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61.
Synthesis of 15-Hydroxy[9]metacyclophane 3-(1-Nitro-2-oxocyclododecyl)propanal ( 1 ) was converted to 15-hydroxy[9]metacyclophane ( 3 ) on two different routes. In the first case the internal aldol reaction product of 1 was treated with K2CO3/THF to give 3 in 29 % yield with regard to cyclododecanone. Alternatively, the aldehyde 1 reacted with a primary amine to form e.g. 4 which gave 3 in the presence of CH3I/K2CO3 in 48 % yield. 相似文献
62.
Alkylation of bicyclo[3.3.0]octane-2,8-dione ( 1 ), which is prepared by a modification of the procedure described in the literature, gives the methyl- and propynyl-derivatives 6 and 7 (Scheme 1). In addition to the method described previously (Scheme 2), 9-methyl-cis-decalin-1,8-dione 9 is obtainable stereoselectively either by cyclization of keto-acid 16 , or by aldol cyclization of keto-aldehyde 26 and oxydation of the resulting alcohols 24 and 25 (Scheme 4). The β-keto-alcohols 24 and 25 undergo a base-catalyzed isomerization; the trans-decalin isomers 27 and 28 are not detected in this equilibrium mixture (Schemes 4 and 5)l. Monoreduction of cis-dione 9 gives the endo-alcohol 25 , while 27 is the favored product of the reductin of trans-dione 10 (Scheme 4). Optically pure (+)- 25 can be prepared from (9S,10R)-monoacetal 29 (Scheme 5). 相似文献
63.
Analysis of methyl- and ethylmercury (MM and EM) halides in biological and environmental samples is generally performed by gas chromatography with electron capture detection. Tedious sample work-up protocols and poor chromatographic response (using packed columns) have, however, shown the need for the development of new methods in this field. This paper reports a sensitive method, free from these deficiencies, for the determination of methyl- and ethylmercury. The organomercury compounds (MM and EM) are first released from the sample matrix, by the combined action of acidic potassium bromide and cupric ions, and then extracted into dichloromethane. The initial extracts are subjected to thiosulfate clean-up and the organomercury species are isolated as their chloride derivatives by addition of cupric chloride, and subsequent extraction into a small volume of organic solvent. Capillary GC coupled with atomic fluorescence detection provided excellent separation efficiencies for methyl- and ethylmercury and proved to be a very selective and sensitive technique. The absolute detection limit for both MM and EM was found to be 0.2 pg. 相似文献
64.
A simple preparation of the chloronitrosylcarbonylmolybdenum(0) complexes Mo(NO)(CO)4(AlCl4) and MoCl(NO)(CO)2(PPh3)2 is described. The homogeneous system MoCl(NO)(CO)2(PPh3)2/RAlCl2 (R = Et, Me) represents a new highly active long-living catalyst for the metathesis of 2-pentene. 相似文献
65.
Formation of CoAl3Cl11 at higher Al2Cl6 Pressures The reaction of CoCl2,f with Al2Cl6,g (≈ 3 atm) is investigated considering every component of the gas phase (Al2Cl6, AlCl3, Al3Cl9, CoAlCl5, CoAl2Cl8, CoAl3Cl11) and the deviation from the ideal behaviour. The conclusion is derived that at 600 K from CoCl2,s and larger pressures of Al2Cl6 besides CoAl2Cl8 a small amount of CoAl3Cl11 is formed. 相似文献
66.
In a comparative study the in vitro corrosion behavior of a selection of nickel- and cobalt-based alloys for application in
dentistry containing no noble metals was studied with slow scan cyclic voltammetry. The obtained breakthrough potentials,
the repassivation behavior and further typical features of the cyclic voltamograms are correlated with the chemical composition
as measured with electron beam microanalysis. Surface inhomogenities detected with the latter method are discussed with respect
to the electrochemical behavior. For all alloys stabilities in terms of breakthrough potential superior to previously reported
data for nickel-base alloys are found. 相似文献
67.
Sitnikova NL Sprik R Wegdam G Eiser E 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7083-7089
We studied the spontaneous emulsification and droplet growth mechanism in trans-anethol/water/ethanol solutions, also known as the beverage ouzo, using dynamic light scattering spectroscopy. This simple ternary mixture is a generic example of a system that forms microemulsions spontaneously when brought into the two-phase region. The volume fraction of the dispersed phase was found to profoundly affect the growth rates of the droplets, which is a new finding that has not been predicted by the Lifshitz-Slyozov-Wagner theory. Time-dependent measurements show that the droplet growth is governed by Ostwald ripening (OR), and no coalescence was observed. Furthermore, the OR rates increase with increasing oil concentration at low alcohol content. We attribute this behavior to enhanced droplet-droplet interactions. At high ethanol concentrations, we found that the measured rates decreased as the oil concentration increased. The OR growth mechanism completely correlates with changes in droplet size. The kinetics of droplet growth shows that the ripening has a saturation limit at a droplet radius of about 1.5 mum. Thus, formed emulsions remain stable for months. 相似文献
68.
Siegers C Biesalski M Haag R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(11):2831-2838
Highly protein-resistant, self-assembled monolayers (SAMs) of dendritic polyglycerols (PGs) on gold can easily be obtained by simple chemical modification of these readily available polymers with a surface-active disulfide linker group. Several disulfide-functionalized PGs were synthesized by N,N'-dicyclohexylcarbodiimide-mediated ester coupling of thioctic acid. Monolayers of the disulfide-functionalized PG derivatives spontaneously form on a semitransparent gold surface and effectively prevent the adsorption of proteins, as demonstrated by surface plasmon resonance (SPR) kinetic measurements. A structure-activity relationship relating the polymer architecture to its ability to effectuate protein resistance has been derived from results of different surface characterization techniques (SPR, attenuated total reflectance infrared (ATR-IR), and contact-angle measurements). Dendritic PGs combine the characteristic structural features of several highly protein-resistant surfaces: a highly flexible aliphatic polyether, hydrophilic surface groups, and a highly branched architecture. PG monolayers are as protein resistant as poly(ethylene glycol) (PEG) SAMs and are significantly better than dextran-coated surfaces, which are currently used as the background for SPR spectroscopy. Due to the higher thermal and oxidative stability of the bulk PG as compared to the PEG and the easy accessibility of these materials, dendritic polyglycerols are novel and promising candidates as surface coatings for biomedical applications. 相似文献
69.
Repeatable ring expansions by [2,3]-sigmatropic shifts in cyclic allylsulfonium allylides; synthesis of medium- and large-sized thiacycles Allylation of a 2-vinyl thiacyclus with allyl bromide in 2,2,2-trifluoroethanol followed by ylide generation by use of aqueous potassium hydroxide results in a [2,3]-sigmatropic rearrangement with formation of a new 2-vinyl thiacyclus enlarged by three carbon atoms (Scheme 1). In this way, starting from the 5-membered ring 1 , a series of four ring enlargement sequences leads to the 17-membered thiacycles 9 and 10 via the 8-, 11- and 14-membered rings 4 , 7 and 8 (Scheme 2). 相似文献
70.
Dr. Rudolf J. Taschner 《Monatshefte für Mathematik》1978,86(3):221-237
It is the aim of this paper to introduce two new notions of discrepancy. They are defined by the formulas $$\begin{gathered} \Delta _N^r \left( {\omega ;f} \right) = \mathop {\sup }\limits_{\left| z \right| = r} \left| {\left( {{1 \mathord{\left/ {\vphantom {1 N}} \right. \kern-\nulldelimiterspace} N}} \right)\sum\limits_{n = 1}^N {f\left( {z e^2 \pi i\omega \left( n \right)} \right)} - f\left( 0 \right)} \right|, and \hfill \\ \delta _N^r \left( {\omega ;f} \right) = \mathop {\sup }\limits_{\left| z \right| = r} \left| {\left( {{1 \mathord{\left/ {\vphantom {1 N}} \right. \kern-\nulldelimiterspace} N}} \right)\sum\limits_{n = 1}^N {f\left( {z \omega \left( n \right)} \right)} \cdot z - \int\limits_0^z {f\left( \zeta \right)d\zeta } } \right|, \hfill \\ \end{gathered} $$ wheref is a holomorphic function defined in the unit disc withf (k) (0)≠0 for allk∈?,r<1 is a positive number, and ω is a sequence in [0, 1]. The first of these discrepancies can be generalized for multidimensional sequences. ω is uniform distributed if and only if lim N→∞ Δ N r (ω;f)=0 resp. lim N→∞δ N r (ω;f)=0. These results are proved in a quantitative way by estimating the classical discrepancyD N (ω) by means ofΔ N r (ω;f) and δ N r (ω;f): $$\begin{gathered} \Delta _N^r \left( {\omega ;f} \right) \ll D_N \left( \omega \right) \ll \Phi \left( {\Delta _N^r \left( {\omega ;f} \right)} \right), \hfill \\ \delta _N^r \left( {\omega ;f} \right) \ll D_N \left( \omega \right) \ll \Psi \left( {\delta _N^r \left( {\omega ;f} \right)} \right). \hfill \\ \end{gathered} $$ The functions Φ and Ψ only depend onf andr. These estimations are based on the inequalities ofKoksma-Hlawka andErdös-Turán. 相似文献