Partitioning of quencher ions in the micellar microenvironment of polyoxyethylene nonyl phenol

This paper has explored the quenching of fluorescence of the dye safranine T (ST) by the inorganic cations viz Cu2+, Co2+, Ni2+ and Mn2+ in micellar solutions of the surfactant dioxyethylene nonyl phenol (Igepal CO-210), pentaoxyethylene nonyl phenol (Igepal CO-520) and dodecaoxyethylene nonyl phenol (Igepal CO-720). The quenching results have been calculated in light of stern volmer equation (SV) to evaluate the extent of interaction between the fluorophore (ST) and quencher. The average concentration of the quencher ions in the micelle have been determined. The quenching efficiency of ST by inorganic ions in micellar medium is lower than that in aqueous medium. The results show that the ions get partitioned in the micellar medium. The values of the partition coefficient of the ions decrease with increase in HLB value and number of oxyethylene groups in Igepal.     

Rhodamine-derived Schiff base for the selective determination of mercuric ions in water media

A new rhodamine-derived Schiff base (RS) was synthesized and its sensing property to metal ions was investigated by UV/vis and fluorescence spectroscopies. Addition of Hg2+ ions to the aqueous solution of RS gave a visual color change as well as significantly fluorescent enhancement, while other ions including Pb2+, Cd2+, Cr3+, Zn2+, Cu2+, Fe2+, Co3+, Ni2+, Ca2+, Mg2+, K+ and Na+ ions did not induce any distinct color/spectral changes, which constituted a Hg2+-selective fluorescent OFF-ON chemosensor. The Hg2+-induced ring-opening of spirolactam of rhodamine in RS resulted in the dual chromo- and fluorogenic observation.     

Density functional theory-based prediction of the formation constants of complexes of ammonia in aqueous solution: indications of the role of relativistic effects in the solution chemistry of gold(I)

A prediction of the formation constants (log K1) for complexes of metal ions with a single NH3 ligand in aqueous solution, using quantum mechanical calculations, is reported. DeltaG values at 298 K in the gas phase for eq 1 (DeltaG(DFT)) were calculated for 34 metal ions using density functional theory (DFT), with the expectation that these would correlate with the free energy of complex formation in aqueous solution (DeltaG(aq)). [M(H2O)6]n+(g) + NH(3)(g) = [M(H2O)5NH3]n+(g) + H2O(g) (eq 1). The DeltaG(aq) values include the effects of complex changes in solvation on complex formation, which are not included in eq 1. It was anticipated that such changes in solvation would be constant or vary systematically with changes in the log K(1) value for different metal ions; therefore, simple correlations between DeltaG(DFT) and DeltaG(aq) were sought. The bulk of the log K1(NH3) values used to calculate DeltaG(aq) were not experimental, but estimated previously (Hancock 1978, 1980) from a variety of empirical correlations. Separate linear correlations between DeltaG(DFT) and DeltaG(aq) for metal ions of different charges (M2+, M3+, and M4+) were found. In plots of DeltaG(DFT) versus DeltaG(aq), the slopes ranged from 2.201 for M2+ ions down to 1.076 for M4+ ions, with intercepts increasing from M2+ to M4+ ions. Two separate correlations occurred for the M3+ ions, which appeared to correspond to small metal ions with a coordination number (CN) of 6 and to large metal ions with a higher CN in the vicinity of 7-9. The good correlation coefficients (R) in the range of 0.97-0.99 for all these separate correlations suggest that the approach used here may be the basis for future predictions of aqueous phase chemistry that would otherwise be experimentally inaccessible. Thus, the log K1(NH3) value for the transuranic Lr3+, which has a half-life of 3.6 h in its most stable isotope, is predicted to be 1.46. These calculations should also lead to a greater insight into the factors governing complex formation in aqueous solution. All of the above DFT calculations involved corrections for scalar relativistic effects (RE). Au has been described (Koltsoyannis 1997) as a "relativistic element". The chief effect of RE for group 11 ions is to favor linear coordination geometry and greatly increase covalence in the M-L bond. The correlation for M+ ions (H+, Cu+, Ag+, Au+) involved the preferred linear coordination of the [M(H2O)2]+ complexes, so that the DFT calculations of DeltaG for the gas-phase reaction in eq 2 were carried out for M = H+, Cu+, Ag+, and Au+. [M(H2O)2]+(g) + NH3(g) = [M(H2O)NH3]+(g) + H2O(g) (eq 2). Additional DFT calculations for eq 2 were carried out omitting corrections for RE. These indicated, in the absence of RE, virtually no change in the log K1(NH3) value for H+, a small decrease for Cu+, and a larger decrease for Ag+. There would, however, be a very large decrease in the log K1(NH3) value for Au(I) from 9.8 (RE included) to 1.6 (RE omitted). These results suggest that much of "soft" acid behavior in aqueous solution in the hard and soft acid-base classification of Pearson may be the result of RE in the elements close to Au in the periodic table.     

Determination of environmentally important metal ions by fluorescence quenching in anionic micellar solution

This work describes the effect of a variety of metal ions as quenchers of the fluorescence of naphthalene, in aqueous micellar solutions of sodium dodecyl sulfate (SDS). The quenching by the metal ions can be adequately described by the Stern-Volmer equation and the best signal to noise ratios are obtained with low micellized detergent concentrations. Apparent Stern-Volmer constants decrease in the order: Fe3+ > Cu2+ > Pb2+ > Cr3+ > Ni2+ and directly reflect the relative sensitivity of the method for these ions. Detection limits (defined as three times the standard deviation of the blank for n= 10) for the fluorescence quenching of naphthalene by the metal ions in aqueous micellar SDS are in the range of 1.0 x 10(-6) to 1.0 x 10(-5) mol dm(-3). The proposed fluorescence quenching method shows good repeatibility for a variety of added quencher metal ions, indicating that anionic micelle-enhanced fluorescence quenching by metal ions constitutes an analytical method of rather general application.     

4-[2-(二甲氨基)乙氧基]-N-十八烷基-1,8-萘酰亚胺荧光染料的合成及其性能研究

以4-溴-1,8-萘酐为原料,合成脂溶性4-[2-(二甲氨基)乙氧基]-N-十八烷基-1,8-萘酰亚胺。对其进行了1H NMR和IR表征。考察了荧光染料在DMF、乙腈、丙酮、乙酸乙酯和乙醚5种溶剂中的荧光光谱和吸收光谱,发现由于溶剂效应,随溶剂极性由小到大,荧光光谱和吸收光谱的最大峰值波长逐渐红移。考察了不同金属离子和pH对荧光染料荧光光谱的影响,结果表明荧光强度随Fe3+、Zn2+、Co2+浓度增大而逐渐增强,Fe3+的影响最为显著;当pH<7时,荧光强度随着pH的降低逐渐增强;进一步考察了Fe3+、Zn2+、Co2+对吸收光谱的影响,结果发现吸收光谱均蓝移。分析认为荧光染料的光致电子转移被阻碍,实验结果表明,合成的新型荧光染料可用于溶液中金属离子和pH的检测。     

Separation of transition metals in nonaqueous media with capillary electrophoresis

The separation of transition metal Ni2+, Cu2+, Co2+, Zn2+, Cd2+ and Fe3+ in methanol was investigated by using different types of organic acids as complexing agents. In pure methanol, the weaker and simpler acetic, propionic, butyric and valeric acids could enhance metal ions selectivity by increasing acid concentration and metal ions could be separated with high efficiency. However, hydroxycarboxylic acids obviously made separation efficiency worse. The effect of mixed organic acids, mixture solvent (methanol-acetonitrile, methanol-water) on metal ions separation was discussed further. The advantages of using nonaqueous solvent over aqueous for metal ions separation were shown finally.     

Use of nonionic poly(ethylene glycol) p-isooctyl-phenyl ether (Triton X-1 00) surfactant mobile phases in the thin-layer chromatography of heavy-metal cations

The analytical potential of poly(ethylene glycol) p-isooctyl-phenyl ether (Triton X-100), a nonionic surfactant, is used as a mobile phase in the thin-layer chromatographic separation of heavy-metal cations. The surfactant concentration below its critical micellar concentration (CMC) as well as above the CMC value is used to investigate the migrational behavior of some heavy-metal ions on silica gel layers. The mobility of the metal ions is found to change marginally with the increase of surfactant concentration from 0.001M (below CMC) to 0.1M (above CMC). The influence of the pH of the medium, nonelectrolyte organic (urea and alkanols), and inorganic electrolyte (NaCI) additives in the surfactant containing mobile phase on the mobility of heavy metals on the silica gel layer is examined. For separating metal ions, surfactant must be used in the presence of buffers. Triton X-100 (0.02M) at pH 2.3 is found to be the best mobile phase for the separation of heavy-metal cations. In general, the presence of alcohol in aqueous surfactant solutions results in a decrease in the mobility of metal ions. Besides Cu2+ and Fe3+, all of the metal ions show a trend of increasing the retardation factor beyond a minima at 0.1 or 0.3M of added urea or NaCl. The proposed method is successfully applied for the simultaneous detection of Zn2+ and Cd2+ from a spiked human blood sample.     

Properties of a new 4-imidazolyl derivative of a 14-membered tetraazamacrocyclic chelating agent

A new bis-N,N'-(5-methylimidazol-4-ylmethyl) derivative of a 14-membered tetraazamacrocycle, L1, has been synthesized. The protonation constants of this compound and the stability constants of its complexes with divalent first-row transition metal ions and Fe3+ were determined at 298.2 K in aqueous 0.10 mol dm(-3) KNO3. Compound L1 exhibits high overall basicity, which is mainly conferred by the imidazolyl groups. The complexes of the divalent first row-transition metal ions of L1 follow the Irving-Williams order of stability with the maximum for Cu2+ as expected, but a steep fall of constants is verified for the Mn2+, Fe2+ and Co2+, in one side, and for the Zn2+ complexes, in the other side. Additionally, L1 shows a large affinity for Fe3+, and the relative stability constants for its Cd2+ and Pb2+ complexes indicate that L1 may be useful for the complexometric determination of these two toxic metal ions in solutions containing both metal ions. These studies together with NMR, UV-vis and EPR spectroscopic data indicated the presence of mononuclear complexes, which adopt distorted pyramidal or octahedral geometries depending on the metal centre. The X-ray crystal structure of [Cu(HL1)](PF6)2(NO3).H2O showed that the coordination sphere of the copper centre can be described as a distorted square pyramid with the basal plane defined by three nitrogen donors of the macrocycle backbone and one nitrogen atom from one imidazolyl pendant arm. The apical position is occupied by the nitrogen atom of the macrocycle trans to the pyridine ring. To achieve this coordination environment, the macrocycle is folded along the axis defined by the two N atoms contiguous to the pyridine ring. The free methylimidazolyl arm points away from the metal centre leading to an intramolecular Cu[dot dot dot]N distance of 5.155(1) A.     

A copper(II) ion-selective on-off-type fluoroionophore based on zinc porphyrin-dipyridylamino

A new copper(II) fluorescent sensor 5,10,15,20-tetra((p-N,N-bis(2-pyridyl)amino)phenyl)porphyrin zinc (1) has been designed and synthesized by the Ullmann-type condensation of bromoporphyrin zinc with 2,2'-dipyridylamine (dpa) under copper powder as a catalyst as well as with K2CO3 as the base in a DMF solution. It consists of two separately functional moieties: the zinc porphyrin performs as a fluorophore, and the dpa-linked-to-zinc porphyrin acts as a selected binding site for metal ions. It displays a high selectivity and antidisturbance for the Cu2+ ion among the metal ions examined (Na+, Mg2+, Cr3+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Ag+, Zn2+, Cd2+, Hg2+, and Fe3+) and exhibits fluorescence quenching upon the binding of the Cu2+ ion with an "on-off"-type fluoroionophoric switching property. The detection limit is found to be 3.3 x 10(-7) M (3s blank) for Cu2+ ion in methanol solution, and its fluorescence can be revived by the addition of EDTA disodium solution. The design strategy and remarkable photophysical properties of sensor 1 help to extend the development of fluorescent sensors for metal ions.     

螯合树脂研究 Ⅻ.以聚硫醚为主链的异丙巯基胺树脂的合成及其吸附性能

由聚环硫氟丙烷与多乙烯多胺反应制得的聚合物(PB)再与环硫丙烷反应,合成了四种以聚硫醚为主链的异丙巯基胺树脂(PBM_1-4)。树脂对Au~(3+)、Pd~(2+)、Pt~(4+)、Ag~+和Hg~(2+)等离子具有强的吸附能力,对Cu~(2+)次之,对Zn~(2+)和Pb~(2+)很弱。树脂对贵金属具有高的选择性,能从含Au~(3+)、Cr~(3+)、Co~(2+)、Ni~(2+)、Cu~(2+)、Mn~(2+)、Zn~(2+)和Fe~(3+)的溶液中定量吸附Au~(3+)而不吸附其它离子。     

Potentiometric study of binary complexes of methyl 2-pyridyl ketone oxime, phenyl 2-pyridyl ketone oxime and diacetyl monooxime with some transition and heavy metal ions in aqueous solution

The complexation reaction between some oximes including methyl-2-pyridylketone oxime (MPKO), phenyl-2-pyridylketone oxime (PPKO) and diacetyl monooxime (DMO) with some transition and heavy metal ions Co2+, Ni2+, Zn2+, Pb2+, Fe2+, Fe3+, Cr3+ and La3+ has been studied potentiometrically in aqueous solution at 25+/-0.1 degrees C and ionic strength (mu) of 0.1M supported by KCl. The overall stability constants logbeta's of respective species were obtained by computer refinement of pH-volume data using BEST program. The best model among the several proposed models was selected according to the lowest sigma(fit) value. The main species in binary systems are ML, ML2, MLH, MLH2, ML2H, ML2H2, MOHL, M(OH)2L, M(OH)L2 and M(OH)2L2 (L = MPKO or PPKO or DMO).     

金属离子与腺嘌呤异构体复合物的稳定性

在B3LYP/6-311++G**//6-31+G*基组水平上结合PCM模型系统的优化了气相和液相环境中14种腺嘌呤异构体与四种金属离子(Na+,K+,Mg2+,Ca2+)形成的132个稳定复合物。通过能量对比,得到了所有复合物异构体在气液两相中的稳定性顺序及不同金属离子与同一异构体形成的复合物的能量排序,首次给出了液相中这些不同金属离子复合物的最稳定结构。结果发现溶剂效应导致了液相中的复合物稳定性顺序与气相中的相比发生了很大变化;同一异构体与不同金属离子形成的复合物其稳定性在排序中也变化很大。对于这些变化,本文分别从金属离子与腺嘌呤的复合物在气相中的结合能(EBE)及在液相中的溶质溶剂相互作用能(Epol)能等方面进行了系统的阐述     

多种金属离子对一株双齿相手蟹肠道共生真菌生长代谢影响的研究

对一株双齿相手蟹肠道共生真菌Sporothrixsp．（ZJSEF-7）,测定了12种金属离子对该菌生长代谢的影响。结果表明,Fe^3＋、K^＋、Mn^2＋、Mg^2＋、Ca^2＋和Sb^3＋可明显促进菌体的生长;Cu^2＋、Sn^2＋和Pb^2＋对菌体生长没有明显的影响;Fe^2＋对菌体生长有强的抑制作用;Al^3＋和Zn^2＋完全抑制菌体生长。相手蟹共生菌对部分重金属显示了一定的抗性和强的化学防御功能,深入研究其作用机制,将有助于了解相手蟹共生菌的生物学本质及其生态学作用,对于保护红树林生态环境具有重要的意义。     

CMC-Na/DETA-B62型蛇笼树脂对金属离子的吸附性能

本文研究了自合成的蛇笼型螯合树脂-二乙烯三胺交联甘油环氧树脂/羰甲基纤维素体系对Cd^2 ,Pb^2 ,Fe^2 的吸附量，吸附动力学，等温吸附过程等静态吸附性能，同时研究了pH值等因素对吸附性能的影响。实验结果表明，该树脂对Cd^2 具有较强的吸附选择性，能在Cd^2 ,Pb^2 ,Fe^2 3种离子共存时选择吸附Cd^2 ，其选择性系数分别为Kcd^2 /pb^2 =3.77,Kcd^2 /Fe^2 =9.61。该树脂对上述3种离子的吸附量可分别达4.00,1.06,0.42mmol/g。该类树脂可用于含重金属离子污水的处理和金属离子的分离等方面。     

Highly selective and efficient membrane transport of silver as AgBr2- ion using K+-decyl-18-crown-6 as carrier.

Potassium-decyl-18-crown-6 was used as a highly selective and efficient carrier for uphill transport of silver as AgBr2-complex ion through a chloroform bulk liquid membrane. When thiosulfate anion was used as a metal ion acceptor in the receiving phase the amounts of silver transported across the liquid membrane after 120 and 180 min were 87.0 +/- 1.8% and 96.0 +/- 1.9%, respectively. The selectivity and efficiency of silver transport from aqueous solution containing Cu2+, Zn2+, Ni2+, Cd2+, Pb2+ and Fe3+ ions were investigated. In the presence of EDTA at pH = 4 as suitable masking agent in the source phase, the interfering effects of Pb2+ and Fe3+ ions were diminished drastically.     

低压离子分离-化学发光在线检测过渡金属离子

 研究了低压离子 (LPIC)分离 柱后鲁米诺化学发光 (CL)检测方法 ,并分离测定了Cu2 + ,Co2 + ,Cr3 + ,Fe2 + ,Mn2 + 等 5种过渡金属离子。以草酸 柠檬酸混合溶液作为洗脱液 ,Luminol H2 O2 Mn + 作为化学发光检测体系 ,对过渡金属离子进行在线检测。测定的线性范围分别为 (mg·L-1) :Co2 + ,0 0 0 1～ 0 .1;Cu2 + ,0 1～ 6 ;Mn2 + ,0 0 6～ 4 ;Fe2 + ,0 0 3～ 5 ;Cr3 + ,0 0 2 5～ 1。检测限分别为 (μg·L-1) :Co2 + ,0 85 ;Cu2 + ,85 ;Mn2 + ,4 2 ;Fe2 + ,2 1;Cr3 + ,2 0。     

基于双控荧光开关的NOR和OR分子逻辑门

合成了L-精氨酸蒽衍生物1, 考察了碱土及过渡金属离子对主体分子1荧光光谱的影响, 结果发现, 在中性水溶液条件下只有Cu2＋能有效地猝灭其荧光. 另外, 通过OH－/H＋和Cu2＋/乙二胺四乙酸(EDTA)均能对化合物1的荧光强度进行可逆性调控. 在此基础上, 我们以化合物1水溶液作为起始状态, 以OH－和Cu2＋为两化学输入, 构建了一个“或非”(NOR)分子逻辑门; 以1-Cu2＋水溶液体系作为起始状态, 以H＋和EDTA为两化学输入, 构建了一个“或”(OR)分子逻辑门.     

Promotion of cyclization of linear pentapeptides and heptapeptide by different univalent metal ions

Univalent metal ions such as Na+, K+ and Cs+ can enhance not only the cyclization yields of some linear pentapeptides and heptapeptide but also their cyclization rates while some bivalent and trivalent metal ions such as Mg2+, Ca2+, Zn2+, Fe2+, Ni2+ and Cr3+ elevate neither the cyclization yields nor the cyclization rates and some of them prevent the cyclization.     

硫氰酸钾-氯化十六烷基吡啶-水体系浮选分离钛

研究了氯化十六烷基吡啶和KSCN分离钛的行为及与一些金属离子分离的条件。结果表明,在水溶液中,Ti4+与氯化十六烷基吡啶和KSCN形成不溶于水的三元缔合物[Ti(SCN)62-][CPC+]2,此三元缔合物沉淀浮于水相上层形成界面清晰的液-固两相。当溶液中氯化十六烷基吡啶和KSCN的浓度分别为8.0×10-4mol/L和6.0×10-2 mol/L时,Ti4+可与V5+、Mg2+、Al3+、Cd2+、Mn2+、Ga3+、Fe2+、Ni2+和Cr3+进行分离,该方法在微量Ti的分离和富集分析中有一定的实用价值。