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121.
Hai Yu Eric M. Kennedy Md. Azhar Uddin Simon P. Sullivan Bogdan Z. Dlugogorski 《国际化学动力学杂志》2005,37(3):134-146
Thermal pyrolysis of halon 1211 (CBrClF2), diluted in nitrogen, in a tubular alumina reactor, has been studied over the temperature range of 773–1073 K at residence times from 0.3 to 2 s. At temperatures below 973 K, the major products were CCl2F2, CBr2F2, C2Cl2F4, C2BrClF4, C2F4, and C2Br2F4. Further increasing temperature resulted in the formation of CBrF3, CClF3, and many other species whose formation necessitated the rupture of C? F bonds. Coke formation was also observed on the surface of the reactor at high temperatures. A kinetic reaction scheme involving 16 species and 25 reaction steps was developed and applied to model the thermal pyrolysis of halon 1211 over the temperature range of 773–973 K. Sensitivity analysis suggests that the reaction CBrClF2 + CClF2→CCl2F2 + CBrF2 constitutes the major pathway for the decomposition of halon 1211 under the conditions investigated. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 134–146, 2005 相似文献
122.
Dilute gas Bose-Einstein condensates (BEC's), currently used to cool fermionic atoms in atom traps, can also probe the superfluidity of these fermions. The damping rate of BEC-acoustic excitations (phonon modes), measured in the middle of the trap as a function of the phonon momentum, yields an unambiguous signature of BCS-like superfluidity, provides a measurement of the superfluid gap parameter, and gives an estimate of the size of the Cooper pairs in the BEC-BCS crossover regime. We also predict kinks in the momentum dependence of the damping rate which can reveal detailed information about the fermion quasiparticle dispersion relation. 相似文献
123.
Dr. Yuriy Rebets Dr. Elke Brötz Niko Manderscheid Dr. Bogdan Tokovenko Dr. Maksym Myronovskyi Prof. Dr. Peter Metz Dr. Lutz Petzke Dr. Andriy Luzhetskyy 《Angewandte Chemie (International ed. in English)》2015,54(7):2280-2284
Pamamycins are macrodiolides of polyketide origin with antibacterial activities. Their biosynthesis has been proposed to utilize succinate as a building block. However, the mechanism of succinate incorporation into a polyketide was unclear. Here, we report identification of a pamamycin biosynthesis gene cluster by aligning genomes of two pamamycin‐producing strains. This unique cluster contains polyketide synthase (PKS) genes encoding seven discrete ketosynthase (KS) enzymes and one acyl‐carrier protein (ACP)‐encoding gene. A cosmid containing the entire set of genes required for pamamycin biosynthesis was successfully expressed in a heterologous host. Genetic and biochemical studies allowed complete delineation of pamamycin biosynthesis. The pathway proceeds through 3‐oxoadipyl‐CoA, a key intermediate in the primary metabolism of the degradation of aromatic compounds. 3‐Oxoadipyl‐CoA could be used as an extender unit in polyketide assembly to facilitate the incorporation of succinate. 相似文献
124.
125.
A. N. Kalenchuk A. E. Koklin V. I. Bogdan L. M. Kustov 《Russian Chemical Bulletin》2017,66(7):1208-1212
Catalytic hydrogenation of benzene, biphenyl, and ortho-, metha-, and para-isomers of terphenyl over a 3 wt.% Pt/C at 180 °C and 70 atm was studied. The directions of hydrogenation of each substrate were revealed. Relationships between structures of the substrate and hydrogen consumption rates were found. It was shown that hydrogenation rate decreases on going from benzene to terphenyl and with increasing degree of the substrate hydrogenation. Hydrogenation rate of terphenyl isomers decreases in the following order: p-terphenyl > > m-terphenyl > o-terphenyl. 相似文献
126.
Higher order elements were first design for linear problems where, in certain situations, they present advantages over the lower order elements. A method to efficiently extend their use to geometrical nonlinear problems as panel flutter and postbuckling behavior is presented. The chaotic and limit-cycle oscillations of an isotropic plate are obtained based on direct integration of the discretized equation of motion. The plate is modeled using the von Karman theory and the geometrical nonlinearities are separated in a nonlinear term of the first kind which manifests especially in the prebuckling and buckling regimes, and a nonlinear term of the second kind which is responsible for the postbuckling behavior. A fifth order, fully compatible element has been used to model thin plates while the inplane loads where introduced through a membrane element. The aerodynamics was modeled using the first order 'piston theory. The method introduces the concept of a deteriorated form of the second geometric matrix which is equivalent to neglecting higher order terms in the strain energy of the plate. This allows for a drastic reduction in the computational effort with no observable loss of accuracy. Well established results in the literature are used to validate the method. 相似文献
127.
Chirea M Freitas A Vasile BS Ghitulica C Pereira CM Silva F 《Langmuir : the ACS journal of surfaces and colloids》2011,27(7):3906-3913
Gold nanowire networks (AuNWNs) with average widths of 17.74 nm (AuNWN(1)) or 23.54 nm (AuNWN(2)) were synthesized by direct reduction of HAuCl(4) with sodium borohydride powder in deep eutectic solvents, such as ethaline or reline, at 40 °C. Their width and length were dependent on the type of solvent and the NaBH(4)/HAuCl(4) molar ratio (32 in ethaline and 5.2 in reline). High resolution transmission electron microscopy (HR-TEM) analysis of the gold nanowire networks showed clear lattice fringes of polycrystalline nanopowder of d = 2.36, 2.04, 1.44, and 1.23 ? corresponding to the (111), (200), (220), or (311) crystallographic planes of face centered cubic gold. The purified AuNWNs were used as catalysts for the chemical reduction of p-nitroaniline to diaminophenylene with sodium borohydride in aqueous solution. The reaction was monitored in real time by UV-vis spectroscopy. The results show that the reduction process is six times faster in the presence of gold nanowire networks stabilized by urea from the reline (AuNWN(2)) than in the presence of gold nanowire networks stabilized by ethylene glycol from ethaline (AuNWN(1)). This is due to a higher number of corners and edges on the gold nanowires synthesized in reline than on those synthesized in ethaline as proven by X-ray diffraction (XRD) patterns recorded for both types of gold nanowire networks. Nevertheless, both types of nanomaterials determined short times of reaction and high conversion of p-nitroaniline to diaminophenylene. These gold nanomaterials represent a new addition to a new generation of catalysts: gold based catalysts. 相似文献
128.
Vukomanović M Skapin SD Poljanšek I Zagar E Kralj B Ignjatović N Uskoković D 《Colloids and surfaces. B, Biointerfaces》2011,82(2):414-421
The novel concept of a simultaneous, controlled release of a drug and a prodrug with different physico-chemical properties was applied in order to prolong the release period of antibiotics and estimate their high local concentrations, which are the necessary preconditions for the treatment of some chronic infection diseases. For this purpose poly(D,L-lactide-co-glycolide)/hydroxyapatite (PLGA/HAp) core-shell nanostructures were used as the carrier of clindamycin-base, as a drug, and clindamycin-2-phosphate, as a prodrug model. As a result, a two-step release was observed: the controlled release of the more soluble phosphate form and the sustained release of the less-soluble base form of clindamycin, resulting in a high overall concentration of the released drug during the period of 30 days in vitro. The HAp phase within the PLGA core-shells, applied as a drug carrier, delayed the process of the degradation of the polymer; however, the presence of the drug affected the process of degradation and this influence was the dominant factor in the control over the degradation of the polymer phase of PLGA/HAp and the consequent kinetics of the drug release. 相似文献
129.
Nakayama S Kelsey I Wang J Roelofs K Stefane B Luo Y Lee VT Sintim HO 《Journal of the American Chemical Society》2011,133(13):4856-4864
Recently, there has been an explosion of research activities in the cyclic dinucleotides field. Cyclic dinucleotides, such as c-di-GMP and c-di-AMP, have been shown to regulate bacterial virulence and biofilm formation. c-di-GMP can exist in different aggregate forms, and it has been demonstrated that the polymorphism of c-di-GMP is influenced by the nature of cation that is present in solution. In previous work, polymorphism of c-di-GMP could only be demonstrated at hundreds of micromolar concentrations of the dinucleotide, and it has been a matter of debate if polymorphism of c-di-GMP exists under in vivo conditions. In this Article, we demonstrate that c-di-GMP can form G-quadruplexes at low micromolar concentrations when aromatic molecules such as thiazole orange template the quadruplex formation. We then use this property of aromatic molecule-induced G-quadruplex formation of c-di-GMP to design a thiazole orange-based fluorescent detection of this important signaling molecule. We determine, using this thiazole orange assay on a crude bacterial cell lysate, that WspR D70E (a constitutively activated diguanylate cyclase) is functional in vivo when overexpressed in E. Coli . The intracellular concentration of c-di-GMP in an E. Coli cell that is overexpressed with WspR D70E is very high and can reach 2.92 mM. 相似文献
130.
Zhao Y Zhang J Wang B Kim SH Fang A Bogdanov B Zhou Z McClain C Zhang X 《Journal of chromatography. A》2011,1218(18):2577-2583
A method was developed to calculate the second dimension retention index of comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC/TOF-MS) data using n-alkanes as reference compounds. The retention times of the C(7)-C(31) alkanes acquired during 24 isothermal experiments cover the 0-6s retention time area in the second dimension retention time space, which makes it possible to calculate the retention indices of target compounds from the corresponding retention time values without the extension of the retention space of the reference compounds. An empirical function was proposed to show the relationship among the second dimension retention time, the temperature of the second dimension column, and the carbon number of the n-alkanes. The proposed function is able to extend the second dimension retention time beyond the reference n-alkanes by increasing the carbon number. The extension of carbon numbers in reference n-alkanes up to two more carbon atoms introduces <10 retention index units (iu) of deviation. The effectiveness of using the proposed method was demonstrated by analyzing a mixture of compound standards in temperature programmed experiments using 6 different initial column temperatures. The standard deviation of the calculated retention index values of the compound standards fluctuated from 1 to 12 iu with a mean standard deviation of 5 iu. 相似文献