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排序方式: 共有82条查询结果,搜索用时 15 毫秒
1.
A cumulative selection procedure for choosing configuration functions for inclusion in CI calculations is described. The objective of the method is to obtain equal energy loss, relative to unselected calculations, for different states and different regions of the potential surface. Results obtained from calculations on the BH molecule indicate an overall advantage in comparison to the threshold selection procedure, particularly with regard to molecular geometry changes. 相似文献
2.
Ab initio (SCF and CI) calculations have been performed for the linear approach (C∝v) of C+ to H2. For the 2 Σ+ surface the saddle point and barrier height were determined. The interaction of the 2Σ+ and 2Π surfaces was investigated, leading to the conclusion that in near-C∝v symmetry a low-energy path exists by which CH+1 Σ+ can be formed, with negligible barrier in excess of endothermicity. 相似文献
3.
Rolando Ramirez Carlos Eduardo Schnorr Jordana Georgin Matias Schadeck Netto Dison S. P. Franco Elvis Carissimi Delmira Wolff Luis F. O. Silva Guilherme Luiz Dotto 《Molecules (Basel, Switzerland)》2022,27(22)
Brazil’s production and consumption of açai pulp (Euterpe oleracea) occur on a large scale. Most of the fruit is formed by the pit, which generates countless tons of residual biomass. A new purpose for this biomass, making its consumption highly sustainable, was presented in this study, where activated carbon (AC) was produced with zinc chloride for later use as an adsorbent. AC carbon formed by carbon and with a yield of 28 % was satisfactorily used as an adsorbent in removing the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Removal efficiency was due to the highly porous surface (Vp = 0.467 cm3 g−1; Dp = 1.126 nm) and good surface área (SBET = 920.56 m2 g−1). The equilibrium data fit the Sips heterogeneous and homogeneous surface model better. It was observed that the increase in temperature favored adsorption, reaching a maximum experimental capacity of 218 mg g−1 at 328 K. The thermodynamic behavior indicated a spontaneous, favorable, and endothermic behavior. The magnitude of the enthalpy of adsorption was in agreement with the physical adsorption. Regardless of the herbicide concentration, the adsorbent displayed fast kinetics, reaching equilibrium within 120 min. The linear driving force (LDF) model provided a strong statistical match to the kinetic curves. AC with zinc chloride (ZnCl2), created from leftover açai biomass, is a potential alternative as an adsorbent for treating effluents containing 2,4-D. 相似文献
4.
Isaiah R. Speight Dr. Igor Huskić Dr. Mihails Arhangelskis Dr. Hatem M. Titi Dr. Robin S. Stein Prof. Timothy P. Hanusa Prof. Tomislav Friščić 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(8):1811-1818
The “disappearing polymorph” phenomenon is well established in organic solids, and has had a profound effect in pharmaceutical materials science. The first example of this effect in metal-containing systems in general, and in coordination-network solids in particular, is here reported. Specifically, attempts to mechanochemically synthesize a known interpenetrated diamondoid (dia) mercury(II) imidazolate metal–organic framework (MOF) yielded a novel, more stable polymorph based on square-grid (sql) layers. Simultaneously, the dia-form was found to be highly elusive, observed only as a short-lived intermediate in monitoring solvent-free synthesis and not at all from solution. The destabilization of a dense dia-framework relative to a lower dimensionality one is in contrast to the behavior of other imidazolate MOFs, with periodic density functional theory (DFT) calculations showing that it arises from weak interactions, including structure-stabilizing agostic C−H⋅⋅⋅Hg contacts. While providing a new link between MOFs and crystal engineering of organic solids, these findings highlight a possible role for agostic interactions in directing topology and stability of MOF polymorphs. 相似文献
5.
Isaiah Adelabu Patrick TomHon Mohammad S. H. Kabir Shiraz Nantogma Mustapha Abdulmojeed Iuliia Mandzhieva Dr. Jessica Ettedgui Dr. Rolf E. Swenson Dr. Murali C. Krishna Prof. Thomas Theis Prof. Boyd M. Goodson Prof. Eduard Y. Chekmenev 《Chemphyschem》2022,23(2):e202100839
Signal Amplification By Reversible Exchange in SHield Enabled Alignment Transfer (SABRE-SHEATH) is investigated to achieve rapid hyperpolarization of 13C1 spins of [1-13C]pyruvate, using parahydrogen as the source of nuclear spin order. Pyruvate exchange with an iridium polarization transfer complex can be modulated via a sensitive interplay between temperature and co-ligation of DMSO and H2O. Order-unity 13C (>50 %) polarization of catalyst-bound [1-13C]pyruvate is achieved in less than 30 s by restricting the chemical exchange of [1-13C]pyruvate at lower temperatures. On the catalyst bound pyruvate, 39 % polarization is measured using a 1.4 T NMR spectrometer, and extrapolated to >50 % at the end of build-up in situ. The highest measured polarization of a 30-mM pyruvate sample, including free and bound pyruvate is 13 % when using 20 mM DMSO and 0.5 M water in CD3OD. Efficient 13C polarization is also enabled by favorable relaxation dynamics in sub-microtesla magnetic fields, as indicated by fast polarization buildup rates compared to the T1 spin-relaxation rates (e. g., ∼0.2 s−1 versus ∼0.1 s−1, respectively, for a 6 mM catalyst-[1-13C]pyruvate sample). Finally, the catalyst-bound hyperpolarized [1-13C]pyruvate can be released rapidly by cycling the temperature and/or by optimizing the amount of water, paving the way to future biomedical applications of hyperpolarized [1-13C]pyruvate produced via comparatively fast and simple SABRE-SHEATH-based approaches. 相似文献
6.
Due to the apolar nature of the lipid bilayer, the weak Calpha-H...O H-bond is thought to contribute significantly toward the stability of transmembrane helical bundles such as glycophorin A (GPA). Here for the first time we measured the strength of such a bond, using vibrational frequency shifts of a dimeric and nondimeric variants of GPA containing a Gly CD2 label. Although the resulting estimated bond strength of 0.88 kcal/mol is relatively weak, several such bonds could contribute significantly toward bundle stabilization. 相似文献
7.
8.
Elvis J. De França Elisabete A. De Nadai Fernandes Márcio A. Bacchi Peter Bode Rob T. M. van Soldt 《Journal of Radioanalytical and Nuclear Chemistry》2009,282(1):125-132
For environmental quality assessment, INAA has been applied for determining chemical elements in small (200 mg) and large
(200 g) samples of leaves from 200 trees. By applying the Ingamells’ constant, the expected percent standard deviation was
estimated in 0.9–2.2% for 200 mg samples. Otherwise, for composite samples (200 g), expected standard deviation varied from
0.5 to 10% in spite of analytical uncertainties ranging from 2 to 30%. Results thereby suggested the expression of the degree
of representativeness as a source of uncertainty, contributing for increasing of the reliability of environmental studies
mainly in the case of composite samples. 相似文献
9.
A bounded operator defined on a Banach space is said to be polaroid if every isolated point of the spectrum is a pole of the
resolvent. In this paper we consider the two related notions of left and right polaroid, and explore them together with the
condition of being a-polaroid. Moreover, the equivalences of Weyl type theorems and generalized Weyl type theorems are investigated for left and
a-polaroid operators. As a consequence, we obtain a general framework which allows us to derive in a unified way many recent
results, concerning Weyl type theorems (generalized or not) for important classes of operators. 相似文献
10.
Walker M. Jones Aaron G. Davis R. Hunter Wilson Katherine L. Elliott Isaiah Sumner 《Journal of computational chemistry》2019,40(22):1969-1977
The mechanism used by the ubiquitin-conjugating enzyme, Ubc13, to catalyze ubiquitination is probed with three computational techniques: Born–Oppenheimer molecular dynamics, single point quantum mechanics/molecular mechanics energies, and classical molecular dynamics. These simulations support a long-held hypothesis and show that Ubc13-catalyzed ubiquitination uses a stepwise, nucleophilic attack mechanism. Furthermore, they show that the first step—the formation of a tetrahedral, zwitterionic intermediate—is rate limiting. However, these simulations contradict another popular hypothesis that supposes that the negative charge on the intermediate is stabilized by a highly conserved asparagine (Asn79 in Ubc13). Instead, calculated reaction profiles of the N79A mutant illustrate how charge stabilization actually increases the barrier to product formation. Finally, an alternate role for Asn79 is suggested by simulations of wild-type, N79A, N79D, and H77A Ubc13: it stabilizes the motion of the electrophile prior to the reaction, positioning it for nucleophilic attack. © 2019 Wiley Periodicals, Inc. 相似文献