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101.
Pascu SI Waghorn PA Conry TD Betts HM Dilworth JR Churchill GC Pokrovska T Christlieb M Aigbirhio FI Warren JE 《Dalton transactions (Cambridge, England : 2003)》2007,(43):4988-4997
New M(II) bis(thiosemicarbazonato) complexes (M = Ni(II), Cu(II) and Zn(II)) featuring allyl groups at the exocyclic nitrogens have been synthesised. The complexes were characterised in solution by spectroscopic methods and their solid state structures determined by single crystal X-ray diffraction using synchrotron radiation. The Zn(II) complex was found to be intrinsically fluorescent and soluble in biocompatible media. The uptake of this Zn(II) complex in HeLa, MCF-7 and IGROV cancer cells was monitored by fluorescence microscopies (epi- and confocal fluorescence imaging). The radiolabelling to (64)Cu(II) bis(thiosemicarbazonato) complex was performed cleanly by transmetallation from the corresponding Zn(II) species using (64)Cu(OAc)(2). 相似文献
102.
The time-of-flight mass spectra of tris(2,2,6,6-tetramethyl-3,5-heptanedionato) lanthanide(III) [or Ln(thd)3 with Ln = Eu, Tb, Gd] produced by laser-induced multiphoton ionization in a supersonic expansion were studied as a function of laser excitation wavelength. Resonance-enhanced multiphoton ionization (REMPI), monitoring the Eu(I) ion signal from gas-phase Eu(thd)3, was observed in three distinct visible-excitation regions, corresponding to electronic absorption transitions on neutral Eu(0) atoms. The confirmation of the presence of Eu(0) atoms in the beam supports the proposed mechanism for the production of Ln atoms through sequential dissociation of neutral thd ligands from the metal following photoexcitation into ligand-to-metal charge-transfer (LMCT) states. Evidence is also presented that the LnO+ and LnOH+ fragments observed in the mass spectrum are produced via a separate, competing fragmentation pathway. The branching ratios between the two fragmentation pathways are compared for Ln(thd)3 (Ln = Eu, Tb, Gd). The ligand-dissociation pathway that produces Ln atoms appears to be more favorable in Ln(thd)3 complexes with low-lying LMCT states. Finally, the observation of the Tb2(thd)6+ dimer and its associated fragmentation pattern, as well as the presence of metal carbides, which are relevant to carbon contamination in chemical vapor deposition, is discussed. 相似文献
103.
This review is concerned with recent studies of electrospray ionisation-mass spectrometry (ESI-MS) of selected small molecular mass drugs and their application in qualitative and quantitative analytical methods using the techniques liquid chromatography mass spectrometry (LC-ESI-MS) and capillary electrophoresis mass spectrometry (CE-ESI-MS). The publications reviewed are taken from the Web of Knowledge database for the year 2006. The drugs have molecular mass less than 1000 Da and are chosen according to selected drug classifications in which they give ESI signals primarily as [M+H]+ ions. The drug classifications are antibiotics/antibacterials, steroids, anti-tumour drugs, erectile dysfunction agents, anti-epileptic drugs, antiasthmatic drugs, psychoactive drugs and miscellaneous drugs. Details are given on the fragmentations, where available, that these ionic species exhibit in-source and in ion trap, triple quadrupole and time-of-flight mass spectrometers. Analytical methods for the detection and determination of these small molecular mass drug molecules are also discussed, where appropriate, under the particular drug classifications. Analytical information on, for example, sample concentration techniques, separation conditions, recoveries from biological media and limits of detection/quantitation (LODs and LOQs) are provided. 相似文献
104.
Lihua Bai Jianxia Guo Franklin A. Bontempo III Julie L. Eiseman 《Photochemistry and photobiology》2009,85(4):1011-1019
The ability to noninvasively measure photosensitizer concentration at target tissues will allow optimization of photodynamic therapy (PDT) and could improve outcome. In this study, we evaluated whether preirradiation tumor phthalocyanine 4 (Pc 4) concentrations, measured noninvasively by the optical pharmacokinetic system (OPS), correlated with tumor response to PDT. Mice bearing human breast cancer xenografts were treated with 2 mg kg−1 Pc 4 iv only, laser irradiation (150 J cm−2 ) only, Pc 4 followed by fractionated irradiation or Pc 4 followed by continuous irradiation. Laser irradiation treatment was initiated when the tumor to skin ratio of Pc 4 concentration reached a maximum of 2.1 at 48 h after administration. Pc 4 concentrations in tumor, as well as in Intralipid in vitro , decreased monoexponentially with laser fluence. Pc 4-PDT resulted in significant tumor regression, and tumor response was similar in the groups receiving either fractionated or continuous irradiation treatment after Pc 4. Tumor growth delay following Pc 4-PDT correlated with OPS-measured tumor Pc 4 concentrations at 24 h prior to PDT ( R 2 = 0.86). In excised tumors, OPS-measured Pc 4 concentrations were similar to the HPLC-measured concentrations. Thus, OPS measurements of photosensitizer concentrations can be used to assist in the scheduling of Pc 4-PDT. 相似文献
105.
Bond constraint algorithms for molecular dynamics typically take, as the target constraint lengths, the values of the equilibrium bond lengths defined in the potential. In Langevin form, the equations of motion are temperature dependent, which gives the average value for the individual bond lengths a temperature dependence. In addition to this, locally constant force fields can shift the local equilibrium bond lengths. To restore the average bond lengths in constrained integration to their unconstrained values, we suggest changing the constraint length used by popular constraint methods such as RATTLE [H. C. Andersen, J. Comput. Phys. 52, 23 (1983)] at each step. This allows us to more accurately capture the equilibrium bond length changes (with respect to the potential) due to the local equilibration and temperature effects. In addition, the approximations to the unconstrained nonbonded energies are closer using the dynamic constraint method than a traditional fixed constraint algorithm. The mechanism for finding the new constrained lengths involves one extra calculation of the bonded components of the force, and therefore adds O(N) time to the constraint algorithm. Since most molecular dynamics calculations are dominated by the O(N2) nonbonded forces, this new method does not take significantly more time than a fixed constraint algorithm. 相似文献
106.
Smyth WF 《Electrophoresis》2006,27(11):2051-2062
This review considers applications in 2004-2005 of capillary electrophoresis-electrospray ionisation-mass spectrometry (CE-ESI-MS) to the detection and determination of small molecular mass drug molecules, taken from the Web of Knowledge database. The molecules of small molecular mass less than 1000 Da are chosen according to selected structural classes in which they give ESI signals primarily as [M + H](+) ions. These structural classes are drugs with amine-containing side chains, drugs with N-containing saturated ring structures, 1,4-benzodiazepines, other heterocyclic hypnotics, steroids, bioactive compounds containing phenolic groups, and miscellaneous molecules. Details are given on the fragmentations, where available, that these ionic species exhibit in-source and in ion-trap, triple quadrupole and time-of flight mass spectrometers. The review then gives a critical evaluation of these recent CE-ESI-MS analytical methods for the detection and determination of these small molecular mass drug molecules. Analytical information on, for example, sample concentration techniques, CE separation conditions, recoveries from biological media and limits of detection are provided. 相似文献
107.
Jingwei Xie Bing Ma Praveesuda Lorwattanapongsa Michael Franklin D. Shuler 《Macromolecular bioscience》2012,12(10):1336-1341
A new and simple method for fabrication of nanofiber scaffolds with gradations in fiber organization is reported. The nanofiber organization, achieved by deposition of random fibers on the uniaxially aligned nanofiber mat in a gradient manner, directed morphological changes of applied adipose‐derived stem cells. These morphological changes and resultant biochemical changes can help mimic the structural orientation of complex biomechanical structures like the collagen fiber structure at the tendon‐to‐bone insertion site. In addition, chemical gradients can be established through nanoencapsulation in this novel scaffold allowing for enhanced biomedical applications.
108.
Toman B Duewer DL Aragon HG Guenther FR Rhoderick GC 《Analytical and bioanalytical chemistry》2012,403(2):537-548
Several recent international comparison studies used a relatively novel experimental design to evaluate the measurement capabilities
of participating organizations. These studies compared the values assigned by each participant to one or more qualitatively
similar materials with measurements made on all of the materials by one laboratory under repeatability conditions. A statistical
model was then established relating the values to the repeatability measurements; the extent of agreement between the assigned
value(s) and the consensus model reflected the participants’ measurement capabilities. Since each participant used their own
supplies, equipment, and methods to produce and value-assign their material(s), the agreement between the assigned value(s)
and the model was a fairer reflection of their intrinsic capabilities than provided by studies that directly compared time-
and material-constrained measurements on unknown samples prepared elsewhere. A new statistical procedure is presented for
the analysis of such data. The procedure incorporates several novel concepts, most importantly a leave-one-out strategy for
the estimation of the consensus value of the measurand, model fitting via Bayesian posterior probabilities, and posterior
coverage probability calculation for the assigned 95% uncertainty intervals. The benefits of the new procedure are illustrated
using data from the CCQM-K54 comparison of eight cylinders of n-hexane in methane. 相似文献
109.
Androić D Armstrong DS Arvieux J Bailey SL Beck DH Beise EJ Benesch J Benmokhtar F Bimbot L Birchall J Bosted P Breuer H Capuano CL Chao YC Coppens A Davis CA Ellis C Flores G Franklin G Furget C Gaskell D Gericke MT Grames J Guillard G Hansknecht J Horn T Jones MK King PM Korsch W Kox S Lee L Liu J Lung A Mammei J Martin JW McKeown RD Micherdzinska A Mihovilovic M Mkrtchyan H Muether M Page SA Papavassiliou V Pate SF Phillips SK Pillot P Pitt ML Poelker M Quinn B Ramsay WD Real JS Roche J 《Physical review letters》2012,108(12):122002
The parity-violating (PV) asymmetry of inclusive π- production in electron scattering from a liquid deuterium target was measured at backward angles. The measurement was conducted as a part of the G0 experiment, at a beam energy of 360 MeV. The physics process dominating pion production for these kinematics is quasifree photoproduction off the neutron via the Δ0 resonance. In the context of heavy-baryon chiral perturbation theory, this asymmetry is related to a low-energy constant d(Δ)- that characterizes the parity-violating γNΔ coupling. Zhu et al. calculated d(Δ)- in a model benchmarked by the large asymmetries seen in hyperon weak radiative decays, and predicted potentially large asymmetries for this process, ranging from A(γ)-=-5.2 to +5.2 ppm. The measurement performed in this work leads to A(γ)-=-0.36±1.06±0.37±0.03 ppm (where sources of statistical, systematic and theoretical uncertainties are included), which would disfavor enchancements considered by Zhu et al. proportional to V(ud)/V(us). The measurement is part of a program of inelastic scattering measurements that were conducted by the G0 experiment, seeking to determine the N-Δ axial transition form factors using PV electron scattering. 相似文献
110.
Ahmed Z Allada K Aniol KA Armstrong DS Arrington J Baturin P Bellini V Benesch J Beminiwattha R Benmokhtar F Canan M Camsonne A Cates GD Chen JP Chudakov E Cisbani E Dalton MM de Jager CW De Leo R Deconinck W Decowski P Deng X Deur A Dutta C Franklin GB Friend M Frullani S Garibaldi F Giusa A Glamazdin A Golge S Grimm K Hansen O Higinbotham DW Holmes R Holmstrom T Huang J Huang M Hyde CE Jen CM Jin G Jones D Kang H King P Kowalski S Kumar KS Lee JH LeRose JJ Liyanage N Long E McNulty D 《Physical review letters》2012,108(10):102001
The parity-violating cross-section asymmetry in the elastic scattering of polarized electrons from unpolarized protons has been measured at a four-momentum transfer squared Q2 = 0.624 GeV2 and beam energy E(b) = 3.48 GeV to be A(PV) = -23.80 ± 0.78(stat) ± 0.36(syst) parts per million. This result is consistent with zero contribution of strange quarks to the combination of electric and magnetic form factors G(E)(s) + 0.517G(M)(s) = 0.003 ± 0.010(stat) ± 0.004(syst) ± 0.009(ff), where the third error is due to the limits of precision on the electromagnetic form factors and radiative corrections. With this measurement, the world data on strange contributions to nucleon form factors are seen to be consistent with zero and not more than a few percent of the proton form factors. 相似文献