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81.
82.
Yong Huang Wen‐Chou Hung Ming‐Yuan Liao Tsung‐En Tsai Ya‐Liu Peng Chu‐Chieh Lin 《Journal of polymer science. Part A, Polymer chemistry》2009,47(9):2318-2329
Four metal benzylalkoxides, [L2M2(μ‐OBn)2] (M = Mg or Zn), based on NNO‐tridentate ketiminate ligands are synthesized and characterized. X‐ray crystal structural studies of [(L1)2Mg2(μ‐OBn)2] ( 1a ) and [(L1)2Zn2(μ‐OBn)2] ( 1b ) (L1‐H = (Z)‐4‐((2‐(dimethylamino)ethylamino)(phenyl)methylene)‐3‐methyl‐1‐phenyl‐pyrazol‐5‐one) reveal that both complexes 1a and 1b are dinuclear species whereas the geometry around the metal center is penta‐coordinated bridging through the benzylalkoxy oxygen atoms in the solid structure. The activities and stereoselectivities of these four complexes toward the ring‐opening polymerization of L ‐lactide and rac‐lactide are investigated. Polymerization of L ‐lactide initiated by these four metal benzyloxides proceeds rapidly with good molecular weight control and yields polymer with a very narrow molecular weight distribution. The kinetic studies for the polymerization of L ‐lactide with compound 1a show first order in both compound 1a and lactide concentrations with the polymerization rate constant, k, of 6.94 M/min. Besides, experimental results demonstrate that among these metal benzylalkoxides, complex 1a exhibits the highest stereoselectivity with a Pr up to 87% and complex 1b possesses the highest activity indicating that the terminal group of NNO‐tridentate ketimine ligands exerts a significant influence on both the reactivity and stereoselectivity of these complexes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2318–2329, 2009 相似文献
83.
Ni‐Chen Chiang Cheng‐Kang Chiang Zong‐Hong Lin Tai‐Chia Chiu Huan‐Tsung Chang 《Rapid communications in mass spectrometry : RCM》2009,23(19):3063-3068
We have employed mixtures of two differently sized (average diameters: 3.5 and 14 nm) gold nanoparticles (Au NPs) as selective probes and matrices for the determination of aminothiols using surface‐assisted laser desorption/ionization mass spectrometry (SALDI‐MS). When using 38 and 150 pM solutions of the 3.5‐ and 14‐nm Au NPs, respectively, as the probe and matrix, SALDI‐MS provided limits of detection (signal‐to‐noise ratio = 3) of 2, 20, and 44 nM for 1.0 mL solutions of glutathione (GSH), cysteine (Cys), and homocysteine, respectively. The signal intensities of these analytes varied by less than 20% for SALDI‐MS analyses recorded over 50 sample spots; in contrast, they varied by as much as 60% when using a conventional matrix (2,5‐dihydroxybenzoic acid). We validated the practicality of this approach – with its advantages of sensitivity, reproducibility, rapidity, and simplicity – through the analysis of GSH in MCF‐7 cell lysates and Cys in plasma. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
84.
P‐113, AKRHHGYKRKFH‐NH2, was derived from human saliva and found to possess clinical activity against fungus infections in HIV patients with oral candidiasis. We have determined the solution structure of P‐113 bound to membrane‐mimetic SDS micelles by two‐dimensional NMR methods. The SDS micelle‐bound structure of P‐113 adopts an α‐helical segment and the positively charged residues are clustered together to form a hydrophilic patch. A variety of biophysical and biochemical experiments, including circular dichroism, fluorescence spectroscopy and microcalorimetry, were used to show that P‐113 interacted with negatively charged phospholipid vesicles and induced dye release from these vesicles. However, its dye leakage efficiency is much less than the results of previously reported antimicrobial peptides. These results suggest that the antimicrobial activity of P‐113, unlike other antimicrobial peptides, may act not only through binding to and destabilization of the microbial membrane but also through a specific protein receptor on the microbial cell surface. 相似文献
85.
Long‐Bin Jeng Wan‐Yu Lo Wei‐Yi Hsu Wei‐De Lin Chiung‐Tsung Lin Chien‐Chen Lai Fuu‐Jen Tsai 《Rapid communications in mass spectrometry : RCM》2009,23(11):1543-1549
Hepatocellular carcinoma (HCC) is a common neoplasm in Taiwan, for which early diagnosis is difficult and the prognosis is usually poor. HCC is usually diagnosed by abdominal sonography and serum alpha‐fetoprotein (AFP) detection. Modified nucleosides, regarded as indicators for the whole‐body turnover of RNAs, are excreted in abnormal amounts in the urine of patients with malignancies and can serve as tumor markers. We analyzed the excretion patterns of urinary nucleosides from 25 HCC patients and 20 healthy volunteers by high‐performance liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC/ESI‐MS/MS) under optimized conditions. The HPLC/ESI‐MS/MS approach with selective reaction monitoring (SRM) allowed for the sensitive determination of nucleosides in human urine samples. The mean levels of the urinary nucleosides adenosine, cytidine, and inosine were significantly higher in HCC patients than healthy volunteers (average of 1.78‐, 2.26‐, and 1.47‐fold, respectively). However, the mean levels of urinary 1‐methyladenosine, 3‐methylcytidine, uridine, and 2′‐deoxyguanosine were not significantly different. Combined with the determination of serum AFP levels, the higher levels of urinary adenosine, cytidine, and inosine may be additional diagnosis markers for HCC in Taiwanese patients. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
86.
Hui‐Ju Chuang Hsiao‐Li Chen Jian‐Li Ye Zn‐Yun Chen Pei‐Ling Huang Tzu‐Ting Liao Tsung‐En Tsai Chu‐Chieh Lin 《Journal of polymer science. Part A, Polymer chemistry》2013,51(3):696-707
A series of magnesium benzylalkoxide complexes, [LnMg(μ‐OBn)]2 ( 1 – 14 ) supported by NNO‐tridentate pyrazolonate ligands with various electron withdrawing‐donating subsituents have been synthesized and characterized. X‐ray crystal structural studies revealed that Complexes 1 – 3 , 5 , 7 , 9 , and 10 are dinuclear bridging through benzylalkoxy oxygen atoms with penta‐coordinated metal centers. All of these complexes acted as efficient initiators for the ring‐opening polymerization of L‐lactide and rac‐lactide. Based on kinetic studies, the activity of these metal complexes is significantly influenced by the electronic effect of the ancillary ligands with the electron‐donating substituents at the phenyl rings enhancing the polymerization rate. In addition, the “living” and “immortal” character of 6 has paved a way to synthesize as much as 40‐fold polymer chains of polylactides with a very narrow polydispersity index in the presence of a small amount of initiator. Among all of magnesium complexes, Complex 6 exhibits the highest stereoselectivity toward ring‐opening polymerization of rac‐lactide with Pr up to 88% in THF at 0 °C. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
87.
Prof. Biing‐Chiau Tzeng Sheng‐Luen Wei Dr. Tsung‐Yi Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(51):16443-16449
We have synthesized a series of 1D double‐zigzag ({[Cd(paps)2(H2O)2](ClO4)2}n ( 1 ), {[Cd(papo)2(H2O)2](ClO4)2}n ( 3 ), and {[Cd(papc)2(H2O)2](ClO4)2}n ( 5 )) and 2D polyrotaxane frameworks ([Cd(papc)2(ClO4)2]n ( 6 )) by the reaction of Cd(ClO4)2 with dipyridylamide ligands N,N′‐bis(pyridylcarbonyl)‐4,4′‐diaminodiphenyl thioether (paps), N,N′‐bis(pyridylcarbonyl)‐4,4′‐diaminodiphenyl ether (papo), and N,N′‐(methylenedi‐p‐phenylene)bispyridine‐4‐carboxamide (papc), respectively, where their molecular structures have been determined by X‐ray diffraction studies. Based on the powder X‐ray data (PXRD) of compound 3 and its ZnII analogue, heating the double‐zigzag framework of compound 3 can give the polyrotaxane framework of [Cd(papo)2(ClO4)2]n ( 4 ) and grinding this powder sample in the presence of moisture resulted in its complete conversion back into the pure double‐zigzag framework. In addition, heating the double‐zigzag frameworks of compounds 1 and 5 can induce structural transformation into their respective polyrotaxanes, whereas grinding these solid samples in the presence of moisture did not lead to the formation of the double zigzags. Herein, we investigated the effect of the metal (from ZnII to CdII) on the assembly process and luminescence properties, as well as on the particularly intriguing structural transformation of a series of papx‐based frameworks. In fact, the assembly behavior and luminescence properties of the CdII? papx and ZnII? papx frameworks were really similar. However, both ZnII? papx (x=s, o) frameworks can perform reversible structural transformation, but only the CdII? papo framework can do it. Therefore, a delicate metal effect on such a new structural transformation can be observed. 相似文献
88.
Min‐Shiun Chao Horng‐Hwa Lu Ming‐Liao Tsai Tsung‐Hsuan Hsieh Chien‐Min Lin 《中国化学会会志》2009,56(5):916-922
The self‐assembly of Co(II) with two diaminodiamide ligands, 4,7‐diazadecanediamide and 4,8‐diazaundecanediamide, gave two different crystals, [(C8H18N4O2)Co(OH)2Co(C8H18N4O2)]Cl2 ( 1 ) [Co(C9H20N4O2)(Cl)(H2O)]·Cl·2H2O ( 2 ). Structures of 1 and 2 were characterized by single‐crystal X‐ray diffraction analysis. Structural data for 1 shows a novel type of binuclear complex with distorted octahederal coordination geometry around the Co atoms through the hydroxo bridges. By using inter‐connector N‐H···N hydrogen bonding interactions as building forces, each cationic moiety [(C8H18N4O2)Co(OH)2Co(C8H18N4O2)]2+ is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chain‐like structure. The chains are further connected into a 2D layer in a (4,4)‐topology via N‐H···Clfree hydrogen‐bonding interactions. Structural data for 2 indicate that the cobalt atom adopts a six‐coordinated N2O4 environment, giving a distorted octahedral geometry, where two N‐ and two O‐donor sets of ligand located at equatorial positions and one water and one chloride occupied at axial positions. Through NH···Cl‐Co and OH···Cl‐Co contacts, each cationic moiety [Co(C9H20N4O2)(Cl)(H2O)]+ in 2 is linked to neighboring ones, producing a charged hydrogen‐bonded 1D chainlike structure. Thus, the crystal‐engineering approach has proved successful in the solid‐state packing due to steric strain effect of the diaminodiamide ligand. 相似文献
89.
The mixed‐valent nickel hexacyanoferrate (NiHCF) and poly(3,4‐ethylenedioxythiophene) (PEDOT) hybrid film (NiHCF‐PEDOT) was prepared on a glassy carbon electrode (GCE) by multiple scan cyclic voltammetry. The films were characterized using atomic force microscopy, field emission scanning electron microscopy, energy dispersive spectroscopy, X‐ray diffraction, and electrochemical impedance spectroscopy (AC impedance). The advantages of these films were demonstrated for the detection of ascorbic acid (AA) using cyclic voltammetry and amperometric techniques. The electrocatalytic oxidation of AA at different electrode surfaces, such as the bare GCE, the NiHCF/GCE, and the NiHCF‐PEDOT/GCE modified electrodes, was determined in phosphate buffer solution (pH 7). The AA electrochemical sensor exhibited a linear response from 5×10−6 to 1.5×10−4 M (R2=0.9973) and from 1.55×10−4 to 3×10−4 M (R2=0.9983), detection limit=1×10−6 M, with a fast response time (3 s) for AA determination. In addition, the NiHCF‐PEDOT/GCE was advantageous in terms of its simple preparation, specificity, stability and reproducibility. 相似文献
90.
Chiy‐Rong Chen Yun‐Wen Liao Wen‐Ling Shih Chih‐Ying Tzeng Hsueh‐Ling Cheng Wei‐Tsung Kao Chi‐I Chang 《Helvetica chimica acta》2010,93(7):1355-1361
Two new cucurbitane triterpenes, (23E)‐7β‐methoxycucurbita‐5,23,25‐trien‐3β‐ol ( 1 ) and 23,25‐dihydroxy‐5β,19‐epoxycucurbit‐6‐ene‐3,24‐dione ( 2 ), and a new D : C‐friedooleanane triterpene, 3α‐[(E)‐feruloyloxy]‐D : C‐friedooleana‐7,9(11)‐dien‐29‐oic acid ( 3 ), together with two known D : C‐friedooleanane triterpenes, 3β‐[(E)‐feruloyloxy]‐D : C‐friedooleana‐7,9(11)‐dien‐29‐oic acid ( 4 ) and 3‐oxo‐D : C‐friedooleana‐7,9(11)‐dien‐29‐oic acid ( 5 ), were isolated from the stems of Momordica charantia. The structures of the new compounds 1 – 3 were determined by spectroscopic methods. 相似文献