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61.
Liu L Michelsen K Kitova EN Schnier PD Brown A Klassen JS 《Journal of the American Chemical Society》2012,134(13):5931-5937
Deuterium kinetic isotope effects (KIEs) are reported for the first time for the dissociation of a protein-ligand complex in the gas phase. Temperature-dependent rate constants were measured for the loss of neutral ligand from the deprotonated ions of the 1:1 complex of bovine β-lactoglobulin (Lg) and palmitic acid (PA), (Lg + PA)(n-) → Lg(n-) + PA, at the 6- and 7- charge states. At 25 °C, partial or complete deuteration of the acyl chain of PA results in a measurable inverse KIE for both charge states. The magnitude of the KIEs is temperature dependent, and Arrhenius analysis of the rate constants reveals that deuteration of PA results in a decrease in activation energy. In contrast, there is no measurable deuterium KIE for the dissociation of the (Lg + PA) complex in aqueous solution at pH 8. Deuterium KIEs were calculated using conventional transition-state theory with an assumption of a late dissociative transition state (TS), in which the ligand is free of the binding pocket. The vibrational frequencies of deuterated and non-deuterated PA in the gas phase and in various solvents (n-hexane, 1-chlorohexane, acetone, and water) were established computationally. The KIEs calculated from the corresponding differences in zero-point energies account qualitatively for the observation of an inverse KIE but do not account for the magnitude of the KIEs nor their temperature dependence. It is proposed that the dissociation of the (Lg + PA) complex in aqueous solution also proceeds through a late TS in which the acyl chain is extensively hydrated such that there is no significant differential change in the vibrational frequencies along the reaction coordinate and, consequently, no significant KIE. 相似文献
62.
M K Malik R V Raghavan P Chaddah PK Mishra G Ravi Kumar BA Dasannacharya 《Pramana》1987,29(1):L111-L112
We report critical current measurements on sintered Y0.35Ba0.65CuOy. The sample, in the perovskite phase, shows zero resistance at 87 K. The critical current transition is seen, in zero field
and at 77 K, at a current densityJ
c of 50 A/cm2. 相似文献
63.
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66.
The electronic structure of derivatives of VO(acac)(2) is probed using gas-phase UV-photoelectron spectroscopy [acac = 2,4-pentanedione]. The effect on the metal center of electron-donating and -withdrawing groups on the acac ligands is examined. Ionizations from metal-based, acac-based, and V=O-based orbitals are clearly observed. We find that changes at the ligand periphery lead to equivalent changes in the energies of the metal-based and ligand-based ionizations. Additionally, we find that a linear correlation exists between the ionization energies of the metalated complexes and the pK(a) values of the free ligands, indicating that the pK(a) is a good indication of the overall electron-donating abilities of acac ligands. 相似文献
67.
68.
MVN Murthy Urjit A Yajnik KRS Balaji G Bhattacharyya Amol Dighe Shashikant Dugad ND Hari Dass PK Kabir Kamales Kar D Indumathi John G Learned Debasish Majumdar NK Mondal MVN Murthy SN Nayak Sandip Pakvasa Amitava Raychaudhuri RS Raghavan G Rajasekaran R Ramachandran Alak K Ray Asim K Ray Saurabh Rindani HS Sharatchandra Rahul Sinha Nita Sinha S Umasankar Urjit A Yajnik 《Pramana》2000,55(1-2):347-355
We have identified some important and worthwhile physics opportunities with a possible neutrino detector located in India.
Particular emphasis is placed on the geographical advantage with a stress on the complimentary aspects with respect to other
neutrino detectors already in operation. 相似文献
69.
Sidsel M. Nielsen Alexander A. Shapiro Michael L. Michelsen Erling H. Stenby 《Transport in Porous Media》2010,85(3):785-802
We have developed a mathematical model describing the process of microbial enhanced oil recovery (MEOR). The one-dimensional
isothermal model comprises displacement of oil by water containing bacteria and substrate for their feeding. The bacterial
products are both bacteria and metabolites. In the context of MEOR modeling, a novel approach is partitioning of metabolites
between the oil and the water phases. The partitioning is determined by a distribution coefficient. The transfer part of the
metabolite to oil phase is equivalent to its ”disappearance,” so that the total effect from of metabolite in the water phase
is reduced. The metabolite produced is surfactant reducing oil–water interfacial tension, which results in oil mobilization.
The reduction of interfacial tension is implemented through relative permeability curve modifications primarily by lowering
residual oil saturation. The characteristics for the water phase saturation profiles and the oil recovery curves are elucidated.
However, the effect from the surfactant is not necessarily restricted to influence only interfacial tension, but it can also
be an approach for changing, e.g., wettability. The distribution coefficient determines the time lag, until residual oil mobilization
is initialized. It has also been found that the final recovery depends on the distance from the inlet before the surfactant
effect takes place. The surfactant effect position is sensitive to changes in maximum growth rate, and injection concentrations
of bacteria and substrate, thus determining the final recovery. Different methods for incorporating surfactant-induced reduction
of interfacial tension into models are investigated. We have suggested one method, where several parameters can be estimated
in order to obtain a better fit with experimental data. For all the methods, the incremental recovery is very similar, only
coming from small differences in water phase saturation profiles. Overall, a significant incremental oil recovery can be achieved,
when the sensitive parameters in the context of MEOR are carefully dealt with. 相似文献
70.
The effect of sub-nanosecond fluence fluctuations and triggering on time-resolved laser-induced incandescence (LII) from soot
has been studied using an injection-seeded pulsed Nd:YAG laser that produces a smooth laser temporal profile. Without injection
seeding, this multi-mode laser generates pulses with large intensity fluctuations with sub-nanosecond rise times. The experimental
results described here demonstrate that at fluences below 0.6 J/cm2 LII signals are insensitive to fluence fluctuations on nanosecond time scales. At fluences above 0.6 J/cm2 fluctuations in the laser profile cause the rising edge of the LII profile to move around in time relative to the center
of the laser pulse causing a broader average profile that shifts to earlier times. Such fluctuations also lead to a decrease
in the average LII temporal profile by up to 12% at a fluence of 3.5 J/cm2. A timing jitter on the trigger of the data acquisition, such as that produced by triggering on the laser Q-switch synchronization
pulse, has a negligible effect on the shape and temporal maximum of the LII signal. Additional jitter, however, considerably
reduces the peak of the LII temporal profiles at fluences as low as 0.15 J/cm2. Neither fast fluence fluctuations nor trigger jitter have a significant effect on gated LII signals, such as those used
to infer soot volume fraction. 相似文献