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71.
Angelo J. Amoroso Brian F. G. Johnson Jack Lewis Chi-Keung Li Catherine A. Morewood Paul R. Raithby Maria D. Vargas Wing-Tak Wong 《Journal of Cluster Science》1995,6(1):163-173
Reduction of the heptaosmium cluster [Os7(CO)21] With [Et4N][NH4) gives the cluster dianion [Os7(CO)20]2–,1, in high yield. The reaction of the dianion with [AuPR
3Cl] (R=Et or Ph) in the presence of TlPF6 forms [Os7((CO)20(AuPR
3)2] [R=Et (2a);R = Ph(2b)] in 80% yield, while the corresponding reaction with (Os(C6H6)(CH3CN)3]2+ gives [Os8(CO)20 (
6-C6H6)] (3) in reasonable yield (ca. 30%). The dianion,1, and the clusters2 and3 have been fully characterized by bout spectroscopic and crystallographic methods. The crystal structure of the [Ph4P]+ salt of1 shows that the metals in the anion adopt a capped octahedral geometry, with all twenty carbonyl ligands in terminal sites. The metal core geometry in2a is best described as a tricapped octahedron, and is based on the structure of the dianion1 with two adjacent octahedral faces capped by the Au atoms of the two AuPEt3 groups. In a similar fashion, the geometry of3 is related to that of1 with the addition of an Os(C6H6) unit capped to a triangular face, to give a bicapped octahedral framework. 相似文献
72.
Ifk
1 andk
2 are positive integers, the partitionP = (1,2,...,
n
) ofk
1+k
2 is said to be a Ramsey partition for the pairk
1,k
2 if for any sublistL ofP, either there is a sublist ofL which sums tok
1 or a sublist ofP –L which sums tok
2. Properties of Ramsey partitions are discussed. In particular it is shown that there is a unique Ramsey partition fork
1,k
2 having the smallest numbern of terms, and in this casen is one more than the sum of the quotients in the Euclidean algorithm fork
1 andk
2.An application of Ramsey partitions to the following fair division problem is also discussed: Suppose two persons are to divide a cake fairly in the ratiok
1k
2. This can be done trivially usingk
1+k
2-1 cuts. However, every Ramsey partition ofk
1+k
2 also yields a fair division algorithm. This method yields fewer cuts except whenk
1=1 andk
2=1, 2 or 4. 相似文献
73.
Jack Huet 《Tetrahedron》1978,34(16):2473-2479
The measure of relative stabilities of β-alcoxystyrene isomers I: C6H5-CHCH-OR shows that the trans compound is the most stable when RCH3 and C2H5 and the cis compound is the most stable when Ri-C3H7 and t-C4H9. The orientation of the OR group can be determined by RMN 13C. The stabilities of these molecules are discussed in terms of non bounded attractive interactions. This interpretation is confirmed by the measure of relative stabilities of α-methyl β-alcoxy (and acetoxy)-styrene isomers II: C6H5-C(CH3)CH-OR. (RCH3, C2H5 et COCH3). 相似文献
74.
[3-3H]-valine was efficiently synthesised from sodium α-ketoisovalerate. With a β-lactam negative mutant of C. acremonium, l-[1-14C-3-3H]-valine and dl-[1-14C-3-3H]-valine were independently incorporated into the Arnstein tripeptide dimer, i.e. Bis-δ-(l-α-aminodipyl)-l-cystinyl-bis-d-valine, with full retention of trieium at C-3 of the d-valine residue. This result strongly suggested retention of configuration at C-3 of valine when the tripeptide was biosynthesised, and further limited the number of possible mechanisms for the biosynthesis of penicillins. 相似文献
75.
Josephson K Hartman MC Szostak JW 《Journal of the American Chemical Society》2005,127(33):11727-11735
Combinatorial libraries of non-biological polymers and drug-like peptides could in principle be synthesized from unnatural amino acids by exploiting the broad substrate specificity of the ribosome. The ribosomal synthesis of such libraries would allow rare functional molecules to be identified using technologies developed for the in vitro selection of peptides and proteins. Here, we use a reconstituted E. coli translation system to simultaneously re-assign 35 of the 61 sense codons to 12 unnatural amino acid analogues. This reprogrammed genetic code was used to direct the synthesis of a single peptide containing 10 different unnatural amino acids. This system is compatible with mRNA-display, enabling the synthesis of unnatural peptide libraries of 10(14) unique members for the in vitro selection of functional unnatural molecules. We also show that the chemical space sampled by these libraries can be expanded using mutant aminoacyl-tRNA synthetases for the incorporation of additional unnatural amino acids or by the specific posttranslational chemical derivitization of reactive groups with small molecules. This system represents a first step toward a platform for the synthesis by enzymatic tRNA aminoacylation and ribosomal translation of cyclic peptides comprised of unnatural amino acids that are similar to the nonribosomal peptides. 相似文献
76.
A comparative study has been made of the reactions of metal ions with dithizone in the two media, chloroform and molten naphthalene. The absorption spectra of several metal dithizonates, prepared in molten naphthalene, were recorded and were found to be the same as those of the dithizonates obtained by extraction of metal ions from aqueous solution with chloroform dithizone. 相似文献
77.
Abstract— We have devised a method of obtaining simultaneous action spectra for photoreactions I and II by analysis of direct and indirect effects involved in enhancement. The method requires previous determination of the neutral wavelength which gives maximum quantum yield by virtue of equal fractions of open reaction centers ( p and q ) for each photoreaction. A sufficient intensity of the neutral wavelength is used as a constant background. Upon addition of a weak modulated measuring light of intensity Im and wavelength λ m two amperometric signals are obtained for rate of oxygen evolution. A modulated signal (AC¯) isolates the direct effect of Im and gives action of photoreaction II as AC/ Im . An increment in total rate (ΔDC) also includes an indirect effect of Im in perturbing reaction center conditions ( p and q ). From analysis of interaction of the two photoreactions, action for photoreaction I can be estimated as (2 ΔDC-AC)/ Im . The method is applicable to whole cells, properly scales the two action spectra to each other, and removes contribution of the State 1-State 2 phenomena. Action spectra were obtained for Chlorella. 相似文献
78.
Abstract It is shown that the McMillan parameter M = T SAN/T N1 (where T SAN and T NI are respectively the temperatures of the smectic A to nematic (SAN) and the nematic to isotropic (NI) phase transitions) is useful in analysing the crossover between second and first order behaviour of the SNN transition in the nO.m homologous liquid crystal series (the 4-n-alkoxybenzylidene-4′-n-alkylanilines). Using a phase diagram of orientational ordering versus M for this series, as obtained in this work (from E.S.R. and D.S.C), a symmetric tricritical point with mean field exponent β2 = 1 is demonstrated. In a preliminary study of E.S.R. linewidth parameters B and C of nitroxide spin probes dissolved in members of the nO.m series exhibiting a first order SAN transition, critical-type divergences are observed near this transition. In the case where M is closer to 0.959 (the value at the tricritical point), these divergences appear similar to those previously observed in related nO.m members with a second order SAN transition; however, they are considerably enhanced for an M value closer to unity (i.e. more removed from the tricritical point). This indicates the importance of coupling between orientational and positional order parameters in the observed critical-type divergences. 相似文献
79.
Mark P. Waller Thomas Dresselhaus Jack Yang 《Journal of computational chemistry》2013,34(16):1420-1428
Here, we present just a collection of beans (JACOB): an integrated batch‐based framework designed for the rapid development of computational chemistry applications. The framework expedites developer productivity by handling the generic infrastructure tier, and can be easily extended by user‐specific scientific code. Paradigms from enterprise software engineering were rigorously applied to create a scalable, testable, secure, and robust framework. A centralized web application is used to configure and control the operation of the framework. The application‐programming interface provides a set of generic tools for processing large‐scale noninteractive jobs (e.g., systematic studies), or for coordinating systems integration (e.g., complex workflows). The code for the JACOB framework is open sourced and is available at: www.wallerlab.org/jacob . © 2013 Wiley Periodicals, Inc. 相似文献
80.