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991.
Carl R. Kemnitz Prof. Joel L. Mackey Mark J. Loewen Julie L. Hargrove Joshua L. Lewis Whitney E. Hawkins Adam F. Nielsen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(23):6942-6949
The potential origins of stability in branched alkanes are investigated, paying close attention to two recent hypotheses: geminal steric repulsion and protobranching. All alkane isomers through C6H14 along with heptane and octane were investigated at the MPW1B95/6‐311++G(d,p) level. Their geminal steric repulsion, total steric repulsion, and orbital interactions were evaluated by using natural bond orbital analysis. All measures of steric repulsion fail to explain the stability of branched alkanes. The extra stability of branched alkanes and protobranching, in general, is tied to stabilizing geminal σ→σ* delocalization, particularly of the type that involves adjacent C? C bonds and, thus, preferentially stabilizes branched alkanes. This picture is corroborated by valence bond calculations that attribute the effect to additional ionic structures (e.g., CH3+ :CH2 :CH3? and CH3:? CH2: CH3+ for propane) that are not possible without protobranching. 相似文献
992.
993.
Wang J Aubry A Bolgar MS Gu H Olah TV Arnold M Jemal M 《Rapid communications in mass spectrometry : RCM》2010,24(22):3221-3229
Liquid chromatography/tandem mass spectrometry (LC/MS/MS) based on selected reaction monitoring (SRM) is the standard methodology in quantitative analysis of administered xenobiotics in biological samples. Utilizing two SRM channels during positive electrospray ionization (ESI) LC/MS/MS method development for a drug compound containing two basic functional groups, we found that the response ratio (SRM1/SRM2) obtained using an acidic mobile phase was dramatically different from that obtained using a basic mobile phase. This observation is different from the well-established phenomenon of mobile phase affecting the [M+H](+) response, which is directly related to the amount of the [M+H](+) ions produced during the ionization. Results from follow-up work reported herein revealed that the MS/MS fragmentation patterns of four drug or drug-like compounds are affected not only by the pH, but also by the aqueous-organic ratio of the mobile phase and the buffer concentration at a given apparent pH. The observed phenomenon can be explained by invoking that a mixture of [M+H](+) ions of the same m/z value for the analyte is produced that is composed of two or more species which differ only in the site of the proton attachment, which in turn affects their MS/MS fragmentation pattern. The ratio of the different protonated species changes depending on the pH, aqueous-organic ratio, or ionic strength of the mobile phase used. The awareness of the mobile phase dependency of the MS/MS fragmentation pattern of precursor ions of identical m/z value will influence LC/MS/MS-based bioanalytical method development strategies. Specifically, we are recommending that multiple SRM transitions be monitored during mobile phase screening, with the MS/MS parameters used for each SRM optimized for the composition of the mobile phase (pH, organic percentage, and ionic strength) in which the analyte elutes. 相似文献
994.
Ladie Kimberly De La Cruz Xiaoxiao Yang Anna Menshikh Maya Brewer Wen Lu Minjia Wang Siming Wang Xingyue Ji Alyssa Cachuela Haichun Yang David Gallo Chalet Tan Leo Otterbein Mark de Caestecker Binghe Wang 《Chemical science》2021,12(31):10649
Carbon monoxide as an endogenous signaling molecule exhibits pharmacological efficacy in various animal models of organ injury. To address the difficulty in using CO gas as a therapeutic agent for widespread applications, we are interested in developing CO prodrugs through bioreversible caging of CO in an organic compound. Specifically, we have explored the decarboxylation–decarbonylation chemistry of 1,2-dicarbonyl compounds. Examination and optimization of factors favorable for maximal CO release under physiological conditions led to organic CO prodrugs using non-calorific sweeteners as leaving groups attached to the 1,2-dicarbonyl core. Attaching a leaving group with appropriate properties promotes the desired hydrolysis–decarboxylation–decarbonylation sequence of reactions that leads to CO generation. One such CO prodrug was selected to recapitulate the anti-inflammatory effects of CO against LPS-induced TNF-α production in cell culture studies. Oral administration in mice elevated COHb levels to the safe and efficacious levels established in various preclinical and clinical studies. Furthermore, its pharmacological efficacy was demonstrated in mouse models of acute kidney injury. These studies demonstrate the potential of these prodrugs with benign carriers as orally active CO-based therapeutics. This represents the very first example of orally active organic CO prodrugs with a benign carrier that is an FDA-approved sweetener with demonstrated safety profiles in vivo.1,2-Dicarbonyl compounds with FDA-approved sweeteners as leaving groups deliver CO for protection against acute kidney injury in mice. 相似文献
995.
Mark E. Erupe Allegra Liberman-Martin Philip J. Silva Quentin G.J. Malloy Naomi Yonis David R. Cocker III Kathleen L. Purvis-Roberts 《Journal of chromatography. A》2010,1217(13):2070-2073
An ion chromatography method with non-suppressed conductivity detection was developed for the simultaneous determination of methylamines (methylamine, dimethylamine, trimethylamine) and trimethylamine-N-oxide in particulate matter air samples. The analytes were well separated by means of cation-exchange chromatography using a 3 mM nitric acid/3.5% acetonitrile (v/v) eluent solution and a Metrosep C 2 250 (250 mm × 4 mm i.d.) separation column. The effects of the different chromatographic parameters on the separation were also investigated. Detection limits of methylamine, dimethylamine, trimethylamine, and trimethylamine-N-oxide were 43, 46, 76 and 72 μg/L, respectively. The relative standard deviations of the retention times were between 0.42% and 1.14% while the recoveries were between 78.8% and 88.3%. The method is suitable for determining if methylamines and trimethylamine-N-oxide are a significant component of organic nitrogen aerosol in areas with high concentration of these species. 相似文献
996.
Johannes Hatzl Toufik Mansour Mark Shattuck 《Journal of Mathematical Modelling and Algorithms》2011,10(2):193-203
Consider the set S of points in the plane consisting of the ordered pairs (i, j ), where
1 \leqslant i \leqslant m1 \leqslant i \leqslant m and
1 \leqslant j \leqslant n1 \leqslant j \leqslant n. A problem related to the study of segmentation evaluation of visual images concerns finding a permutation σ of the points of S for which the sum
?s ? Sd(s, s(s)) \sum\limits_{s \in S}d(s, \sigma(s)) 相似文献
997.
Mark Comerford 《Central European Journal of Mathematics》2011,9(5):984-996
We consider the following questions: given a hyperbolic plane domain and a separation of its complement into two disjoint closed sets each of which contains at least two points, what is the shortest closed hyperbolic geodesic which separates these sets and is it a simple closed curve? We show that a shortest geodesic always exists although in general it may not be simple. However, one can also always find a shortest simple curve and we call such a geodesic a meridian of the domain. We prove that, although they are not in general uniquely defined, if one of the sets of the separation of the complement is connected, then they are unique and are also the shortest possible geodesics which separate the complement in this fashion. 相似文献
998.
Passive acoustic monitoring allows the assessment of marine mammal occurrence and distribution at greater temporal and spatial scales than is now possible with traditional visual surveys. However, the large volume of acoustic data and the lengthy and laborious task of manually analyzing these data have hindered broad application of this technique. To overcome these limitations, a generalized automated detection and classification system (DCS) was developed to efficiently and accurately identify low-frequency baleen whale calls. The DCS (1) accounts for persistent narrowband and transient broadband noise, (2) characterizes temporal variation of dominant call frequencies via pitch-tracking, and (3) classifies calls based on attributes of the resulting pitch tracks using quadratic discriminant function analysis (QDFA). Automated detections of sei whale (Balaenoptera borealis) downsweep calls and North Atlantic right whale (Eubalaena glacialis) upcalls were evaluated using recordings collected in the southwestern Gulf of Maine during the spring seasons of 2006 and 2007. The accuracy of the DCS was similar to that of a human analyst: variability in differences between the DCS and an analyst was similar to that between independent analysts, and temporal variability in call rates was similar among the DCS and several analysts. 相似文献
999.
Kurihara E Hay TA Ilinskii YA Zabolotskaya EA Hamilton MF 《The Journal of the Acoustical Society of America》2011,130(5):3357-3369
Interaction between acoustically driven or laser-generated bubbles causes the bubble surfaces to deform. Dynamical equations describing the motion of two translating, nominally spherical bubbles undergoing small shape oscillations in a viscous liquid are derived using Lagrangian mechanics. Deformation of the bubble surfaces is taken into account by including quadrupole and octupole perturbations in the spherical-harmonic expansion of the boundary conditions on the bubbles. Quadratic terms in the quadrupole and octupole amplitudes are retained, and surface tension and shear viscosity are included in a consistent manner. A set of eight coupled second-order ordinary differential equations is obtained. Simulation results, obtained by numerical integration of the model equations, exhibit qualitative agreement with experimental observations by predicting the formation of liquid jets. Simulations also suggest that bubble-bubble interactions act to enhance surface mode instability. 相似文献
1000.
An ocean acoustic waveguide remote sensing system can instantaneously image and continuously monitor fish populations distributed over continental shelf-scale regions. Here it is shown theoretically that the areal population density of fish groups can be estimated from their incoherently averaged broadband matched filtered scattered intensities measured using a waveguide remote sensing system with less than 10% error. A numerical Monte-Carlo model is developed to determine the statistical moments of the scattered returns from a fish group. It uses the parabolic equation to simulate acoustic field propagation in a random range-dependent ocean waveguide. The effects of (1) multiple scattering, (2) attenuation due to scattering, and (3) modal dispersion on fish population density imaging are examined. The model is applied to investigate population density imaging of shoaling Atlantic herring during the 2006 Gulf of Maine Experiment. Multiple scattering, attenuation and dispersion are found to be negligible at the imaging frequencies employed and for the herring densities observed. Coherent multiple scattering effects, such as resonance shifts, which can be significant for small highly dense fish groups on the order of the acoustic wavelength, are found to be negligible for the much larger groups typically imaged with a waveguide remote sensing system. 相似文献
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