(C(wedge)N(wedge)N)Pt(C identical to C)nR] (HC(wedge)N(wedge)N = 6-aryl-2,2'-bipyridine,n = 1-4, R = aryl,SiMe3) as a new class of light-emitting materials and their applications in electrophosphorescent devices

Tridentate cyclometalated platinum(II) complexes bearing sigma-alkynyl ligands exhibit tunable photoluminescence and enhanced stability during vacuum deposition; OLEDs based on these materials display orange to red electrophosphorescence with low turn-on voltages (approximately 4 V), maximum luminance approaching 10,000 cd m-2 and efficiency up to 4.2 cd A-1.     

Reactivity of iron(II) 5,10,15,20-tetraaryl-21-oxaporphyrin with arylmagnesium bromide: formation of paramagnetic six-coordinate complexes with two axial aryl groups

Coordination of sigma-aryl carbanions by chloroiron(II) 5,20-ditolyl-10,15-diphenyl-21-oxaporphyrin (ODTDPP)Fe(II)Cl has been followed by (1)H NMR spectroscopy. Addition of pentafluorophenyl Grignard reagent (C(6)F(5))MgBr to the toluene solution of (ODTDPP)Fe(II)Cl in the absence of dioxygen at 205 K resulted in the formation of the high-spin (ODTDPP)Fe(II)(C(6)F(5)). The titration of (ODTDPP)Fe(II)Cl with a solution of (C(6)H(5))MgBr carried at 205 K yields a rare six-coordinate species which binds two sigma-aryl ligands [(ODTDPP)Fe(II)(C(6)H(5))(2)](-). Warming of the [(ODTDPP)Fe(II)(C(6)H(5))(2)](-) solution above 270 K results in the decomposition to mono-sigma-phenyliron species (ODTDPP)Fe(II)(C(6)H(5)). Controlled oxidation of [(ODTDPP)Fe(II)(C(6)H(5))(2)](-) with Br(2) affords (ODTDPP)Fe(III)(C(6)H(5))Br, which demonstrates a typical (1)H NMR pattern of low-spin sigma-aryl iron(III) porphyrin. The considered oxidation mechanism involves the (ODTDPP)Fe(III)(C(6)H(5))(2) species, which is readily reduced to the iron(I) 21-oxaporphyrin, followed by oxidation with Br(2) and replacement of one bromide anion by aryl substituent. The (1)H NMR spectra of paramagnetic iron complexes have been examined in detail. Functional group assignments have been made with the use of selective deuteration. The peculiar (1)H NMR spectral features of [(ODTDPP)Fe(II)(p-CH(3)C(6)H(4))(2)](-) (sigma-p-tolyl: ortho, 30.8; meta, 53.6; para-CH(3), 42.1; furan: -16.0; beta-H pyrrole: -27.5, -34.3, -41.8 ppm, at 205 K) are without a parallel to any iron(II) porphyrin or heteroporphyrin and indicate a profound alteration of the electronic structure of iron(II) porphyrin upon the coordination of two sigma-aryls.     

含金鸡纳碱的光活性聚合物──Ⅰ．金鸡纳碱／丙烯酰胺共聚物的合成与表征

研究了金鸡纳碱与丙烯酰胺的自由基共聚反应。发现在氯仿／乙醇混合溶剂中采用硫酸奎宁作为金鸡纳碱共聚单体可以合成收率和金鸡纳碱含量均较高的新型水溶性共聚物。对共聚物用元素分析、核磁共振、粘度和旋光度测定等方法进行表征，发现在假定丙烯酰胺链节为非光活性的条件下共聚物中金鸡纳碱链节的比旋光度随聚合配方中金鸡纳碱含量的增加而增加。     

Cure behavior and thermal stability of an epoxy: new bismaleimide blends for composite matrices

A new bismaleimide (BMI) resin was synthesized to formulate epoxy(tetraglycidyl diaminodiphenyl methane; TGDDM) – bismaleimide thermoset blends for composite matrix applications. 4,4′-diaminodiphenyl methane (DDM) was used as an amine curing agent for the TGDDM. A Fourier transform infrared (FTIR) spectroscopy was employed to characterize the new BMI resin. Cure behavior of the epoxy–BMI blends was studied using a differential scanning calorimeter (DSC). DSC thermograms of the thermoset blends indicated two exothermic peaks. The glass transition temperature of the thermoset blends decreased with BMI content. Thermogravimetric analysis (TGA) was carried out to investigate thermal degradation behavior of the cured epoxy–BMI thermoset blends. The new BMI resin reacted partially with the DDM and weak intercrosslinking polymer networks were formed during cure of the thermoset blends.     

Xanthine Sensors Based on Anodic and Cathodic Detection of Enzymatically Generated Hydrogen Peroxide

A xanthine biosensor was fabricated by the covalent immobilization of xanthine oxidase (XO) onto a functionalized conducting polymer (Poly‐5, 2′: 5′, 2″‐terthiophine‐3‐carboxylic acid), poly‐TTCA through the formation of amide bond between carboxylic acid groups of poly‐TTCA and amine groups of enzyme. The immobilization of XO onto the conducting polymer (XO/poly‐TTCA) was characterized using cyclic voltammetry, quartz crystal microbalance (QCM), and X‐ray photoelectron spectroscopy (XPS) techniques. The direct electron transfer of the immobilized XO at poly‐TTCA was found to be quasireversible and the electron transfer rate constant was determined to be 0.73 s^?1. The biosensor efficiently detected xanthine through oxidation at +0.35 V and reduction at ?0.25 V (versus Ag/AgCl) of enzymatically generated hydrogen peroxide. Various experimental parameters, such as pH, temperature, and applied potential were optimized. The linear dynamic ranges of anodic and cathodic detections of xanthine were between 5.0×10^?6?1.0×10^?4 M and 5.0×10^?7 to 1.0×10^?4 M, respectively. The detection limits were determined to be of 1.0×10^?6 M and 9.0×10^?8 M with anodic and cathodic processes, respectively. The applicability of the biosensor was tested by detecting xanthine in blood serum and urine real samples.     

Electrolytic production of metallic uranium from U3O8 in a 20-kg batch scale reactor</p> </p>

Summary The electrolytic reduction of U₃O₈ powder was carried out using LiCl-Li₂O molten salt in a 20-kg U₃O₈ batch cell to verify the feasibility of the process. As the current passes the cell, the decomposition of Li₂O and the reduction of U₃O₈ occur simultaneously in a cathode assembly and oxygen gas evolvs at the anode. The results from a 20-kg U₃O₈ scale cell were compared with data obtained from a bench scale cell. The results suggest a successful demonstration of this process, exhibiting a reduction conversion of U₃O₈ of more than 99% in a batch.</p> </p>     

Dynamic identification of phosphopeptides using immobilized metal ion affinity chromatography enrichment, subsequent partial beta-elimination/chemical tagging and matrix-assisted laser desorption/ionization mass spectrometric analysis

The enrichment of phosphopeptides using immobilized metal ion affinity chromatography (IMAC) and subsequent mass spectrometric analysis is a powerful protocol for detecting phosphopeptides and analyzing their phosphorylation state. However, nonspecific binding peptides, such as acidic, nonphosphorylated peptides, often coelute and make analyses of mass spectra difficult. This study used a partial chemical tagging reaction of a phosphopeptide mixture, enriched by IMAC and contaminated with nonspecific binding peptides, following a modified beta-elimination/Michael addition method, and dynamic mass analysis of the resulting peptide pool. Mercaptoethanol was used as a chemical tag and nitrilotriacetic acid (NTA) immobilized on Sepharose beads was used for IMAC enrichment. The time-dependent dynamic mass analysis of the partially tagged reaction mixture detected intact phosphopeptides and their mercaptoethanol-tagged derivatives simultaneously by their mass difference (-20 Da for each phosphorylation site). The number of new peaks appearing with the mass shift gave the number of multiply phosphorylated sites in a phosphopeptide. Therefore, this partial chemical tagging/dynamic mass analysis method can be a powerful tool for rapid and efficient phosphopeptide identification and analysis of the phosphorylation state concurrently using only MS analysis data.     

Enzyme-linked immunosorbent assay for the determination of 20(S)-protopanaxatriol

A highly sensitive and specific enzyme-linked immunosorbent assay (ELISA) method has been developed for the determination of 20(S)-protopanaxatriol (PPT), one of the major aglycones of dammarane-type ginseng saponins. Polyclonal antibodies raised against ginsenoside F₁ (GF₁)-bovine serum albumin showed high reactivities to PPT and GF₁, whereas they exhibited minor or even no cross-reactivities to other ginsenosides and protopanaxadiol (0.19%). The working range of this method extends from 50 pg ml⁻¹ to 20 ng ml⁻¹ of PPT. The assay reported here has been validated against an HPLC technique using PPT-containing samples and was shown to correlate closely (γ=0.993). This ELISA could be a useful tool for the determination of PPT contained in biological fluids and plant materials.     

Synthesis of nanosized TiO2/SiO2 particles using microwave processes and their photocatalytic activity on the decomposition of orange II

The nanosized titania and TiO₂/SiO₂ particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination temperature has been investigated. The major phase of the pure TiO₂ particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO₂/SiO₂ particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO₂/SiO₂ particles decreases as compared to pure TiO₂ at high calcination temperatures. The TiO₂/SiO₂ particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO₂ particles.     

Self-assembled amphiphilic fluorescent probe: detecting pH-fluctuations within cancer cells and tumour tissues

Abnormal anaerobic metabolism leads to a lowering of the pH of many tumours, both within specific intracellular organelles and in the surrounding extracellular regions. Information relating to pH-fluctuations in cells and tissues could aid in the identification of neoplastic lesions and in understanding the determinants of carcinogenesis. Here we report an amphiphilic fluorescent pH probe (CS-1) that, as a result of its temporal motion, provides pH-related information in cancer cell membranes and selected intracellular organelles without the need for specific tumour targeting. Time-dependent cell imaging studies reveal that CS-1 localizes within the cancer cell-membrane about 20 min post-incubation. This is followed by migration to the lysosomes at 30 min before being taken up in the mitochondria after about 60 min. Probe CS-1 can selectively label cancer cells and 3D cancer spheroids and be readily observed using the green fluorescence channel (λ_em = 532 nm). In contrast, CS-1 only labels normal cells marginally, with relatively low Pearson''s correlation coefficients being found when co-incubated with standard intracellular organelle probes. Both in vivo and ex vivo experiments provide support for the suggestion that CS-1 acts as a fluorescent label for the periphery of tumours, an effect ascribed to proton-induced aggregation. A much lower response is seen for muscle and liver. Based on the present results, we propose that sensors such as CS-1 may have a role to play in the clinical and pathological detection of tumour tissues or serve as guiding aids for surgery.

A self-assembled amphiphilic fluorescent probe allows pH-fluctuations within cancer cells and tumour tissues to be readily detected.