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11.
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Rahul S. Pawar Erich Grundel Eugene Mazzola Kevin D. White Alexander J. Krynitsky Jeanne I. Rader 《Journal of separation science》2010,33(2):200-205
Enantioseparation of the pyrrolizidine alkaloid isomers intermedine and lycopsamine, isolated from Symphytum uplandicum, is discussed. The separatory power of two immobilized carbohydrate‐based chiral HPLC columns, Chiralpak IA and IC, in different chromatographic conditions is compared. The study demonstrated the importance of solvent and column selection while developing such chiral HPLC separation methods. The baseline HPLC separation of the two alkaloid isomers in preparatory scale is reported for the first time. The optimized separations were achieved on a Chiralpak IA column with mobile phases of ACN/methanol (80:20) and methanol/methyl‐t‐butyl ether (90:10), both containing 0.1% diethylamine. 相似文献
13.
Popova A. A. Shikin A. M. Rybkin A. G. Marchenko D. E. Vilkov O. Yu. Makarova A. A. Varykhalov A. Yu. Rader O. 《Physics of the Solid State》2011,53(12):2539-2544
A study is reported of the role played by covalent interaction in the coupling of graphene formed on Ni(111) to the Ni substrate
and after intercalation of Au and Cu monolayers underneath the graphene. Covalent interaction of the graphene π states with
d states of the underlying metal (Ni, Au, Cu) has been shown to bring about noticeable distortion of the dispersion relations
of the graphene electronic π states in the region of crossing with d states, which can be described in terms of avoided-crossing effects and formation of bonding and antibonding d-π states. The overall graphene coupling to a substrate is mediated by the energy and occupation of the hybridized states
involved. Because graphene formed directly on the Ni(111) surface has only bonding-type occupied states, the coupling to the
substrate is very strong. Interaction with intercalated Au and Cu layers makes occupation of states of the antibonding and
bonding types comparable, which translates into a weak resultant overall coupling of graphene to the substrate. As a result,
after intercalation of Au atoms, the electronic structure becomes similar to that of quasi-free-standing graphene, with linear
dispersion of π states at the K point of the Brillouin zone and the Dirac point localized close to the Fermi level. Intercalation of Cu atoms under the graphene
monolayer results, besides generation of covalent interaction, in a slight charge transport, with a partial occupation of
the previously unoccupied π* states and the Dirac point shifted by 0.35 eV toward increasing binding energy. 相似文献
14.
A chance constrained stochastic program is considered that arises from an application to college enrollments and in which the objective function is the expectation of a linear function of the random variables. When these random variables are independent and normally distributed with mean and variance that are linear in the decision variables, the deterministic equivalent of the problem is a nonconvex nonlinear knapsack problem. The optimal solution to this problem is characterized and a greedy-type heuristic algorithm that exploits this structure is employed. Computational results show that the algorithm performs well, especially when the normal random variables are approximations of binomial random variables. 相似文献
15.
A rapid method for the simultaneous determination of Ac-EEMQRR-amide and H(2)N-EEMQRR-amide in cosmetic products was developed and evaluated. This analytical procedure involved extracting samples with 0.1:0.1:85:15 (v:v) trifluoroacetic acid (TFA):formic acid:acetonitrile (ACN):water and determination by hydrophilic interaction liquid chromatography with tandem mass spectrometry (HILIC-MS/MS). Samples showing serious ion suppression were further cleaned up using HILIC-SPE prior to HILIC-MS/MS analysis. Stable isotopically labeled peptides, corresponding to the above two peptides, were used as internal standards to correct for loss of recovery and matrix effects. Electrospray ionization (ESI) in the positive mode was used. The linear range was 2.0-1000 ng/mL for Ac-EEMQRR-amide and 25.0-2500 ng/mL for H(2)N-EEMQRR-amide. Thirteen commercial products were analyzed for the two peptides using this method. The amounts of Ac-EEMQRR-amide in the samples ranged from none detected to 42.3 μg/g. H(2)N-EEMQRR-amide was not detected in any of the samples. The recoveries for Ac-EEMQRR-amide and H(2)N-EEMQRR-amide ranged from 85% to 110% and 84% to 119%, respectively, at the spiking level of 30 μg/g. 相似文献
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17.
Varykhalov A Sánchez-Barriga J Shikin AM Biswas C Vescovo E Rybkin A Marchenko D Rader O 《Physical review letters》2008,101(15):157601
For the purpose of recovering the intriguing electronic properties of freestanding graphene at a solid surface, graphene self-organized on a Au monolayer on Ni(111) is prepared and characterized by scanning tunneling microscopy. Angle-resolved photoemission reveals a gapless linear pi-band dispersion near K[over] as a fingerprint of strictly monolayer graphene and a Dirac crossing energy equal to the Fermi energy (EF) within 25 meV meaning charge neutrality. Spin resolution shows a Rashba effect on the pi states with a large (approximately 13 meV) spin-orbit splitting up to EF which is independent of k. 相似文献
18.
M.A. Gallis J.R. Torczynski D.J. Rader G.A. Bird 《Journal of computational physics》2009,228(12):4532-4548
The convergence rate of a new direct simulation Monte Carlo (DSMC) method, termed “sophisticated DSMC”, is investigated for one-dimensional Fourier flow. An argon-like hard-sphere gas at 273.15 K and 266.644 Pa is confined between two parallel, fully accommodating walls 1 mm apart that have unequal temperatures. The simulations are performed using a one-dimensional implementation of the sophisticated DSMC algorithm. In harmony with previous work, the primary convergence metric studied is the ratio of the DSMC-calculated thermal conductivity to its corresponding infinite-approximation Chapman–Enskog theoretical value. As discretization errors are reduced, the sophisticated DSMC algorithm is shown to approach the theoretical values to high precision. The convergence behavior of sophisticated DSMC is compared to that of original DSMC. The convergence of the new algorithm in a three-dimensional implementation is also characterized. Implementations using transient adaptive sub-cells and virtual sub-cells are compared. The new algorithm is shown to significantly reduce the computational resources required for a DSMC simulation to achieve a particular level of accuracy, thus improving the efficiency of the method by a factor of 2. 相似文献
19.
Chakraborty S Cole S Rader N King C Rajnarayanan R Biswas PK 《Molecular diversity》2012,16(3):441-451
Human estrogen receptor alpha (ERα), which acts as a biomarker and as a therapeutic target for breast cancers, is activated by agonist ligands and co-activator proteins. Selective estrogen receptor modulators (SERM) act as antagonists in specific tissues and tamoxifen, a SERM, has served as a drug for decades for ERα-positive breast cancers. However, the ligand-selective and tissue-specific response of ERα biological activity and the resistance to tamoxifen treatment in advanced stages of ERα-positive breast cancers underscores the need to find a ligand-independent inhibitor for ERα. Here we present a ligand-independent approach of inhibiting ERα transactivation targeting its dimerization-a key process of ERα biological activity. Using in silico techniques, we first elucidated the hydrogen bond interactions involved in dimerization and identified three interfacial sequence motifs, where sequence I (DKITD) and sequence II (QQQHQRLAQ) of one monomer form hydrogen bonding with sequence II and sequence I of the second monomer, respectively, and sequence III (LSHIRHMSNK) hydrogen bonds with the same from the second monomer. Studying the structural stability and the binding affinity of the peptides derived from these sequence motifs, we found that an extended and ARG mutated version (LQQQHQQLAQ) of sequence II can act as a suitable template for designing peptidic inhibitors. It provides additional structural stability and interacts more strongly with ERα dimer interface groove formed by helices 9 and 10/11 and prevent ERα dimerization. Our result provides a novel therapeutic designing pipeline for ligand-independent inhibition of ERα. 相似文献
20.