Fluorescence amplification by electrochemically deposited silver nanowires with fractal architecture

Electrochemically deposited silver structures with nanowires 50-100 nm in diameter show high fluorescence amplification and strongly reduced fluorescence lifetimes. Both quantities depend on the structure thickness. With increasing thickness the fluorescence amplification proportionally increases and the fluorescence lifetime decreases. This thickness dependence is caused by fluorophore interaction with a system of plasmon excitations in coupled nanowires extending over micrometer size regions. Thus the amplification is attributed to a combination of extended structure area and strong plasmonic coupling between nanowires which also help to radiatively scatter the fluorescence emission.     

Synthesis and solid-state photochromism of 1,3-diphenyl-4- (2-chlorobenzal)-5-hydroxypyrazole 4-methylthiosemicarbazone

A new photochromic compound containing a pyrazole-ring unit, 1,3-diphenyl-4-(2-chlorobenzal)-5-hydroxypyrazole 4-methylthiosemicarbazone, was synthesized. Its structure, photochromic properties, and photochemical kinetics were characterized. The results show that the title compound exhibits reversible enol-keto photoisomerization, excellent photostability, and high fatigue resistance. An intra- and intermolecular proton-transfer mechanism is proposed.     

Assay of aromatic amino acid enantiomers in rice-brewed suspensions by chiral ligand-exchange CE

The aim of this work was to assay seasoning D- or L-aromatic amino acids (AAs) in rice-brewed suspensions, Laozao in Chinese, by chiral ligand-exchange CE with UV detection and Zn(II) complex as a chiral selecting system. Resolution and peak retention were found to be parallel to the basicity of the AA chiral ligands, and basic L-Arg was known to work the best at pH 8.20 compared with L-Lys and other AA ligands. Baseline separation of DL-aromatic AAs and partially separation of some FMOC-labeled nonaromatic AAs have been achieved using a running buffer of 5 mM ammonium acetate, 100 mM boric acid, 3 mM ZnSO(4), and 6 mM L-Arg at pH 8.20. The aromatic amino acids in four brands of Laozao were measured in a range of 0.25-20 microg/mL for Typ, 1.00-120 microg/mL for Phe, and 2.50-200 microg/mL for Tyr, with linear regression coefficient all over 0.999. The LOD (S/N=3) was 0.15 microg/mL for Typ, 0.50 microg/mL for Phe, and 1.25 microg/mL for Tyr. The recovery of the method determined by spiking with the supernates of Laozao as background was 94.0-112.9%. The RSDs of migration time and peak area measured from six injections of tyrosine were 0.2 and 2.7%, respectively, for run-to-run, and 1.6 and 3.2%, respectively for day-to-day. Interestingly, there were only L-Trp, D-Tyr, and L-Tyr found in the assayed four brands of Laozao. They may serve as an index to recognize the brand of Laozao.     

Spectroscopic detection and theoretical confirmation of the role of Cr2(CO)5(C5R5)2 and .Cr(CO)2(ketene)(C5R5) as intermediates in carbonylation of N=N=CHSiMe3 to O=C=CHSiMe3 by .Cr(CO)3(C5R5) (R = H, CH3)

Conversion of N=N=CHSiMe3 to O=C=CHSiMe3 by the radical complexes .Cr(CO)3C5R5 (R = H, CH3) derived from dissociation of [Cr(CO)3(C5R5)]2 have been investigated under CO, Ar, and N2 atmospheres. Under an Ar or N2 atmosphere the reaction is stoichiometric and produces the Cr[triple bond]Cr triply bonded complex [Cr(CO)2(C5R5)]2. Under a CO atmosphere regeneration of [Cr(CO)3(C5R5)]2 (R = H, CH3) occurs competitively and conversion of diazo to ketene occurs catalytically as well as stoichiometrically. Two key intermediates in the reaction, .Cr(CO)2(ketene)(C5R5) and Cr2(CO)5(C5R5)2 have been detected spectroscopically. The complex .Cr(13CO)2(O=13C=CHSiMe3)(C5Me5) has been studied by electron spin resonance spectroscopy in toluene solution: g(iso) = 2.007; A(53Cr) = 125 MHz; A(13CO) = 22.5 MHz; A(O=13C=CHSiMe3) = 12.0 MHz. The complex Cr2(CO)5(C5H5)2, generated in situ, does not show a signal in its 1H NMR and reacts relatively slowly with CO. It is proposed to be a ground-state triplet in keeping with predictions based on high level density functional theory (DFT) studies. Computed vibrational frequencies are also in good agreement with experimental data. The rates of CO loss from 3Cr2(CO)5(C5H5)2 producing 1[Cr(CO)2(C5H5)]2 and CO addition to 3Cr2(CO)5(C5H5)2 producing 1[Cr(CO)3(C5H5)]2 have been measured by kinetics and show DeltaH approximately equal 23 kcal mol(-1) for both processes. Enthalpies of reduction by Na/Hg under CO atmosphere of [Cr(CO)n(C5H5)]2 (n = 2,3) have been measured by solution calorimetry and provide data for estimation of the Cr[triple bond]Cr bond strength in [Cr(CO)2(C5H5)]2 as 72 kcal mol(-1). The complex [Cr(CO)2(C5H5)]2 does not readily undergo 13CO exchange at room temperature or 50 degrees C implying that 3Cr2(CO)5(C5H5)2 is not readily accessed from the thermodynamically stable complex [Cr(CO)2(C5H5)]2. A detailed mechanism for metalloradical based conversion of diazo and CO to ketene and N2 is proposed on the basis of a combination of experimental and theoretical data.     

Analysis of urinary metabolites for metabolomic study by pressurized CEC

A new approach for the metabolomic study of urinary samples using pressurized CEC (pCEC) with gradient elution is proposed as an alternative chromatographic separation tool with higher degree of resolution, selectivity, sensitivity, and efficiency. The pCEC separation of urinary samples was performed on a RP column packed with C(18), 5 microm particles with an ACN/water mobile phase containing TFA. The effects of the acid modifiers, applied voltage, mobile phase, and detection wavelength were systematically evaluated using eight spiked standards, as well as urine samples. A typical analytical trial of urine samples from Sprague Dawley (S.D.) rats exposed to high-energy diet was carried out following sample pretreatment. Significant differences in urinary metabolic profiles were observed between the high energy diet-induced obesity rats and the healthy control rats at the 6th wk postdose. Multivariate statistical analysis revealed the differential metabolites in response to the diet, which were partially validated with the putative standards. This work suggests that such a pCEC-based separation and analysis method may provide a new and cost-effective platform for metabolomic study uniquely positioned between the conventional chromatographic tools such as HPLC, and hyphenated analytical techniques such as LC-MS.     

“逐步偶联聚合反应”在研制有序交联高分子及复合物中的应用

用“逐步偶联聚合反应”这一新的合成方法可制备不同等级的微观结构可控的有序交联网状高分子,包括可溶性的一维梯形或管状高分子、不溶性的二维或三维筛板状高分子,新型的反应性梯形聚硅氧烷包括氢梯、乙烯基或丙烯基梯、乙氧基梯及其共聚物是功能性梯形高分子的前体,由此衍生出“鱼骨形”和“划艇形”液晶和非线性高分子、盘状金属络合物液晶高分子以及管状聚硅氧烷。对功能化梯形降硅氧烷进行了有趣的应用探索,包括用于稳定液     

A Re2O7 catalyzed cycloetherification of monoallylic diols

A Re₂O₇ catalyzed cycloetherification of monoallylic diols is described. The reaction features short reaction time, mild reaction conditions and exclusive E selectivity. A wide range of monoallylic alcohols with alkyl or aryl substituents on olefin smoothly undergo ring closure to deliver corresponding oxa-heterocycles. The reaction is also operationally simple and not sensitive to air and moisture.     

Preparation and evaluation of <Superscript>131</Superscript>I-quercetin as a novel radiotherapy agent against dedifferentiated thyroid cancer

Here we reported the radiolabeling and evaluation of a novel ¹³¹I-radiolabeled quercetin for the treatment of dedifferentiated thyroid cancers. The human thyroid cancer cell lines (FTC-133, TT and DRO) experienced much higher uptake of ¹³¹I-quercetin as compared to the free ¹³¹I. And the proliferation inhibition rate of ¹³¹I-quercetin on in vitro DRO cell line was 86.87 ± 7.15%. Biodistribution and SPECT analysis demonstrated that the injected radioactivity mainly accumulated in tumors. The tumor volume in the treatment group was dramatically inhibited in comparison with the control group.     

Organometallic Compounds of the Lanthanoides. LXVI. Synthesis and X-ray crystal structure of [O(CH2CH2C5H4)2Y(μ-OH]2 and (MeC5H4)3Ho(H2O), two unusual products of the hydrolysis of organolanthanoide compounds

The partial hydrolysis of [O(CH₂CH₂C₅H₄)₂]Y(C₅H₄CH₃) 1 , [O(CH₂CH₂C₅H₄)₂]Y(C₅H₅) 3 , and [O(CH₂CH₂C₅H₄)₂]Ho(C₅H₄CH₃) 5 results in the formation of [O(CH₂CH₂CH₂C₅H₄)₂Y(μ-OH)₂]₂ 2 , (C₅H₅)₃Y(OH₂) 9 and (MeC₅H₄)₃Ho(OH₂) 11 . The new compounds have been characterized by elemental analyses, IR and NMR spectra. The X-ray structural analyses shows 2 to be monoclinic, space group P2₁/n with a = 1146.0(3), b= 1046.6(3), c = 1514.9(3) pm, β = 94.83(2)°. The molecular structure shows bridging hydroxyl groups with a mean distance Y? O = 223.8(3) pm. 11 crystallizes in the cubic space group 14 3d with a = 1847.9(3)pm with Z = 16 molecules per unit cell. The molecules posses symmetry C₃-3, the coordination is trigonal pyramidal with three methylcyclopentadienyl anions and one water molecule as ligands. The distance Ho? O is 231 pm.     

The structure of the bitetrahedryl molecule—A major shift due to electron correlation: Effects of carbonyl substituents,implications for the structure of coupled tricyclo[3.1.0.02,6]hexyl,and extension to cubylcubane

Ab initio molecular quantum mechanics has been applied to a number of coupled ring systems including biterahedryl and cubylcubane. Basis sets at least as large as double zeta augmented by carbon d functions (DZ +d) were used throughout. For biterahedryl, electron correlation effects qualitatively alter the molecular structure, decreasing the central C? C bond distance while increasing the adjacent C? C distance. Carbonyl substituents, contrary to some previous thinking, do not qualitatively alter the bitetrahedryl structure. This finding points to a structural problem with the monomer bicyclo[3.1.0.0^2,6]hexane that carries over to the coupled bicyclo[3.1.0.0^2,6]hexyl molecule. Finally, for the cubylcubane molecule synthesized in 1988, the only significant difference between Hartree–Fock theory and experiment occurs for the central C? C distance, which, as in the other coupled molecules, is too long. These results significantly lengthen the (still very short) list of closed-shell hydrocarbon molecules for which Hartree–Fock theory encounters structural difficulties.