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41.
The ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) was successfully used as alternative solvent for native chemical ligation of peptide fragments to produce model peptide LYRAXCRANK (X = G, A, L, N, Q, K, and F). The commonly used buffer system including thiol additives such as thiophenol and benzyl mercaptan can be replaced by the nontoxic ionic liquid [C2mim][OAc]. In addition to improving the solubility of the peptides in [C2mim][OAc], yields and rates of the ligation reactions were found to be efficiently enhanced. 相似文献
42.
Senka Djaković Ivan Kodrin Vilko Smrečki Predrag Novak Zlatko Mihalić Dinko Žiher Jasmina Lapić Vladimir Rapić 《Tetrahedron》2014
In this study we present a synthesis and conformational analysis of 1′-acetylferrocene amino acid derivatives of type Ac–Fn–CO–AA–Y (Fn=ferrocene-1,1-diyl; AA=Gly, Ala or Val; Y=OMe or NHMe) as a simple model for parallel β-helical peptides. Derivatives with only one amino acid adopt a reduced number of total conformations and allow a more exact analysis of intramolecular hydrogen bonds (IHB) close to the ferrocene unit. Conformational analysis of these bioconjugates was performed by a combination of spectroscopic techniques (IR, NMR and CD) and corroborated by solution-phase DFT calculations. The investigation of ester conjugates 1–3 indicates the coexistence of non-bonded (an open forms) and hydrogen bonded NHa group forming a 7-membered ring (γ-turn). The amide derivatives 4–6 with an additional NHb hydrogen bond donor are mostly constituted of conformers with a 10-membered ring (β-turn) as a single IHB pattern or the β-turn accompanied by a 7-membered ring (γ-turn) containing NHa group. The exchange of the amino acid side-chain does not significantly affect the conformational properties and IHB pattern of the studied conjugates 1–6. 相似文献
43.
Margaret Rak Murielle Salome Susan G. W. Kaminskyj Kathleen M. Gough 《Analytical and bioanalytical chemistry》2014,406(12):2809-2816
We used synchrotron X-ray fluorescence to create the first semiquantitative, submicron resolution, element distribution maps of P, S, K, and Ca, in situ, in fungal samples. Data collection was performed at the European Synchrotron Radiation Facility beam line ID21, Grenoble, France. We studied developing hyphae, septa, and conidiophores in Aspergillus nidulans, comparing wild type and two cell wall biosynthesis gene deletion strains. The latter encode sequential enzymes for biosynthesis of galactofuranose, a minor wall carbohydrate. Each gene deletion caused hyphal morphogenesis defects, and reduced both colony growth and sporulation 500-fold. Elemental imaging has helped elucidate biochemical changes in the phenotype induced by the gene deletions that were not apparent from morphological examination. Here, we examined S as a proxy for protein content, P for nucleic acid content, as well as Ca and K, which also have important metabolic roles. Element distributions in wild-type fungi reflect biological aspects already known or expected from other types of analysis; however, the application of X-ray fluorescence (XRF) imaging reveals aspects of gene deletion phenotypes that were not previously available. We have demonstrated that deleting a dispensable gene involved in galactose metabolism (ugeA) and one involved in biosynthesis of a minor cell wall component (ugmA) led to changes in hyphal elemental distribution that may have resulted from compromised wall composition. 相似文献
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46.
The He I and He II photoelectron spectra of 4-methylmorpholine, 4-morpholinecarbonitrile, and 4-morpholinepropionitrile have been measured. The electronic structure and heteroatom lone pair interactions, in particular, were analyzed with the aid of HeII/HeI intensity variations, comparison with the spectra of related compounds, and AM1 semiempirical calculations. We present an example of combined inductive and resonance interactions operating in the morpholine ring system. 相似文献
47.
Igor Novak 《Heteroatom Chemistry》1992,3(4):431-434
Molecular and electronic structures of MX4 (M = Se, Te: X = F, Cl) were studied by the ab initio method with extended basis sets. The study is aimed at supplementing very scarce experimental information about these molecules. The results indicate that all molecules favour distorted disphenoidal geometries (C2v point group) in preference to a C4v geometry. A possibly interesting phenomenon of energy stabilisation by having bonds of different polarities within the same molecule has been observed in SeCl4 and TeCl4. 相似文献
48.
Trevor M. Grant David S. Josey Kathleen L. Sampson Thanmayee Mudigonda Timothy P. Bender Benoît H. Lessard 《Chemical record (New York, N.Y.)》2019,19(6):1093-1112
Organic photovoltaics (OPVs) have experienced continued interest over the last 25 years as a viable technology for the generation of power. Phthalocyanines are among the oldest commercial dyes and have been utilized in some of the earliest examples of OPVs. In recent years, the use of boron subphthalocyanines (BsubPcs) and silicon phthalocyanines (SiPcs) has attracted a flurry of interest with some examples of fullerene‐free devices reaching power conversion efficiencies >8 %. Unlike other more common divalent phthalocyanines such as copper or zinc, BsubPcs and SiPcs contain additional axial groups that can easily be functionalized without significantly affecting the optoelectronic properties of the macrocycle. This handle facilitates our ability to tune the solid‐state arrangement and other physical characteristics such as solubility ultimately giving us the ability to improve the thin film processing and final device performance. This review covers recent studies on the development of BsubPcs and SiPcs for use as active materials in organic photovoltaics. 相似文献
49.
Angelo Sala Kathleen Kayganich Joseph A. Zirrolli Robert C. Murphy 《Journal of the American Society for Mass Spectrometry》1991,2(4):314-321
The sulfidopeptide leukotrienes, leukotriene E4, (LTE4,) and its N-acetyl derivative and several ω? and β-oxidized metabolites of LTE4, have been analyzed by tandem mass spectrometry. [M?H]? ions were produced by continuous flow fast atom bombardment, and collision-induced dissociation of these ions was studied by using a triple quadrupole instrument. The product ion spectra obtained were characteristic of the structure of LTE4, and mechanisms of ion formation were investigated by using deuterated compounds. β-Elimination of the peptide portion of LTE4, by loss of CO2, and ethylene amine leaves the C-l carboxyl group ionized in the most abundant fragment ion for LTE4, and all metabolites. Tandem mass spectrometry of fast atom bombardment-generated anions from ω? and β-oxidized metabolites of LTE4, produced similar ions with only a minor influence of the third carboxyl group at the omega terminus evident. Tandem mass spectrometry was used to identify unequivocally the presence of unmodified LTE4, in a high performance liquid chromatography-purified fraction of urine from a normal healthy volunteer after infusion with LTE4. 相似文献
50.
The Raman and infrared spectra of (NH4)3H(SO4)2 crystal were investigated in the range 20–300 K. An assignment of bands due to internal and external vibrations is given. The crystalline phases designated II, III, V and VII were identified and characterized spectroscopically. Hydrogen bonding, the nature and degree of structural (dis)order and the mechanisms of the phase transitions are discussed. The NH4+ ions show an important orientational disorder and become fully ordered in phase VII only. They are involved in all transitions and seem the main cause of the ferroelectricity at low temperature. 相似文献