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21.
S M Holmes D F Schafer P T Wolczanski E B Lobkovsky 《Journal of the American Chemical Society》2001,123(43):10571-10583
Treatment of NaW2Cl7(THF)5 with 4 equiv of (t)Bu3SiNHLi afforded the C2 W(III) dimer [((t)Bu3SiNH)2WCl]2 (1, d(W triple bond W) = 2.337(2) A), which is a rare, primary amide M2X4Y2 species. Its degradation provided evidence of NH bond activation by the ditungsten bond. Addition of 2 equiv of (t)Bu3SiNHLi or TlOSi(t)Bu3 to 1 yielded H2 and hydride ((t)Bu3SiN)2((t)Bu3SiNH)WH (2, d(WH) = 1.67(3) A) or ((t)Bu3SiN)2((t)Bu3SiO)WH (3). Thermolysis (60 degrees C, 16 h) of 1 in py gave ((t)Bu3SiN)2WHCl(py) (4-py, 40-50%), ((t)Bu3SiN)2WCl2(py) (6-py, 10%), and ((t)Bu3SiN)2HW(mu-Cl)(mu-H)2W(NSi(t)Bu3)py2 (5-py2, 5%), whereas thermolysis in DME produced ((t)Bu3SiN)2WCl(OMe) (7, 30%), ((t)Bu3SiN)2WCl2 (6, 20%), and ((t)Bu3SiN)2HW(mu-Cl)(mu-H)2W(NSi(t)Bu3)DME (5-DME, 3%). Compound 7 was independently produced via thermolysis of 4-py and DME (-MeOEt, -py), and THF and ethylene oxide addition to hydride 2 gave ((t)Bu3SiN)2((t)Bu3SiNH)WO(n)Bu (8) and ((t)Bu3SiN)2((t)Bu3SiNH)WOEt (9), respectively. Dichloride 6 was isolated from SnCl4 treatment of 1 with the loss of H2. Sequential NH bond activations by the W2 core lead to "((t)Bu3SiN)2WHCl" (4) and subsequent thermal degradation products. Thermolysis of 1 in the presence of H2C=CH(t)Bu and PhC triple bond CPh trapped 4 and generated ((t)Bu3SiN)2W((neo)Hex)Cl (10) and a approximately 6:1 mixture of ((t)Bu3SiN)2WCl(cis-CPh=CPhH) (11-cis) and ((t)Bu(3)SiN)2WCl(trans-CPh=CPhH) (11-trans), respectively. Thermolysis of the latter mixture afforded ((t)Bu3SiNH)((t)Bu3SiN)WCl(eta2-PhCCPh) (12) as the major constituent. Alkylation of 1 with MeMgBr produced ((t)Bu3SiN)2W(CH3)2 (13), as did addition of 2 equiv of MeMgBr to 6. X-ray crystal structure determinations of 1, 2, 5-py2, 6-py, 11-trans, and 12 confirmed spectroscopic identifications. A general mechanism that features a sequence of NH activations to generate 4, followed by chloride metathesis, olefin insertion, etc., explains the formation of all products. 相似文献
22.
23.
Sebastian G. Spain Matthew I. Gibson Neil R. Cameron 《Journal of polymer science. Part A, Polymer chemistry》2007,45(11):2059-2072
Glycopolymers are receiving increasing interest due to their application in areas, such as glycomics, medicine, biotechnology, sensors, and separation science. Consequently, new methods for their synthesis are constantly being developed, with an increasing emphasis on the preparation of well-defined polymers and on the production of complex macromolecular architectures such as stars. This review covers recent developments in the synthesis of glycopolymers, with a particular emphasis on (i) the use of controlled radical polymerization to prepare well-defined glycopolymers from unprotected monomers and (ii) postpolymerization modification strategies using reactive polymer precursors (including “click” reactions). Recent work on the production of glycosylated polypeptides, which are under investigation as mimics of naturally occurring glycoproteins, is also included. The authors offer some suggestions as to future developments and remaining challenges in this topical area of polymer chemistry. © 2007 Wiley Periodicals, Inc. J Polym Sci PartA: Polym Chem45: 2059–2072, 2007 相似文献
24.
Albrecht M Mirtschin S de Groot M Janser I Runsink J Raabe G Kogej M Schalley CA Fröhlich R 《Journal of the American Chemical Society》2005,127(29):10371-10387
The ligands 4-7-H(2) were used in coordination studies with titanium(IV) and gallium(III) ions to obtain dimeric complexes Li(4)[(4-7)(6)Ti(2)] and Li(6)[(4/5a)(6)Ga(2)]. The X-ray crystal structures of Li(4)[(4)(6)Ti(2)], Li(4)[(5b)(6)Ti(2)], and Li(4)[(7a)(6)Ti(2)] could be obtained. While these complexes are triply lithium-bridged dimers in the solid state, a monomer/dimer equilibrium is observed in solution by NMR spectroscopy and ESI FT-ICR MS. The stability of the dimer is enhanced by high negative charges (Ti(IV) versus Ga(III)) of the monomers, when the carbonyl units are good donors (aldehydes versus ketones and esters), when the solvent does not efficiently solvate the bridging lithium ions (DMSO versus acetone), and when sterical hindrance is minimized (methyl versus primary and secondary carbon substituents). The dimer is thermodynamically favored by enthalpy as well as entropy. ESI FT-ICR mass spectrometry provides detailed insight into the mechanisms with which monomeric triscatecholate complexes as well as single catechol ligands exchange in the dimers. Tandem mass spectrometric experiments in the gas phase show the dimers to decompose either in a symmetric (Ti) or in an unsymmetric (Ga) fashion when collisionally activated. The differences between the Ti and Ga complexes can be attributed to different electronic properties and a charge-controlled reactivity of the ions in the gas phase. The complexes represent an excellent example for hierarchical self-assembly, in which two different noncovalent interactions of well balanced strengths bring together eleven individual components into one well-defined aggregate. 相似文献
25.
Herbert Schumann Sebastian Dechert Frank Girgsdies Bernd Heymer Markus Hummert Ji‐Young Hyeon Jens Kaufmann Stefan Schutte Sonja Wernik Birgit C. Wassermann 《无机化学与普通化学杂志》2006,632(2):251-263
Synthesis and Characterization of New Intramolecularly Nitrogen‐stabilized Organoaluminium‐ and Organogallium Alkoxides The intramolecularly nitrogen stabilized organoaluminium alkoxides [Me2Al{μ‐O(CH2)3NMe2}]2 ( 1a ), Me2AlOC6H2(CH2NMe2)3‐2,4,6 ( 2a ), [(S)‐Me2Al{μ‐OCH2CH(i‐Pr)NH‐i‐Pr}]2 ( 3a ) and [(S)‐Me2Al{μ‐OCH2CH(i‐Pr)NHCH2Ph}]2 ( 4 ) are formed by reacting equimolar amounts of AlMe3 and Me2N(CH2)3OH, C6H2[(CH2NMe2)3‐2,4,6]OH, (S)‐i‐PrNHCH(i‐Pr)CH2OH, or (S)‐PhCH2NHCH(i‐Pr)CH2OH, respectively. An excess of AlMe3 reacts with Me2N(CH2)2OH, Me2N(CH2)3OH, C6H2[(CH2NMe2)3‐2,4,6]OH, and (S)‐i‐PrNHCH(i‐Pr)CH2OH producing the “pick‐a‐back” complexes [Me2AlO(CH2)2NMe2](AlMe3) ( 5 ), [Me2AlO(CH2)3NMe2](AlMe3) ( 1b ), [Me2AlOC6H2(CH2NMe2)3‐2,4,6](AlMe3)2 ( 2b ), and [(S)‐Me2AlOCH2CH(i‐Pr)NH‐i‐Pr](AlMe3) ( 3b ), respectively. The mixed alkyl‐ or alkenylchloroaluminium alkoxides [Me(Cl)Al{μ‐O(CH2)2NMe2}]2 ( 6 ) and [{CH2=C(CH3)}(Cl)Al{μ‐O(CH2)2NMe2}]2 ( 8 ) are to obtain from Me2AlCl and Me2N(CH2)2OH and from [Cl2Al{μ‐O(CH2)2NMe2}]2 ( 7 ) and CH2=C(CH3)MgBr, respectively. The analogous dimethylgallium alkoxides [Me2Ga{μ‐O(CH2)3NMe2}]2 ( 9 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)NH‐i‐Pr}]n ( 10 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)NHCH2Ph}]n ( 11 ), [(S)‐Me2Ga{μ‐OCH2CH(i‐Pr)N(Me)CH2Ph}]n ( 12 ) and [(S)‐Me2Ga{μ‐OCH2(C4H7NHCH2Ph)}]n ( 13 ) result from the equimolar reactions of GaMe3 with the corresponding alcohols. The new compounds were characterized by elemental analyses, 1H‐, 13C‐ and 27Al‐NMR spectroscopy, and mass spectrometry. Additionally, the structures of 1a , 1b , 2a , 2b , 3a , 5 , 6 and 8 were determined by single crystal X‐ray diffraction. 相似文献
26.
Jacob M. Wurlitzer Aleksa Stanii Sebastian Ziethe Paul M. Jordan Kerstin Günther Oliver Werz Hajo Kries Markus Gressler 《Chemical science》2022,13(31):9091
The realm of natural products of early diverging fungi such as Mortierella species is largely unexplored. Herein, the nonribosomal peptide synthetase (NRPS) MalA catalysing the biosynthesis of the surface-active biosurfactants, malpinins, has been identified and biochemically characterised. The investigation of the substrate specificity of respective adenylation (A) domains indicated a substrate-tolerant enzyme with an unusual, inactive C-terminal NRPS module. Specificity-based precursor-directed biosynthesis yielded 20 new congeners produced by a single enzyme. Moreover, MalA incorporates artificial, click-functionalised amino acids which allowed postbiosynthetic coupling to a fluorophore. The fluorescent malpinin conjugate penetrates mammalian cell membranes via an phagocytosis-mediated mechanism, suggesting Mortierella oligopeptides as carrier peptides for directed cell targeting. The current study demonstrates substrate-specificity testing as a powerful tool to identify flexible NRPS modules and highlights basal fungi as reservoir for chemically tractable compounds in pharmaceutical applications.Specificity profiling of a nonribosomal peptide synthetase of an early diverging fungus revealed high substrate flexibility. Feeding studies with click-functionalised amino acids enabled the production of fluorescent peptides targeting macrophages. 相似文献
27.
Reyhaneh Armin Sebastian Zühlke Gisela Grunewaldt-Stcker Felix Mahnkopp-Dirks Souvik Kusari 《Molecules (Basel, Switzerland)》2021,26(12)
Apple Replant Disease (ARD) is a significant problem in apple orchards that causes root tissue damage, stunted plant growth, and decline in fruit quality, size, and overall yield. Dysbiosis of apple root-associated microbiome and selective richness of Streptomyces species in the rhizosphere typically concurs root impairment associated with ARD. However, possible roles of Streptomyces secondary metabolites within these observations remain unstudied. Therefore, we employed the One Strain Many Compounds (OSMAC) approach coupled to high-performance liquid chromatography-high-resolution tandem mass spectrometry (HPLC-HRMSn) to evaluate the chemical ecology of an apple root-associated Streptomyces ciscaucasicus strain GS2, temporally over 14 days. The chemical OSMAC approach comprised cultivation media alterations using six different media compositions, which led to the biosynthesis of the iron-chelated siderophores, ferrioxamines. The biological OSMAC approach was concomitantly applied by dual-culture cultivation for microorganismal interactions with an endophytic Streptomyces pulveraceus strain ES16 and the pathogen Cylindrocarpon olidum. This led to the modulation of ferrioxamines produced and further triggered biosynthesis of the unchelated siderophores, desferrioxamines. The structures of the compounds were elucidated using HRMSn and by comparison with the literature. We evaluated the dynamics of siderophore production under the combined influence of chemical and biological OSMAC triggers, temporally over 3, 7, and 14 days, to discern the strain’s siderophore-mediated chemical ecology. We discuss our results based on the plausible chemical implications of S. ciscaucasicus strain GS2 in the rhizosphere. 相似文献
28.
Daniel Loof Oliver Thüringer Dr. Marco Schowalter Dr. Christoph Mahr Anmona Shabnam Pranti Prof. Dr. Walter Lang Prof. Dr. Andreas Rosenauer Dr. Volkmar Zielasek Dr. Sebastian Kunz Prof. Dr. Marcus Bäumer 《ChemistryOpen》2021,10(7):697-712
Porous networks of Pt nanoparticles interlinked by bifunctional organic ligands have shown high potential as catalysts in micro-machined hydrogen gas sensors. By varying the ligand among p-phenylenediamine, benzidine, 4,4‘‘-diamino-p-terphenyl, 1,5-diaminonaphthalene, and trans-1,4-diaminocyclohexane, new variants of such networks were synthesized. Inter-particle distances within the networks, determined via transmission electron microscopy tomography, varied from 0.8 to 1.4 nm in accordance with the nominal length of the respective ligand. While stable structures with intact and coordinatively bonded diamines were formed with all ligands, aromatic diamines showed superior thermal stability. The networks exhibited mesoporous structures depending on ligand and synthesis strategy and performed well as catalysts in hydrogen gas microsensors. They demonstrate the possibility of deliberately tuning micro- and mesoporosity and thereby transport properties and steric demands by choice of the right ligand also for other applications in heterogeneous catalysis. 相似文献
29.
Carlotta Borgarelli Yvonne E. Klingl Dr. Abril Escamilla-Ayala Prof. Dr. Sebastian Munck Prof. Dr. Ludo Van Den Bosch Prof. Dr. Wim M. De Borggraeve Dr. Ermal Ismalaj 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(34):8605-8641
Despite the fact that transmembrane proteins represent the main therapeutic targets for decades, complete and in-depth knowledge about their biochemical and pharmacological profiling is not fully available. In this regard, target-tailored small-molecule fluorescent ligands are a viable approach to fill in the missing pieces of the puzzle. Such tools, coupled with the ability of high-precision optical techniques to image with an unprecedented resolution at a single-molecule level, helped unraveling many of the conundrums related to plasma proteins’ life-cycle and druggability. Herein, we review the recent progress made during the last two decades in fluorescent ligand design and potential applications in fluorescence microscopy of voltage-gated ion channels, ligand-gated ion channels and G-coupled protein receptors. 相似文献
30.
Iurie L. Malaestean Sebastian Schmitz Arkady Ellern Paul Kgerler 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(10):1144-1146
The structure of the title compound, {[Mg(C4H7O2)2(H2O)3]·H2O}n, features one‐dimensional ...(μ2‐ib)Mg(μ2‐ib)Mg... zigzag chains (ib is isobutyrate) parallel to the c axis. The octahedral Mg environment is completed by three fac‐oriented terminal water ligands, as well as one further monodentate end‐on coordinated ib ligand. In the crystal structure, the hydrophobic ib groups are all oriented within one half of the coordination perimeter of each chain, whereas the water ligands, together with hydrogen‐bonded noncoordinated solvent water molecules, define the other half. Along the a axis, neighbouring strands are oriented so that both the hydrophilic and hydrophobic sides are adjacent to each other. This results in an extensive hydrogen‐bonding network within the hydrophilic areas, also involving an additional solvent water molecule per formula unit. There are van der Waals contacts between the aliphatic isopropyl groups of the hydrophobic areas. 相似文献