Cu~(2 )和 Fe~(3 )与明胶的相互作用

利用荧光猝灭法,研究了不同温度、酸度下,Ｃｕ２＋和 Ｆｅ３＋与明胶的相互作用．计算了猝灭常数和结合常数．紫外光谱和显微红外光谱的测定结果表明,Ｃｕ２＋、Ｆｅ３＋与明胶分子中的酰胺键发生了作用．探讨了猝灭机理．计算出的热力学函数表明,在Ｃｕ２＋、Ｆｅ３＋与明胶的相互作用过程中熵变起主要的作用．     

A novel electrochemical method to detect mercury (II) ions

A novel and sensitive electrochemical method for determination of mercury (II) ions (Hg²⁺) based on the formation of thymine–Hg²⁺–thymine complexes and gold nanoparticle-mediated signal amplification is reported. Two 5′ end thiolated complementary oligonucleotides containing six strategically placed thymine–thymine mistakes were introduced in this work. One of the two oligonucleotides was immobilized on a gold electrode and the other one on gold nanoparticles (AuNPs). Due to six thymine–thymine mistakes the two oligonucleotides were not able to be hybridized, so AuNPs could not be immobilized onto the electrode surface after the electrode was immersed in the DNA–AuNPs solution. However, if Hg²⁺ existed, T–Hg²⁺–T complexes could be formed and AuNPs could be immobilized onto the electrode surface. Meanwhile, large numbers of [Ru(NH₃)₆]³⁺ molecules as electrochemical species could be localized onto the electrode surface. The Hg²⁺ detection limit of this assay could be as low as 10 nM, which is the US Environmental Protection Agency (EPA) limit of Hg²⁺ for drinkable water. This method is proven to be simple, convenient, high sensitive and selective.     

The Surface Activity of the Hydrated Proton Is Substantially Higher than That of the Hydroxide Ion

The behavior of hydroxide and hydrated protons, the auto‐ionization products of water, at surfaces is important for a wide range of applications and disciplines. However, it is unknown at which bulk concentration these ions start to become surface active at the water–air interface. Here, we report changes in the D₂O–air interface in the presence of excess D⁺_hyd/OD^?_hyd determined using surface‐sensitive vibrational sum‐frequency generation (SFG) spectroscopy. The onset of the perturbation of the D₂O surface occurs at a bulk concentration as low as 2.7±0.2 mm D⁺_hyd. In contrast, a concentration of several hundred mm OD^?_hyd is required to change the D₂O surface. The hydrated proton is thus orders of magnitude more surface‐active than hydroxide at the water–air interface.     

Quantum dot-based "turn-on" fluorescent probe for detection of zinc and cadmium ions in aqueous media

Health or environmental issue caused by abnormal level of metal ions like Zn²⁺ or Cd²⁺ is a worldwide concern. Developing an inexpensive and facile detection method for Zn²⁺ and Cd²⁺ is in urgent demand. Due to their super optical properties, fluorescent quantum dots (QDs) have been developed as a promising alternative for organic dyes in fluorescence analysis. In this study, a CdTe QDs-based sensitive and selective probe for Zn²⁺ and Cd²⁺ in aqueous media was reported. The proposed probe worked in fluorescence “turn-on” mode. The initial bright fluorescence of CdTe QDs was effectively quenched by sulfur anions (S²⁻). The presence of Zn²⁺ (or Cd²⁺) can “turn-on” the weak fluorescence of QDs quenched by S²⁻ due to the formation of ZnS (or CdS) passivation shell. Under optimal conditions, a good linear relationship between the fluorescence response and concentration of Zn²⁺ (or Cd²⁺) could be obtained in the range from 1.6 to 35 μM (1.3–25 μM for Cd²⁺). The limit of detection (LOD) for Zn²⁺ and Cd²⁺ were found to be 1.2 and 0.5 μM, respectively. Furthermore, the present probe exhibited a high selectivity for Zn²⁺ and Cd²⁺ over other metal ions and was successfully used in the detection of Zn²⁺ or Cd²⁺ in real water samples.     

Conductance of tetraalkylammonium salts in propylene carbonate at 25°C

Conductance measurements of 12 quaternary ammonium salts in propylene carbonate (PC) have been made at 25°C. The cations were either tetramethylammonium, tetraethylammonium, or tetra-n-butylammonium, and the concentrations of salt varied from about 2×10^–4 to 5×10^–3 M. The data were analyzed by the equation of Pitts. The results showed that the benzoate, nitrobenzoate, and pentachlorophenolate salts are completely dissociated. The nitrophenolate, chlorophenolate, methylsulfonate, and nitrate salts are only slightly associated (K _A from 2.5 to 6.5), while the acetate, phenylacetate, and nitrophenolate salts display somewhat more extensive association, with ionpair association constants from 17 to 45. Limiting molar conductances for the anions were derived. The factors affecting ionic mobilities in this dipolar aprotic solvent are discussed.On leave 1973–1975 from the University of Gdask, Poland.     

Enthalpies of dilution of electrolyte solutions by flow microcalorimetry

The enthalpies of dilution of NaCl, Me₄NBr, andn-Bu₄NBr were measured in water at 25°C with a new flow microcalorimeter. The data were analyzed with a polynomial equation, and the derived relative apparent molal enthalpies _L are in good agreement with literature values. Provided care is taken that mixing is complete, flow calorimeters are as reliable and much less time-consuming than cell-type instruments for enthalpies of dilution measurements.     

Metal Chelates of Hydrazo-Dimedon Dyes. Chelating Tendencies of 5,5-Dimethylcyclohexane-2-(2-Carboxyphenyl,and 3-Carboxyphenyl)-Hydrazono 1,3-Dione (DC-2-CPHD and DC-3-CPHD)

The consecutive stepwise formation constants of 1:1 and 1:2 chelate species formed by the interaction of DC-2-CPHD and DC-3-CPHD anions with tripositive lanthanon and divalent copper, nickel, cobalt, zinc, manganese, and cadmium cations were determined potentiometrically at ionic strengh of 0.1 (KNO₃) and 30°C. The results indicate that two different coordination modes, one tridentate (DC-2-CPHD), and one bidentate (DC-3-CPHD), are in evidence.     

Effects of substituted ligands on the mobility of complexed anions

From conductance and viscosities measurements on Pr₄NCl, Et₄NBr, and AgNO₃ in acetonitrile and Et₃NBr in nitrobenzene, the Walden products of the anion at infinite dilution were determined in presence of various concentrations of substituted benzoic acids. From these data it was possible to compute the values of the Walden products of the once complexed anions and to estimate the order of magnitude of the Walden products of twice complexed anions. Stokes' law is not obeyed, and the Walden products are not proportional to the third root of the molar volume of the complexed ions, as a consequence of their lack of sphericity. The assumption that the drag force which acts on the ions is proportional to the volume of the substituents results in a linear expression between the reciprocals of the Walden products and the molar volume of the ligands. The experimental results fit this expression within the limits of the experimental errors, and the slopes of the lines are nearly the same for all the anions and for the two solvents studied here, namely, 2.5×10^–4 ohm-cm^–5 mole-cP^–1.