分光光度法测定水中痕量氰化物含量的方法。以空气为载气,以异烟酸质量浓度为17.20 g·L^-1、巴比妥酸质量浓度为8.40 g·L^-1的溶液为吸收液(pH 5.85),利用特定的分离富集装置,完成空气净化、氰化物转化成氯化氰、氯化氰分离、氯化氰吸收及转化成聚甲炔染料等一系列过程,采用分光光度计测定吸收液在600 nm处的吸光度。结果表明：当样品、吸收液的体积分别为60.0,5.00 mL,空气流量为0.10 L·min^-1,采用3级吸收,以总吸光度作为响应值时,氰化物转化系数为94.2%,富集倍数为11.3倍,检出限(3s/k)为0.1μg·L^-1,测定线性范围为0.4～28.3μg·L^-1;方法用于井水及河水中痕量氰化物的测定,氰化物质量浓度为1.2～8.9μg·L^-1,回...     

胺类吸收剂模拟烟气脱硫

以醇胺和乙二胺为原料,配制0.3 mol/L的水溶液,用于实验室模拟烟气脱硫的研究。通过碘量法测定脱硫率,采用离子色谱测定SO₂吸收容量、吸收液中SO₂的氧化率和解吸率,同时探讨了循环次数对脱硫率和富液中SO₂含量的影响。结果表明,吸收进行30 min时,吸收液的脱硫率均保持在99 %以上,60 min时,乙二胺类溶液的脱硫率仍达99 %,醇胺吸收液脱硫效果明显下降。乙二胺溶液对SO₂ 的吸收容量为455 mg/L,远远高于醇胺类吸收液。若乙二胺溶液中加入硼酸,则其对SO₂的吸收容量略低(450 mg/L),但提高了溶液的抗氧化性,吸收液中SO₂的氧化率由1.14 %减至0.29 %,同时解吸率由38.0 %增至59.0 %。10次吸收-解吸循环实验数据显示,乙二胺/硼酸溶液的平均脱硫率均在99 %以上,富胺液中SO₂含量由0.44 mol/L减至0.40 mol/L,表明吸收液的脱硫性能良好,可以作为烟气脱硫剂。     

高耐盐性吸水树脂的紫外光引发合成及其性能

采用紫外光引发聚合法合成了聚乙烯醇与丙烯酸钠高耐盐性吸水树脂.用红外光谱和热重分析法对产物进行了表征,测定了该树脂的溶胀动力学、可逆性能及温度、pH、离子浓度和有机溶剂等因素对树脂吸附率的影响.结果表明:该树脂在蒸馏水中的吸水率为4 100 g/g,在w=0.9%的NaCl水溶液中的吸盐水率为405 g/g;树脂的吸液率与阳离子的价态有关,其吸液率大小顺序为NaCl＞CaCl2＞FeCl3;其溶胀动力学扩散过程中的膨胀指数0.5＜n＜1,属于non-Fickon扩散.     

大孔强碱树脂从含钼硫酸溶液中提取铼

本文报导D296树脂从含钼硫酸溶液中提取铼的性能。静态实验表明:在pH3—10范围内,铼的吸附率基本恒定,其值为94％;钼的吸附率在pH5.5处达最大。二者分离系数在pH8—10范围内有最大值β_(Re/Mo)=670。动态实验表明:在料液组成和工业料液组成基本相同时,该树脂对铼的吸附容量大于240mg/g,钼的吸附容量低于35mg/g;用8％NH_4OH+10％NH_4NO_3洗脱铼,回收率大于94％;经吸附一一洗脱后,铼富集约10倍。     

酯类交联剂交联丙烯酸钠吸水树脂的紫外引发制备与性能

以部分中和的丙烯酸为原料,分别以乙二醇二甲基丙烯酸（EGDMA）、二甲基丙烯酸甘油酯（GDA）与三乙二醇二甲基丙烯酸（TEGDMA）为交联剂,通过紫外引发合成了聚丙烯酸钠缩乙二醇二甲基丙烯酸（PAANa-E）、聚丙烯酸钠缩二甲基丙烯酸甘油酯（PAANa-GDA）、聚丙烯酸钠缩三乙二醇二甲基丙烯酸（PAANa-TE）3种丙烯酸钠高吸水树脂。考察了交联剂用量、单体体积分数、丙烯酸中和度、辐照时间对树脂吸液率的影响,研究了3种不同链长的酯类交联剂制备的树脂吸液率与温度、pH、盐溶液浓度的关系。采用红外、热失重分析对树脂进行了表征。结果表明：以上3种树脂在最佳条件下吸去离子水率和吸NaCl溶液率分别为2 509,170g/g;2 291,125g/g;3 930,219g/g。其中PAANa-TE的吸液率最高,PAANa-E的吸液率次之,PAANa-GDA的吸液率最低。当极性基团类型相同,数量不同时,PAANa-E、PAANa-TE树脂的吸液率随着交联剂所含醚基数目的增加显著提高。     

聚乙烯吡啶化学修饰电极预富集-石墨炉原子吸收法测定酒石酸锑钾的研究

本文研究了聚乙烯吡啶(PVP)化学修饰电极预富集——石墨炉原子吸收法测定酒石酸锑钾的方法。结果表明,在 pH 为3.5的 HCl 介质中,酒石酸锑钾浓度在5.4×10~(-8)～2.2×10~(-6)g/ml 范围内,与吸光度值呈良好的线性关系。对1.1×10~(-6)g/ml 的酒石酸锑钾溶液平行测定9次,相对标准偏差为4.9%,最低检测限为1.6×10~(-8)g/ml。17种异离子及有机物不干扰测定,回收率在97～103%之间,结果令人满意。     

氧弹燃烧-离子色谱法测定煤中氯含量

建立了氧弹燃烧-离子色谱测定煤中氯含量的方法.在加有(NH4)2CO3溶液和过量氧气的氧弹中燃烧煤样,释放的氯被(NH4)2CO3溶液吸收,过滤溶液后, 采用离子色谱外标法测定滤液中氯的浓度,最后计算出煤中氯的含量.色谱工作条件:淋洗液为1.8 mmol/L Na2CO3与1.7 mmol/L NaHCO3混合液,流速1 mL/min;再生液为40 mmol/L H2SO4,流速0.5 mL/min;进样量20 μL.色谱标准工作曲线线性相关系数0.9996;10次测定1 mg/L Cl-标准溶液的均值为1.0012 mg/L,相对标准偏差为1.34%;8个煤样加标回收率为90.7%～104.3%;测定标准物质GBW11119 及GBW11120的相对误差分别为1.75%和1.36%;对比研究显示,氧弹燃烧-离子色谱测定8个煤样(除两个煤样外)氯含量结果远高于艾士卡剂混合熔样-离子色谱测定结果,表明艾士卡剂混合熔样过程由于煤样未处于完全密闭状态导致部分氯的散失.     

双水相浮选过程中青霉素的分离行为

基于双水相浮选技术(ATPF)分离富集水相中青霉素的方法,研究了双水相浮选过程中青霉素的分离行为.在常温下,2.5 g/L青霉素水溶液300 mL、初始pH 7、(NH4)2SO4浓度350 g/L、浮选溶剂为50%(w/w)PEG1000水溶液10 mL条件下,分别研究了青霉素在双水相浮选过程中的动力学行为和分离后的...     

丙烯酸-淀粉-硅藻土复合耐盐性高吸水树脂的紫外光引发合成及其性能

以丙烯酸、淀粉和硅藻土为原料,使用自制的紫外光聚合装置合成了复合耐盐性高吸水树脂。研究了丙烯酸中和度、硅藻土和淀粉用量、辐照时间等因素对树脂的吸液性能的影响,及pH、盐溶液浓度对树脂吸水率的影响,并用红外光谱和扫描电镜对产物进行了表征。在最佳试验条件下合成的高吸水树脂的吸去离子水率为3 665 g/g,吸生理盐水率(w=0.9%的NaCl水溶液)为280 g/g。     

紫外光聚合法制备棉秆纤维素接枝丙烯酸-腐植酸高吸水树脂及其性能

以丙烯酸(AA)、改性棉秆纤维素(MCSC)和腐植酸(HA)为原料,2,2-二甲氧基-苯基甲酮为引发剂,采用紫外光聚合法制备了降解性复合高吸水树脂(MCSC-g-PAA/HA)。用红外光谱和扫描电镜对产物进行了表征。研究了AA的浓度、MCSC和HA的含量、反应时间和光引发剂的添加量等因素对该树脂溶胀性能的影响。通过测定该树脂的吸水速率和土壤中的保水率及降解性,研究了盐溶液浓度对树脂吸液率的影响。结果表明,在优化条件下,所得树脂在蒸馏水和食盐水(w(NaCl)=0.9%)中的吸液率分别达到870 g/g与94 g/g。     

Converting water absorbent polymer to alcohol absorbent polymer

In this paper, a commercial water absorbent polymer based on poly (sodium acrylate) (PAANa) was converted to an alcohol absorbent polymer. PAANa collapses in alcoholic swelling media such as ethanol and methanol. In the present paper, first, a full interpenetrating polymer network (IPN) gel was prepared through immersing PAANa hydrogel in a solution containing 2‐acrylamido2‐methyl propane sulfonic acid (AMPS), polyethylene glycol dimetahcrylate and ammonium persulfate. The second network was formed in hydrated PAANa through heating. It was synthesized in two conditions by chemical crosslinker and crosslinker‐free. The IPN was acid treated to investigate the effect of removing Na⁺ on alcohol absorbency. The synthesized IPN gels have the ability of absorbing up to 21 and 39 g/g ethanol and methanol, respectively. The samples which were synthesized using the chemical crosslinker in the second stage had more alcohol absorbency in comparison with the crosslinker‐free samples. Unexpectedly, acid treatment caused a decrease in alcohol absorbency. The IPN gels were characterized through thermogravimetric analyses (TGA) and dynamic mechanical thermal analysis (DMTA). The DMTA results confirmed the IPN structure of the gels, two distinctive peaks, which can be attributed to PAANa, and poly (AMPS) was observed in tan delta figures. TGA thermograms demonstrated that IPN had lower thermal stability in comparison with the initial PAANa, which can be attributed to higher vulnerability of SO₃H group for degradation that reduced initial decomposition temperature. Copyright © 2012 John Wiley & Sons, Ltd.     

Ruthenium complexes with tetraphenylimidodiphosphinate: syntheses, structures, and applications to catalytic organic oxidation

Treatment of Ru(PPh3)3Cl2 with K(tpip) (tpip(-)=[N(Ph2PO)2](-)) afforded Ru(tpip)(PPh3)2Cl (1), which reacted with 4- t-Bu-C6H4CN, SO2(g), and NH 3(g) to give Ru(tpip)(PPh3)2Cl(4- t-BuC6H4CN) (2), Ru(tpip)(PPh3)2Cl(SO2) (3), and fac-[Ru(NH3)3(PPh3)2Cl][tpip] (4), respectively. Reaction of [Ru(CO)2Cl2] x with K(tpip) in refluxing tetrahydrofuran (THF) led to isolation of the K/Ru bimetallic compound K 2Ru2(tpip)4(CO)4Cl2 (5). Photolysis of cis-Ru(tpip) 2(NO)Cl in MeCN and wet CH 2Cl 2 afforded cis-Ru(tpip) 2(MeCN)Cl ( 6) and cis-Ru(tpip)2(H2O)Cl (7), respectively. Refluxing 6 in neat THF yielded Ru(tpip) 2(THF)Cl (8). Treatment of Ru(CHR)Cl2(PCy3)2 (Cy=cyclohexyl) with [Ag(tpip)] 4 afforded cis-Ru(tpip)2(CHR)(PCy3) [R=Ph (9), OEt (10)]. Complex 9 is capable of catalyzing oxidation of alcohols and olefins with N-methylmorpholine N-oxide and iodosylbenzene, respectively. The crystal structures of 2-7 and 9 were determined.     

Analysis of metallothioneins by the modified Brdicka procedure

Quantitative analysis of metallothioneins (MTs) by the modified Brdicka procedure is based on the evaluation of the catalytic hydrogen signal (Cat). The effect of the basic physico-chemical parameters, the temperature and the depolarizer concentration (Co(NH(3))(6)Cl(3)), on the Cat signal height and the respective calibration straight lines was studied by means of the differential pulse (DP) mode at the hanging mercury drop electrode (HMDE). The temperature was varied from 7 to 18 degrees C, and the depolarizer concentration from 1.2x10(-4) to 1.0x10(-3) M Co(NH(3))(6)Cl(3). The commercially available rabbit liver MT was used as the calibrant. The parameters of the calibration straight lines, the standard errors of the intercept s(a) and the slope s(b) were evaluated by means of the least-square method. The hypothesis of a significant difference of the estimated value of the intercept on y-axis compared to the zero value was statistically tested. For those conditions for which this hypothesis was rejected the measuring conditions of the catalytic hydrogen signal are selected and they refer to a buffer 1M (NH(4)Cl+NH(4)OH), pH 9.5, (7.0+/-0.5) degrees C and the depolarizer concentration (0.8 or 1.0)x10(-3) M Co(NH(3))(6)Cl(3).     

Remote substituent effects on N-X (X = H,F, Cl,CH3, Li) bond dissociation energies in para-substituted anilines

UB3LYP/6-311++g**//UB3LYP/6-31+g* and ROMP2/6-311++g**//UB3LYP/6-31+g* methods were used to calculate (i) N-X bond dissociation energies (BDE) in 4-YC6H4NH-X and (ii) N-H BDEs in 4-YC6H4NU-H, where Y = H, Me, OCH3, SMe, NH2, NMe2, SiMe3, F, Cl, CN, COOH, CF3, and NO2, X = H, CH3, F, Cl, and Li, and U = H, F, and CH(3). It was found that N-H BDEs of 4-YC6H4NH2 have a positive correlation with the substituent sigma(p+) constants. The slope (rho+) is about 3.0-4.3 kcal/mol, which is in good agreement with the experimental results. It was also found that the substituent effects on N-X BDEs of 4-YC6H4NH-X change considerably when X changes. rho(+)values for N-CH3, N-F, N-Cl, and N-Li BDEs were calculated to be 3.1-4.6, 1.3-1.9, 1.8-2.6, and 4.9-6.8 kcal/mol, respectively. The reason for the variation of substituent effects was proposed to be the ground-state effect, i.e., the interaction between the intact NH-X moiety and the parasubstituents. Finally, alpha-substitution was found to be able to significantly change the substituent effects. rho(+)values for N-H BDEs of 4-C6H4NCH3(-)H and 4-C6H4NF-H are 2.5-4.0 and 1.7-1.9 kcal/mol, respectively.     

13C and 77Se NMR spectra of thienoisoselenazoles,selenoloisothiazoles, selenoloisoselenazoles and thienoisothiazoles

Measurements are reported of NH exchange rates of urea, thiourea, acetamide and thioacetamide, using line-shape analysis with natural-abundance ¹⁵N NMR spectra. Base-catalyzed NH-proton exchange of thiourea is 30–40 times faster than for urea, while the corresponding acid-catalyzed exchange is 150 times slower. The base-catalyzed proton exchange for thioacetamide is about 1000 times faster than that of acetamide at 25°C, while the corresponding acid-catalyzed exchange is some 260 times slower.     

Bioconversion of fumarate to succinate using glycerol as a carbon source

In this study, a facultative bacterium that converts fumarate to succinate at a high yield was isolated. The yield of biocon version was enhanced about 1.2 times by addition of glucose into culture medium at an initial concentration of 6 g/L. When the initial cell density was high (2 g/L), the succinate produced at pH 7.0 for initial fumarate concentrations of 30, 50, 80, and 100 g/L were 29.3, 40.9, 63.6, and 82.5 g/L, respectively, showing an increase with the initial fumarate concentration. The high yield of 96.8%/mole of fumarate in just 4 h was obtained at the initial fumarate concentration of 30 g/L. Comparing these values to those obtained with low cell culture (0.2 g/L), we found that the amount of succinate produced was similar, but the production rate in the high cell culture was about three times higher than was the case in the low cell culture. This strain converted fumarate to succinate at a rate of 3.5 g/L·h under the sparge of CO₂.     

EFFECTS OF NH4CI ON THE INTERACTION BETWEEN POLY(ETHYLENE OXIDE)AND IONIC SURFACTANTS IN AQUEOUS SOLUTIONS

The interaction of poly(ethylene oxide)(PEO)with the ionic surfactants,sodium dodecylsulfate(SDS)and cetyltrimethylammonium chloride(CTAC)respectively,in aqueous solutions containing a certain concentration of NH4Cl,is studied by the viscosity measurement.It has been found that the ion-dipole interaction between PEO and ionic surfactants is changed considerably by the organic salt.For anionic surfactant of SDS,the addition of NH4Cl into solution strengthens the interaction between PEO and the headgroup of SDS.On the other hand,for cationic surfactant of CTAC,the interaction between PEO and the headgroup of CTAC is screened significantly by NH4Cl dissolved in solution.These findings may potentially be attributed to the negative property of the oxygen group of the PEO chain.In the presence of NH4Cl,the cationic ions of the organic salt bind to the oxygen group of the PEO chain so that PEO can be referred to as a pseudopolyelectrolyte in solution.     

Effect of tanshinone IIA on the noncovalent interaction between warfarin and human serum albumin studied by electrospray ionization mass spectrometry

Enhanced anticoagulation and/or even bleeding are often observed when patients on long-term warfarin (WAR) therapy consumed Danshen, a well-known medicinal herb in traditional Chinese medicine (TCM). This study demonstrates that altered WAR metabolism, arising from its interaction with the active components in Danshen, played a significant role in this curative effect. Mass spectrometric techniques including ESI-ITMS (electrospray ionization ion-trap mass spectrometry) and ESI-TOF (time-of-flight)-MS have been developed for the study of such drug-herb interactions. The experimental approach involved a detailed analysis and comparison of WAR metabolites in vivo from blood or urine of rats that had been orally administrated with WAR, either singly or together with the representative bioactive component of Danshen-lipid soluble TIIA (Tanshinon IIA), and a study of the interaction of human serum albumin (HSA), WAR, and water-soluble sodium tanshinone IIA sulfonate (STS) in vitro. Results demonstrate that TIIA accelerates the metabolic rate of WAR, whereas STS displaces WAR from the WAR-HSA complex, resulting in an increase of free WAR concentration in blood. It is suggested that the elevated level and enhanced metabolism of WAR is responsible for the over-anticoagulation effect observed.     

Stereoselectivity of the secondary isotope effect in the aquation of [Co(NH3)5Cl]2+

A careful kinetic study of the acid hydrolysis of [Co(NH(3))(5)Cl](2+) and the selectively deuterated species trans-[Co(NH(3))(4)(ND(3))Cl](2+), trans-[Co(ND(3))(4)(NH(3))Cl](2+), and [Co(ND(3))(5)Cl](2+) reveals that N-deuteration reduces the hydrolysis rate at both the cis and trans sites. On a per-D basis, the rate reduction is three times more effective for trans-Cl deuteration. This result is contrary to conventional wisdom but has never been tested previously. It appears to be the first example of significant stereoselectivity for the secondary isotope effect in a substitution reaction, in either inorganic or organic systems. An explanation is offered in terms of the effect of D-substitution on zero point energies, the different extents of coupling of NH(D) and Co-Cl vibrational modes according to their stereochemical relationship, and the view that the rate of acid hydrolysis of the [Co(NH(3))(5)Cl](2+) involves an aberrant Co-Cl vibration component.     

Synthesis and reactivity of Ir(I) and Ir(III) complexes with MeNH2, Me2C=NR (R = H, Me), C,N-C6H4{C(Me)=N(Me)}-2, and N,N'-RN=C(Me)CH2C(Me2)NHR (R = H, Me) ligands

Complexes [Ir(Cp*)Cl(n)(NH2Me)(3-n)]X(m) (n = 2, m = 0 (1), n = 1, m = 1, X = Cl (2a), n = 0, m = 2, X = OTf (3)) are obtained by reacting [Ir(Cp*)Cl(mu-Cl)]2 with MeNH2 (1:2 or 1:8) or with [Ag(NH2Me)2]OTf (1:4), respectively. Complex 2b (n = 1, m = 1, X = ClO 4) is obtained from 2a and NaClO4 x H2O. The reaction of 3 with MeC(O)Ph at 80 degrees C gives [Ir(Cp*){C,N-C6H4{C(Me)=N(Me)}-2}(NH2Me)]OTf (4), which in turn reacts with RNC to give [Ir(Cp*){C,N-C6H4{C(Me)=N(Me)}-2}(CNR)]OTf (R = (t)Bu (5), Xy (6)). [Ir(mu-Cl)(COD)]2 reacts with [Ag{N(R)=CMe2}2]X (1:2) to give [Ir{N(R)=CMe2}2(COD)]X (R = H, X = ClO4 (7); R = Me, X = OTf (8)). Complexes [Ir(CO)2(NH=CMe2)2]ClO4 (9) and [IrCl{N(R)=CMe2}(COD)] (R = H (10), Me (11)) are obtained from the appropriate [Ir{N(R)=CMe2}2(COD)]X and CO or Me4NCl, respectively. [Ir(Cp*)Cl(mu-Cl)]2 reacts with [Au(NH=CMe2)(PPh3)]ClO4 (1:2) to give [Ir(Cp*)(mu-Cl)(NH=CMe2)]2(ClO4)2 (12) which in turn reacts with PPh 3 or Me4NCl (1:2) to give [Ir(Cp*)Cl(NH=CMe2)(PPh3)]ClO4 (13) or [Ir(Cp*)Cl2(NH=CMe2)] (14), respectively. Complex 14 hydrolyzes in a CH2Cl2/Et2O solution to give [Ir(Cp*)Cl2(NH3)] (15). The reaction of [Ir(Cp*)Cl(mu-Cl)]2 with [Ag(NH=CMe2)2]ClO4 (1:4) gives [Ir(Cp*)(NH=CMe2)3](ClO4)2 (16a), which reacts with PPNCl (PPN = Ph3=P=N=PPh3) under different reaction conditions to give [Ir(Cp*)(NH=CMe2)3]XY (X = Cl, Y = ClO4 (16b); X = Y = Cl (16c)). Equimolar amounts of 14 and 16a react to give [Ir(Cp*)Cl(NH=CMe2)2]ClO4 (17), which in turn reacts with PPNCl to give [Ir(Cp*)Cl(H-imam)]Cl (R-imam = N,N'-N(R)=C(Me)CH2C(Me)2NHR (18a)]. Complexes [Ir(Cp*)Cl(R-imam)]ClO4 (R = H (18b), Me (19)) are obtained from 18a and AgClO4 or by refluxing 2b in acetone for 7 h, respectively. They react with AgClO4 and the appropriate neutral ligand or with [Ag(NH=CMe2)2]ClO4 to give [Ir(Cp*)(R-imam)L](ClO4)2 (R = H, L = (t)BuNC (20), XyNC (21); R = Me, L = MeCN (22)) or [Ir(Cp*)(H-imam)(NH=CMe2)](ClO4)2 (23a), respectively. The later reacts with PPNCl to give [Ir(Cp*)(H-imam)(NH=CMe2)]Cl(ClO4) (23b). The reaction of 22 with XyNC gives [Ir(Cp*)(Me-imam)(CNXy)](ClO4)2 (24). The structures of complexes 15, 16c and 18b have been solved by X-ray diffraction methods.