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111.
Tang X Houchins C Lau KC Ng CY Dressler RA Chiu YH Chu TS Han KL 《The Journal of chemical physics》2007,127(16):164318
Time-dependent wave packet quantum scattering (TWQS) calculations are presented for HD(+) (v = 0 - 3;j(0)=1) + He collisions in the center-of-mass collision energy (E(T)) range of 0.0-2.0 eV. The present TWQS approach accounts for Coriolis coupling and uses the ab initio potential energy surface of Palmieri et al. [Mol. Phys. 98, 1839 (2000)]. For a fixed total angular momentum J, the energy dependence of reaction probabilities exhibits quantum resonance structure. The resonances are more pronounced for low J values and for the HeH(+) + D channel than for the HeD(+) + H channel and are particularly prominent near threshold. The quantum effects are no longer discernable in the integral cross sections, which compare closely to quasiclassical trajectory calculations conducted on the same potential energy surface. The integral cross sections also compare well to recent state-selected experimental values over the same reactant and translational energy range. Classical impulsive dynamics and steric arguments can account for the significant isotope effect in favor of the deuteron transfer channel observed for HD(+)(v<3) and low translational energies. At higher reactant energies, angular momentum constraints favor the proton-transfer channel, and isotopic differences in the integral cross sections are no longer significant. The integral cross sections as well as the J dependence of partial cross sections exhibit a significant alignment effect in favor of collisions with the HD(+) rotational angular momentum vector perpendicular to the Jacobi R coordinate. This effect is most pronounced for the proton-transfer channel at low vibrational and translational energies. 相似文献
112.
Dr. Xiong‐Jie Jiang Dr. Janet T. F. Lau Dr. Qiong Wang Prof. Dennis K. P. Ng Prof. Pui‐Chi Lo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8273-8281
A diiodo distyryl boron dipyrromethene (BODIPY) core was conjugated to two ferrocenyl quenchers through acid‐labile ketal and/or thiol‐cleavable disulfide linkers, of which the fluorescence and photosensitizing properties were significantly quenched through a photoinduced electron‐transfer process. The two symmetrical analogues that contained either the ketal or disulfide linkers could only be activated by a single stimulus, whereas the unsymmetrical analogue was responsive to dual stimuli. Upon interaction with acid and/or dithiothreitol (DTT), these linkers were cleaved selectively. The separation of the BODIPY core and the ferrocenyl moieties restored the photoactivities of the former in phosphate buffered saline and inside the MCF‐7 breast cancer cells, rendering these compounds as potential activable photosensitizers for targeted photodynamic therapy. The dual activable analogue exhibited the greatest enhancement in intracellular fluorescence intensity in both an acidic environment (pH 5) and the presence of DTT (4 mm ). Its photocytotoxicity against MCF‐7 cells also increased by about twofold upon preincubation with 4 mm of DTT. The activation of this compound was also demonstrated in nude mice bearing a HT29 human colorectal carcinoma. A significant increase in fluorescence intensity in the tumor was observed over 9 h after intratumoral injection. 相似文献
113.
Dr. Qian Wang Hong Yan Zhao Dr. Wai‐Lun Man Dr. William W. Y. Lam Dr. Kai‐Chung Lau Prof. Tai‐Chu Lau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(31):10754-10758
The kinetics and mechanism of the reaction of SIV (SO32?+HSO3?) with a ruthenium(VI) nitrido complex, [(L)RuVI(N)(OH2)]+ (RuVIN, L=N,N′‐bis(salicylidene)‐o‐cyclohexyldiamine dianion), in aqueous acidic solutions are reported. The kinetic results are consistent with parallel pathways involving oxidation of HSO3? and SO32? by RuVIN. A deuterium isotope effect of 4.7 is observed in the HSO3? pathway. Based on experimental results and DFT calculations the proposed mechanism involves concerted N?S bond formation (partial N‐atom transfer) between RuVIN and HSO3? and H+ transfer from HSO3? to a H2O molecule. 相似文献
114.
Ultra-performance liquid chromatography/time-of-flight mass spectrometry based metabolomics of raw and steamed Panax notoginseng 总被引:4,自引:0,他引:4
Chan EC Yap SL Lau AJ Leow PC Toh DF Koh HL 《Rapid communications in mass spectrometry : RCM》2007,21(4):519-528
At present, metabolite profiling is of growing importance in herbal medicine fields such as breeding, formulation, quality control and clinical trials. This preliminary study indicated that ultra-performance liquid chromatography/time-of-flight mass spectrometry (UPLC/TOFMS)-based metabolomics allows direct detection of down-stream derivatives of metabolites, arising from the herbal formulation process. This analytical approach allows the discrimination and tentative authentication of unique biomarkers related to different herbal extracts using unsupervised multivariate principal component analysis (PCA). The tentative identification of biomarkers is complemented significantly by the accurate mass measurement of TOFMS and the high resolution and high retention time reproducibility rendered by UPLC. The application of this approach in herbal extract discrimination and ginsenoside biomarker discovery of raw and steamed Panax notoginseng (Burk.) F.H. Chen is demonstrated and discussed. 相似文献
115.
Drug delivery directly to the colon is a very useful approach for treating localised colonic diseases such as inflammatory bowel disease, ulcerative colitis, and Crohn’s disease. The use of disulphide cross-linked polymers in colon targeted drug delivery systems has received much attention because these polymers are redox sensitive, and the disulphide bonds are only cleaved by the low redox potential environment in the colon. The goal of this study was to synthesise tricarballylic acid-based trithiol monomers for polymerisation into branch-chained disulphide polymers. The monomer was synthesised via the amide coupling reaction between tricarballylic acid and (triphenylmethyl) thioethylamine using two synthesis steps. The disulphide cross-linked polymers which were synthesised using the air oxidation method were completely reduced after 1 h of reduction with different thiol concentrations detected for the different disulphide polymers. In simulated gastric and intestinal conditions, all polymers had low thiol concentrations compared to the thiol concentrations in the simulated colon condition with Bacteroides fragilis present. Degradation was more pronounced in polymers with loose polymeric networks, as biodegradability relies on the swelling ability of polymers in an aqueous environment. Polymer P15 which has the loosest polymeric networks showed highest degradation. 相似文献
116.
Constructing Interfacial Energy Transfer for Photon Up‐ and Down‐Conversion from Lanthanides in a Core–Shell Nanostructure 下载免费PDF全文
Dr. Bo Zhou Dr. Lili Tao Dr. Yang Chai Prof. Shu Ping Lau Prof. Qinyuan Zhang Dr. Yuen Hong Tsang 《Angewandte Chemie (International ed. in English)》2016,55(40):12356-12360
We report a new mechanistic strategy for controlling and modifying the photon emission of lanthanides in a core–shell nanostructure by using interfacial energy transfer. By taking advantage of this mechanism with Gd3+ as the energy donor, we have realized efficient up‐ and down‐converted emissions from a series of lanthanide emitters (Eu3+, Tb3+, Dy3+, and Sm3+) in these core–shell nanoparticles, which do not need a migratory host sublattice. Moreover, we have demonstrated that the Gd3+‐mediated interfacial energy transfer, in contrast to energy migration, is the leading process contributing to the photon emission of lanthanide dopants for the NaGdF4@NaGdF4 core–shell system. Our finding suggests a new direction for research into better control of energy transfer at the nanometer length scale, which would help to stimulate new concepts for designing and improving photon emission of the lanthanide‐based luminescent materials. 相似文献
117.
The use of a novel inexpensive photometric device, a paired emitter-detector diode (PEDD) has been applied to the colorimetric determination of phosphate using the malachite green spectrophotometric method. The novel miniaturized flow detector applied within this manifold is a highly sensitive, low cost, miniaturized light emitting diode (LED) based detector. The optical flow cell was constructed from two LEDs, whereby one is the light source and the second is the light detector, with the LED light source forward biased and the LED detector reversed biased. The photocurrent generated by the LED light source discharges the junction capacitance of the detector diode from 5 V (logic 1) to 1.7 V (logic 0) and the time taken for this process to occur is measured using a simple timer circuit.The malachite green (MG) method employed for phosphate determination is based on the formation of a green molybdophosphoric acid complex, the intensity of which is directly related to phosphate concentration. Optimum analytical parameters such as reaction kinetics, reagent to sample concentration ratio and emitter wavelength intensity were investigated for the spectrophotometric method. Linear calibration plots that obeyed the Beer-Lambert law were obtained for phosphate in the range of 0.02-2 μM. The dynamic range, sensitivity and limits of detection are reported. 相似文献
118.
119.
Bob Boyd Gareth Brenton Eddie Clayton Jonathan Curtis R. M. Elliott G. A. Errock B. N. Green R. H. Bateman Simon J. Gaskell Iwan Griffiths Zdenek Herman Philip Jonathan Rich Kondrat Mila Laušević Chris Lock Deepak Mathur John F. J. Todd Károly Vékey 《Rapid communications in mass spectrometry : RCM》2016,30(11):1253-1264
120.
A single, isocratic high-performance liquid chromatographic method is described for the determination of cocaine and three of its metabolites along with caffeine in serum microsamples (50 microliters). The small sample size permits the tracking of pharmacokinetic data over time in individual, small animals. The method also was used to demonstrate that cocaine, benzoylecgonine and norcocaine in rat serum samples were stable for at least a month without the presence of sodium fluoride. 相似文献