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621.
Farha OK Wilmer CE Eryazici I Hauser BG Parilla PA O'Neill K Sarjeant AA Nguyen ST Snurr RQ Hupp JT 《Journal of the American Chemical Society》2012,134(24):9860-9863
We have synthesized, characterized, and computationally validated the high Brunauer-Emmett-Teller surface area and hydrogen uptake of a new, noncatenating metal-organic framework (MOF) material, NU-111. Our results imply that replacing the phenyl spacers of organic linkers with triple-bond spacers is an effective strategy for boosting molecule-accessible gravimetric surface areas of MOFs and related high-porosity materials. 相似文献
622.
Pursley RH Salem G Devasahayam N Subramanian S Koscielniak J Krishna MC Pohida TJ 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2006,178(2):220-227
The integration of modern data acquisition and digital signal processing (DSP) technologies with Fourier transform electron paramagnetic resonance (FT-EPR) imaging at radiofrequencies (RF) is described. The FT-EPR system operates at a Larmor frequency (L(f)) of 300MHz to facilitate in vivo studies. This relatively low frequency L(f), in conjunction with our approximately 10MHz signal bandwidth, enables the use of direct free induction decay time-locked subsampling (TLSS). This particular technique provides advantages by eliminating the traditional analog intermediate frequency downconversion stage along with the corresponding noise sources. TLSS also results in manageable sample rates that facilitate the design of DSP-based data acquisition and image processing platforms. More specifically, we utilize a high-speed field programmable gate array (FPGA) and a DSP processor to perform advanced real-time signal and image processing. The migration to a DSP-based configuration offers the benefits of improved EPR system performance, as well as increased adaptability to various EPR system configurations (i.e., software configurable systems instead of hardware reconfigurations). The required modifications to the FT-EPR system design are described, with focus on the addition of DSP technologies including the application-specific hardware, software, and firmware developed for the FPGA and DSP processor. The first results of using real-time DSP technologies in conjunction with direct detection bandpass sampling to implement EPR imaging at RF frequencies are presented. 相似文献
623.
Molecular dynamics simulations were performed on methane clathrate hydrates at ambient conditions. Thermal expansion results over the temperature range 60-300 K show that the unit cell volume increases with temperature in agreement with experiment. Power spectra were obtained at 273 K from velocity autocorrelation functions for selected atoms, and normal modes were assigned. The spectra were further classified according to individual atom types, allowing the assignment of contributions from methane molecules located in small and large cages within the structure I unit cell. The symmetric C-H stretch of methane in the small cages occurs at a higher frequency than for methane located in the large cages, with a peak separation of 14 cm(-1). Additionally, we determined that the symmetric C-H stretch in methane gas occurs at the same frequency as methane in the large cages. Results of molecular dynamics simulations indicate the use of power spectra obtained from the velocity autocorrelation function is a reliable method to investigate the vibrational behavior of guest molecules in clathrate hydrates. 相似文献
624.
Effects of surface area, free volume, and heat of adsorption on hydrogen uptake in metal-organic frameworks 总被引:1,自引:0,他引:1
Grand canonical Monte Carlo simulations were performed to predict adsorption isotherms for hydrogen in a series of 10 isoreticular metal-organic frameworks (IRMOFs). The results show acceptable agreement with the limited experimental results from the literature. The effects of surface area, free volume, and heat of adsorption on hydrogen uptake were investigated by performing simulations over a wide range of pressures on this set of materials, which all have the same framework topology and surface chemistry but varying pore sizes. The results reveal the existence of three adsorption regimes: at low pressure (loading), hydrogen uptake correlates with the heat of adsorption; at intermediate pressure, uptake correlates with the surface area; and at the highest pressures, uptake correlates with the free volume. The accessible surface area and free volume, calculated from the crystal structures, were also used to estimate the potential of these materials to meet gravimetric and volumetric targets for hydrogen storage in IRMOFs. 相似文献
625.
Miniature toroidal radio frequency ion trap mass analyzer 总被引:1,自引:0,他引:1
Lammert SA Rockwood AA Wang M Lee ML Lee ED Tolley SE Oliphant JR Jones JL Waite RW 《Journal of the American Society for Mass Spectrometry》2006,17(7):916-922
A miniature ion trap mass analyzer is reported. The described analyzer is a 1/5-scale version of a previously reported toroidal radio frequency (rf) ion trap mass analyzer. The toroidal ion trap operates with maximum rf trapping voltages about 1 kVp-p or less; however despite the reduced dimensions, it retains roughly the same ion trapping capacity as conventional 3D quadrupole ion traps. The curved geometry provides for a compact mass analyzer. Unit-mass resolved mass spectra for n-butylbenzene, xenon, and naphthalene are reported and preliminary sensitivity data are shown for naphthalene. The expected linear mass scale with rf amplitude scan is obtained when scanned using a conventional mass-selective instability scan mode combined with resonance ejection. 相似文献
626.
We examine consequences of the non-Boltzmann nature of probability distributions for one-particle kinetic energy, momentum, and velocity for finite systems of classical hard spheres with constant total energy and nonidentical masses. By comparing two cases, reflecting walls (NVE or microcanonical ensemble) and periodic boundaries (NVEPG or molecular dynamics ensemble), we describe three consequences of the center-of-mass constraint in periodic boundary conditions: the equipartition theorem no longer holds for unequal masses, the ratio of the average relative velocity to the average velocity is increased by a factor of [N/(N-1)]1/2, and the ratio of average collision energy to average kinetic energy is increased by a factor of N/(N-1). Simulations in one, two, and three dimensions confirm the analytic results for arbitrary dimension. 相似文献
627.
The methoxymethcathinones are uniquely regioisomeric with the controlled drug substance 3,4-methylenedioxymethamphetamine (3,4-MDMA) or Ecstacy. The various isomeric forms of the methoxymethcathinones have mass spectra essentially equivalent to 3,4-MDMA. They all have a molecular weight of 193 and major fragment ions in their electron ionization mass spectra at m/z 58 and 135/136. Differentiation by mass spectrometry was only possible after formation of the perfluoroacyl derivatives, pentafluoropropionylamides (PFPA), and heptafluorobutrylamides (HFBA). Gas chromatographic separation on nonpolar stationary phases successfully resolved the three methcathinones from 2,3- and 3,4-MDMA as the PFPA and HFBA derivatives. 相似文献
628.
Matthew S. Allen Daniel C. Kammer Randall L. Mayes 《Journal of sound and vibration》2012,331(25):5435-5448
When testing to identify an experimental model of a substructure, it is often beneficial to exercise the interface by attaching a fixture such as a rigid mass. An analytical representation of the fixture must then be used to subtract its effects from the assembly. However, this can cause the mass and stiffness matrices to become indefinite in some situations. This paper presents two new metrics that can be used by the analyst to determine the cause of indefinite mass or stiffness matrices after substructure uncoupling. The metrics rank the experimental and fixture modes based upon their contribution to offending negative eigenvalues. Once the troublesome modes have been identified, they can be inspected and often reveal why the mass has become negative. Two examples are presented to demonstrate the metrics and to illustrate the physical phenomena that they reveal. 相似文献
629.
D. G. Gillies B. Newling E. W. Randall 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2001,151(2):235
Stray-field techniques are reported for 31P studies of solids for a variety of compounds including bone, bone meal and calcium hydroxyapatite. Long Hahn echo trains produced by the application of many pulses were used as in the long echo-train summation technique. Double-resonance enhancements of 31P by use of both direct and indirect experiments were attempted on a sample of NH4PF6:31P{19F} double resonance produced, at most, a 26% increase in the initial level of the 31P echo signal. 相似文献
630.
Sarah L. Westcott Steven J. Oldenburg T. Randall Lee Naomi J. Halas 《Chemical physics letters》1999,300(5-6)
We have developed a colloidal assembly for the study of plasmon–plasmon interactions between gold nanoparticles. Colloidal aggregates of controlled size and interparticle spacing were synthesized on silica nanoparticle substrates. Following the immobilization of isolated gold nanoparticles onto silica nanoparticles, the surfaces of the adsorbed gold nanoparticles were functionalized with 4-aminobenzenethiol. This molecular linker attached additional gold nanoparticles to the ‘parent' gold nanoparticle, forming small nanoparticle aggregates. The optical absorption spectrum of these clusters differed from that of gold colloid in a manner consistent with plasmon–plasmon interactions between the gold nanoparticles. 相似文献