Sorptive thin film microextraction followed by direct solid state spectrofluorimetry: A simple,rapid and sensitive method for determination of carvedilol in human plasma

A poly acrylate-ethylene glycol (PA-EG) thin film is introduced for the first time as a novel polar sorbent for sorptive extraction method coupled directly to solid-state spectrofluorimetry without the necessity of a desorption step. The structure, polarity, fluorescence property and extraction performance of the developed thin film were investigated systematically. Carvedilol was used as the model analyte to evaluate the proposed method. The entire procedure involved one-step extraction of carvedilol from plasma using PA-EG thin film sorptive phase without protein precipitation. Extraction variables were studied in order to establish the best experimental conditions. Optimum extraction conditions were the followings: stirring speed of 1000 rpm, pH of 6.8, extraction temperature of 60 °C, and extraction time of 60 min. Under optimal conditions, extraction of carvedilol was carried out in spiked human plasma; and the linear range of calibration curve was 15–300 ng mL⁻¹ with regression coefficient of 0.998. Limit of detection (LOD) for the method was 4.5 ng mL⁻¹. The intra- and inter-day accuracy and precision of the proposed method were evaluated in plasma sample spiked with three concentration levels of carvedilol; yielding a recovery of 91–112% and relative standard deviation of less than 8%, respectively. The established procedure was successfully applied for quantification of carvedilol in plasma sample of a volunteer patient. The developed PA-EG thin film sorptive phase followed by solid-state spectrofluorimetric method provides a simple, rapid and sensitive approach for the analysis of carvedilol in human plasma.     

Evidence for a transition in deformation mechanism in nanocrystalline pure titanium processed by high-pressure torsion

Nanocrystalline titanium with an average grain size of about 60–70 nm was prepared by high-pressure torsion. The results of hardness and structural evolutions indicate that a strain-induced hardening–softening–hardening–softening behaviour occurs. For coarse-grained titanium, 〈a〉-type dislocation multiplication, twinning and a high pressure-induced α-to-ω phase transformation play major roles to accommodate deformation, leading to a significant strain hardening. As deformation proceeds, dynamic recrystallisation leads to a decrease in dislocation density, especially for 〈a〉-type dislocations, leading to a slight strain softening. The 〈c〉-component dislocation multiplication dominates the deformation when the grain size decreases to 100 nm and 〈c〉-component dislocation multiplication, grain refinement and the α-to-ω phase transformation contribute to the second strain hardening. The following strain softening is attributed to dynamic recovery.     

Linear metal-metal-bonded tetranuclear M-Mo-Mo-M complexes (M = Ir and Rh): oxidative metal-metal bond formation in a tetrametallic system and 1,4-addition reaction of alkyl halides

Reaction of Mo2(pyphos)4 (1) with [MCl(CO)2]2 (M = Ir and Rh) afforded linear tetranuclear complexes of a formula Mo2M2(CO)2(Cl)2(pyphos)4 (2, M = Ir; 3, M = Rh). X-ray diffraction studies confirmed that two "MCl(CO)" fragments are introduced into both axial sites of the Mo2 core in 1 and coordinated by two PPh2 groups in a trans fashion, thereby forming a square-planar geometry around each M(I) metal. Treatment of 2 and 3 with an excess amount of tBuNC and XylNC induced dissociation of the carbonyl and chloride ligands to yield the corresponding dicationic complexes [Mo2M2(pyphos)4(tBuNC)4](Cl)2 (5a, M = Ir; 6a, M = Rh) and [Mo2M2(pyphos)4(XylNC)4](Cl)2 (7, M = Ir; 8, M = Rh). Their molecular structures were characterized by spectroscopic data as well as X-ray diffraction studies of BPh4 derivatives [Mo2M2(pyphos)4(tBuNC)4](BPh4)2 (5b, M = Ir; 6c, M = Rh), which confirmed that there is no direct sigma-bonding interaction between the M(I) atom and the Mo2 core. The M(I) atom in 5 and 6 can be oxidized by either 2 equiv of [Cp2Fe][PF6] or an equimolar amount of I2 to afford Mo(II)2M(II)2 complexes, [Mo2M2(X)2(tBuNC)4(pyphos)4]2+ in which two Mo-M(II) single bonds are formed and the bond order of the Mo-Mo moiety has been decreased to three. The Ir(I) complex 5a reacted not only with methyl iodide but also with dichloromethane to afford the 1,4-oxidative addition products [Mo2Ir2(CH3)(I)(tBuNC)4(pyphos)4](Cl)2 (13) and [Mo2Ir2(CH2Cl)(Cl)(tBuNC)4(pyphos)4](Cl)2 (15), respectively, although the corresponding reactions using the Rh(I) analogue 6 did not proceed. Kinetic analysis of the reaction with CH3I suggested that the 1,4-oxidative addition to the Ir(I) complex occurs in an SN2 reaction mechanism.     

Influence of Short-Chain Alcohols on the Micellization Parameters of Sodium Dodecyl Sulfate (SDS)

The influence of short-chain alcohol on the aggregation behavior of Sodium Dodecyl Sulfate (SDS) is investigated within a wide range of alcohol concentration by potentiometric technique. It is observed that aggregation behavior of SDS is a function of alcohol concentration. Variation of micellization parameters are studied in a wide range of alcohol concentration and the trend of changing of micellization parameters have been investigated. The variations of micellization parameters show several regularities. Finally, the relationships between these regularities and alcohol-surfactant interactions have been explained.     

Gyroscope-like molecules consisting of PdX2/PtX2 rotators encased in three-spoke stators: synthesis via alkene metathesis, and facile substitution and demetalation

Reactions of trans-MCl2(P((CH2)6(CH=CH2)3)2 (M = a, Pd; b, Pt) and Grubbs' catalyst, followed by hydrogenation (ClRh(PPh3)3), give the title compounds trans-MCl2(P((CH2)14)3P) (2a, 37%; 2b, 43%). These react with LiBr, NaI, and KCN to give the corresponding MBr2, MI2, and M(CN)2 species (58-99%). 13C NMR data show that the MX2 moieties rapidly rotate within the diphosphine cage on the NMR time scale, even at -120 degrees C. The reaction of 2b and KSCN gives separable Pt(SCN)2 and Pt(SCN)(NCS) species (5b, 27%; 6b, 30%), and that with Ph2Zn gives a PtPh2 species (7b, 55%). NMR data for 5b-7b show that MX2 rotation is no longer rapid. Reactions of 2b with excess NaCCH or KCN afford the free dibridgehead diphosphine P((CH2)14)3P (66-83%), presumably as an "in/in" isomer, as addition of PtCl2 regenerates 2b. The crystal structures of 2a and 7b are analyzed with respect to MX2 rotation.     

光刻技术:发展路径及未来趋势

光刻技术在半导体器件大规模生产中发挥重要作用.今天,多数先进半导体生产都已经应用ArF准分子激光浸润光刻技术.双重图像曝光和侧壁图像转移技术使ArF准分子激光浸润光刻技术延伸到32纳米半节距(HP)器件的制造成为可能.为了制造更小尺寸的器件,必须开发新的制造工艺.极端紫外线光刻是制造22纳米半节距甚至更小尺寸半导体器件的先进下一代光刻技术解决方案.另外,其他技术解决方案,如纳米压印光刻技术和无掩模直描光刻技术等也被考虑用于制造更小节点尺寸的器件,但是目前这些方案仅仅处在研发阶段,而且在现阶段就已经呈现出在大规模生产中的诸多困难.本文从材料的角度对光刻技术进行一个整体描述,并对光刻技术未来趋势进行讨论.     

Measurement of the 2H(p,n) Breakup Reaction at 170 MeV and the Three-Nucleon Force Effects

The effects of three nucleon force (3NF) have been actively studied via the nucleon–deuteron (Nd) scattering states. The differential cross sections and the vector analyzing powers A _y of the ²H(p, n) inclusive breakup reaction at 170 MeV were measured for the study of 3NF effects in the intermediate energy region. The polarized proton beam of 170 MeV was injected to the deuterated polyethylene (CD₂) target and the energy of scattered neutrons were measured by using TOF method. The data were compared with the Faddeev calculations based on modern nucleon–nucleon (NN) forces with and without the 3NF. Concerning the differential cross sections, we can see large discrepancies between the data and the calculations in the region of scattered neutron energies are low, which is similar to the results of the ²H(p, p) inclusive breakup reaction at 250 MeV.     

Simultaneous enantiomeric determination of MDMA and its phase I and phase II metabolites in urine by liquid chromatography–tandem mass spectrometry with chiral derivatization

A liquid chromatography–electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) procedure was developed for the simultaneous determination of enantiomers of the prevalent designer drug 3,4-methylenedioxymethamphetamine (MDMA) and its phase I and phase II metabolites in urine with chiral derivatization. The analytes in urine were directly derivatized with chiral Marfey’s reagent, N ^α- (5-fluoro-2,4-dinitrophenyl)-d-leucinamide, without extraction. The diastereomers of the N ^α-(2,4-dinitrophenyl)-d-leucinamide derivatives generated were determined by LC-MS/MS. Satisfactory chromatographic separation was achieved for the enantiomers of MDMA and its metabolites 3,4-methylenedioxyamphetamine, 4-hydroxy-3-methoxymethamphetamine (HMMA), HMMA glucuronide, and HMMA sulfate on a semimicro octadecylsilane column using linear gradient elution. With use of multiple reaction monitoring mode, the limits of detection of these analytes ranged from 0.01 to 0.03?μg/mL. Linear calibration curves were obtained for all enantiomers from 0.1 to 20?μg/mL in urine. The method showed sufficient reproducibility and quantitative ability. This is the first report of a simple LC-MS/MS-based analytical procedure with direct chiral derivatization in aqueous media that allows simultaneous enantiomeric determination of drugs and their metabolites, including glucuronide and sulfate derivatives.     

Blind deconvolution for robust signal estimation and approximate source localization

Synthetic time reversal (STR) is a technique for blind deconvolution in an unknown multipath environment that relies on generic features (rays or modes) of multipath sound propagation. This paper describes how ray-based STR signal estimates may be improved and how ray-based STR sound-channel impulse-response estimates may be exploited for approximate source localization in underwater environments. Findings are based on simulations and underwater experiments involving source-array ranges from 100 m to 1 km in 60 -m-deep water and chirp signals with a bandwidth of 1.5-4.0 kHz. Signal estimation performance is quantified by the correlation coefficient between the source-broadcast and the STR-estimated signals for a variable number N of array elements, 2 ≤ N ≤ 32, and a range of signal-to-noise ratio (SNR), -5 dB ≤ SNR ≤ 30 dB. At high SNR, STR-estimated signals are found to have cross-correlation coefficients of ～90% with as few as four array elements, and similar performance may be achieved at a SNR of nearly 0 dB with 32 array elements. When the broadband STR-estimated impulse response is used for source localization via a simple ray-based backpropagation scheme, the results are less ambiguous than those obtained from conventional broadband matched field processing.