Synthesis and mechanism research of an ethylene glycol-based sol-gel method for preparing PZT nanopowders

Lead zirconate titanate nanopowders Pb(Zr_0.52Ti_0.48)O₃ (PZT) were prepared by modified sol-gel process in ethylene glycol system with zirconium nitrate as the zirconium source. The research showed that it was critical to add lead acetate after the reaction of zirconium nitrate and tetrabutyl titanate in ethylene glycol system for preparing PZT of exact titanium content. The reaction mechanisms of the sol synthesis, preparation of xerogel and agglutinating process were characterized through using FT-IR, NMR, TG-FTIR, and GC-MS. The experiment proved that ethylene glycol system did not rely on hydrolysis and condensation reactions in the process of the sol formation, but on the formation of chain or network large molecules from complexation of ethylene glycol and all Ti and minor Pd, Zr. In the preparation of xerogel, the complexation reaction was so completed that it formed large molecules network composed of metal and dioxyethyl. Bulk weight loss happened before 350°C in the process of sintering xerogel to prepare PZT nanopowders. Volatile matters and vapor phase decomposition resultants were primarily oxy-compounds including ethylene glycol, aldehyde-ketone compounds, carbon dioxide and nitrate radical conversion matters. After 350°C, primary vapor phase decomposition resultants were carbon dioxide and minor carbonyl compound.     

铑配合物的抗肿瘤活性及其作用机制研究

自从Rosenberg等人发现顺铂具有抗肿瘤活性以来，金属配合物的抗肿瘤活性引起了人们的广泛关注。本文综述了近年来铑配合物抗肿瘤活性的研究进展，并对铑配合物的抗肿瘤机制和构效关系进行了探讨，为进一步寻找高效低毒和抗肿瘤谱广的新药物揭示了可循的途径。     

Two novel four-coordinated zinc(II) complexes [Zn(dmatrz)<Subscript>2</Subscript>Cl<Subscript>2</Subscript>] and [Zn(dmatrz)<Subscript>2</Subscript>(SCN)<Subscript>2</Subscript>] exhibiting strong blue fluorescent properties

Two novel complexes, [Zn(dmatrz)₂]Cl₂ (1) and [Zn(dmatrz)₂(SCN)₂] (2), have been prepared and characterized by X-ray crystallography, absorption and luminescence spectrometries (dmatrz=3,5-dimethy-4-amino-1,2,4-triazole). The coordination environment of the zinc(II) ions in (1) and (2) has a distorted tetrahedral geometry completed via two independent nitrogen atoms of two triazole ligands and two anions, respectively. Both (1) and (2) show strong blue luminescence properties. Furthermore, (1) displays stronger blue photoluminescence than (2) as the result of different anions (Cl^- and SCN^-) coordinated to the zinc(II) ions.     

Hydrogen peroxide oxidation of di(hydroxo)platinum(II) species in carboxylic acids

A facile procedure for synthesizing the mono(hydroxo)tris(carboxylato)platinum(IV) species has been achieved. The reaction of [Pt^II(OH)₂(dmpda)] (dmpda=2,2-dimethyl-1,3-propanediamine) with a 30% aqueous solution of H₂O₂ in the presence of a carboxylic acid produces a stable [Pt^IV(OOCR)₃(OH)(dmpda)] (R=Me, Et) complex in high yield. The crystal structures of [Pt^IV(OOCMe)₃(OH)(dmpda)] . H₂O (triclinic P1 bar, a=8.761(2) Å, b=9.245(3) Å, c=10.659(2) Å, =106.25(2)°, =93.90(2)°, =98.92(2)°, V=813.1(3) ų, Z=2, R= 0.0474) and [Pt^IV(OOCEt)₃(OH)(dmpda)] (monoclinic P2₁/c, a=12.777(4) Å, b=10.514(2) Å, c=14.971(3) Å, =107.40(2)°, V=1919.2(8) ų, Z=4, R=0.0611) show that the hydroxyl group has been selectively positioned at an axial site. The intramolecular hydrogen bond between the OH and C=O moiety exists (O(H)...=C, 2.83 Å for [Pt^IV(OOCMe)₃(OH)(dmpda)] · H₂O; 2.72 Å for [Pt^IV(OOCEt)₃(OH)(dmpda)]. Formation of the axial-mono(hydroxo)tris(carboxylato)platinum(IV) species may be ascribed to a combination of `reactive-equatorial effects' with `cis-addition' in the carboxylic acid.     

Study on multimers and their structures in molecular association mixture

Self-association system of(R)-1,3-butanediol in dilute carbon tetrachloride(CCl4)solution is studied as a model of molecular association mixture.Analysis methods including FSMWEFA(fixed-size moving window evolving factor analysis)combined with PCA(principal component analysis),SIMPLISMA (simple-to-use interactive self-modeling mixture analysis),and ITTFA(iterative target transformation factor analysis)are adopted to resolve infrared spectra of(R)-1,3-butanediol solution.Association number and equilibrium constant are computed.(R)-1,3-butanediol in dilute inert solution is determined as a monomer-trimer equilibrium system.Theoretical investigation of trimer structures is carried out with DFT(density functional theory),and structural factors are analyzed.     

<Emphasis Type="Italic">Brønsted</Emphasis> Acids in Ionic Liquids: Fundamentals,Organic Reactions,and Comparisons

Summary. A background for studying acids in various solvents is developed, emphasizing the importance of knowing to what extent a solvent conducts electricity and is therefore ionized, the dissociation equilibria of common molecular solvents and the acidic and basic species generated by solvent leveling. Acidity measurements in the atypical solvent water are discussed and the common method of expressing acidity in other systems – by Hammett values – is introduced. Representative examples of reactions involving Br?nsted acids in ionic liquids are presented and attention paid to the questions of speciation and acidity values. It is found that the gas phase proton affinity of a base is often a better guide to the acidity of its conjugate acid in an ionic liquid than is the dissociation constant of the said acid in water.     

Phenanthroline complexes bearing diamide-anion recognition sites

The synthesis and anion binding properties of new ruthenium(II) and cobalt(II) phenanthroline complexes, containing two amide subunits are described. Evidence for anion binding in dimethyl sulfoxide (DMSO) solution was obtained from u.v.–vis titration experiments. Results indicated that these receptors showed strong affinity for F⁻ and AcO⁻, and showed weak affinity for OH⁻ and H₂PO ₄ ⁻ , and showed no affinity for Cl⁻, Br⁻, I⁻. These receptors interacted with various anions examined through hydrogen-bond formation.     

Sensitively probing the cofactor redox species and photo-induced electron transfer of wild-type and pheophytin-replaced photosynthetic proteins reconstituted in self-assembled monolayers

An ultrathin, ordered, and packed protein film, consisting of the 2-mercaptoacetic acid (MAA), polydimethyldiallylammonium chloride (PDDA), and wild-type (WT) photosynthetic reaction center (RC; termed as WT-RC) or its pheophytin (Phe)-replaced counterpart (termed as Phe-RC), was fabricated by self-assembling technique onto gold electrode for facilitating the electron transfer (ET) between RC and the electrode surface. Near-infrared (NIR)-visible (Vis) absorption and fluorescence (FL) emission spectra revealed the influence of pigment substitution on the cofactors arrangement and excitation relaxation of the proteins, respectively. Square wave voltammetry (SWV) and photoelectric tests were employed to systematically address the differences between the WT-RC films and mutant ones on the direct and photo-induced ET. The electrochemical results demonstrated that ET initiated by the oxidation of the primary donor (P) was obviously slowed down, and the formed P⁺ had more population as well as more positive redox potential in the Phe-RC films compared with those in the WT ones. The photoelectrochemical results displayed the dramatically enhanced photoelectric performances of the mutant ones, further suggesting the slow-down formation of final charge-separated state in Phe-RC. The functionalized protein films introduced in this paper provided an efficient approach to sensitively probe the redox cofactors and ET differences resulting from only minor changes in pigment arrangement in the pigment–protein complex. The favored ET process observed for the membrane proteins RC was potentially valuable for a deep understanding of the multi-step biological ET process and development of versatile bioelectronic devices.     

Development of a non-invasive method for the determination of the macroscopic neutron cross sections of a sample matrix in large-sample prompt-gamma neutron activation analysis

In order to correct for neutron self-shielding in large-sample prompt gamma NAA, a method has been developed to determine the macroscopic scattering and absorption cross sections, i.e., Σ _a and Σ _s, using four Cu flux monitors placed around the sample. With Monte Carlo computations, the neutron densities throughout the sample and the resulting and the corresponding self-shielding factor as calculated from the Σ _a and Σ _s as obtained through the Cu monitors were compared to the true values. The derived Σ _a and Σ _s were found to be sufficiently accurate as long as Σ _t = Σ _a + Σ _s was less than 0.6 cm⁻¹ and Σ _s/Σ _t was greater than 0.1.     

Thermal analysis and microscopical characterization of cholesterol in gallstones

Summary Cholesterol constitutes the major component of most gallstones. It was identified and determined in gallstones by thermal analysis technique (DSC and TG-DTA), mainly by the use of the melting temperature (T_onset=145°C and T_max=149°C) and by DTG peak decomposition (T_max=364°C). Cholesterol anhydrous (ChA), which showed endothermic polymorphic peak, T_max=40°C, without mass loss, was differentiated from cholesterol monohydrate (ChH), which showed a broad endothermic peak, T_max=59°C, attributed to loss of water of crystallization (theoretical 4.45%). Morphological studies of gallstones were performed by optical microscopy and scanning electron microscopy (SEM). The stones consisted of a pigmented core with a variably-sized irregular central cavity, surrounded by a radially arranged deposits of plate-like ChH. The outer part of the stones showed ChA crystal arborescences. X-ray microanalysis gave a typical spectrum rich in C and O, and in some instances the presence of P, which was attributed to the presence of phospholipids. CaCO₃ was easily characterized by TG with the use of DTG decomposition peak at 674°C.