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991.
Lignier P Morfin F Mangematin S Massin L Rousset JL Caps V 《Chemical communications (Cambridge, England)》2007,(2):186-188
The gold reference catalyst Au/TiO(2) exhibits high activity in the stereoselective epoxidation of trans-stilbene in methylcyclohexane in the presence of 5 mol% TBHP, by taking part in a chain reaction involving the activation of molecular oxygen by a radical produced from methylcyclohexane. 相似文献
992.
Foltz C Stecker B Marconi G Bellemin-Laponnaz S Wadepohl H Gade LH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9912-9923
The underlying conceptual differences in exploiting two- and threefold rotational symmetry in the design of chiral ligands for asymmetric catalysis have been addressed in a comparative study of the catalytic performance of bisoxazoline (BOX) and tris(oxazolinyl)ethanes (trisox) containing copper(II) Lewis acid catalysts. The differences become apparent in constructing new catalysts by systematically "deforming" the stereodirecting ligand by inverting chiral centres or replacing chiral by achiral oxazolines. The catalytic alpha-amination of ethyl 2-methylacetoacetate with dibenzyl azodicaboxylate, which occurs with high enantioselectivity for both Ph(2)-BOX and Ph(3)-trisox copper catalysts, has been employed as the test reaction. In the trisox-copper complex [Cu(II)(iPr(3)-trisox)(kappa(2)-O,O'-MeCOCHCOOEt)](+)[BF(4)](-) (1), which was characterised by X-ray diffraction, two of the oxazoline groups are coordinated to the central copper atom, whilst the third oxazoline unit is dangling with the N-donor pointing away from the metal centre. A similar arrangement is found for the stereochemically "mixed" C(1)-trisox complex [Cu(II){(Ph(3)-trisox(R,S,S)}(kappa(2)-O,O'-MeCOCHCOOEt)(H(2)O)](+)[ClO(4)](-) (2), in which the phenyl substituents adopt a first coordination sphere meso arrangement. The almost identical selectivity of the Ph(3)-trisox(R,R,R)- and Ph(2)-BOX(R,R)-derived catalysts is as expected from the proposed model of the active catalyst based on a partially decoordinated podand. The behaviour of the "desymmetrised" trisox-Cu catalysts may be rationalised in terms of a general steady-state kinetic model for the three possible active bisoxazoline-copper species, which are expected to be in rapid exchange with each other in solution. This applies to both the trisox derivatives with stereochemically inverted and achiral oxazoline rings. The study underscores previous observations of superior performance of the catalysts bearing C(3)-chiral stereodirecting ligands as compared to systems of lower symmetry. 相似文献
993.
Seggio A Lannou MI Chevallier F Nobuto D Uchiyama M Golhen S Roisnel T Mongin F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9982-9989
Metalation of N-phenylpyrrole by using an in situ mixture of ZnCl(2)TMEDA (0.5 equiv; TMEDA=N,N,N',N'-tetramethylethylenediamine) and LiTMP (1.5 equiv; TMP=2,2,6,6-tetramethylpiperidino) was optimized. The reaction carried out at room temperature in THF resulted in incomplete metalation (56 % conversion) and selectivity (mixture of 2-iodo and 2,2'-diiodo derivatives in an 86:14 ratio after trapping with iodine). By using diethyl ether (DEE), toluene, or hexane instead of THF, low conversions of 17, 38, or 23 % were observed, respectively, but the formation of the diiodide was avoided. When hexane was used as solvent, strong lithium-complexing ligands such as [12]crown-4 and N,N'-dimethylpropylideneurea (DMPU) inhibited the reaction whereas more (hemi)labile ligands (TMEDA>THF approximately DME) favored it. This result shows that a temporary accessibility of lithium to interact with the rest of the base and/or the substrate is a prerequisite for an efficient metalation. A 75 % yield of 2-iodo-N-phenylpyrrole was obtained after reaction with the base in the presence of five equivalents of TMEDA for two hours at room temperature, and subsequent trapping with iodine. We were able to successfully replace the spare TMP with a less expensive butyl group. 相似文献
994.
We have previously reported the unique luminescence properties of ML4 complexes formed between tropolonate ligands and a series of lanthanide cations, several of them emitting in the near-infrared domain. The synthesis and composition of ML4 lanthanide tropolonate complexes have been previously described in the literature, but no structural information has been available so far. In this work, the crystal structures of several lanthanide tropolonate complexes (Ln3+ = Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+) have been isolated and systematically analyzed by X-ray diffraction and compared by using different criteria including the Kepert formalism. Such comparative work is rare in lanthanide coordination chemistry. The analysis of the structures in the solid state reveals that although the packing of the ML4 complexes depends on the nature of the metal ion, the coordination geometries around the different lanthanides is virtually similar for all the cations that have been analyzed; an indication that lanthanide-centered f orbitals play a role in controlling this coordination geometry. Analysis of the solution's behavior by stability constant determination reveals the formation of complexes with similar ML4 stoichiometries as those observed in the solid state. Nevertheless, analysis of the luminescence lifetimes indicates that the coordination environment around the lanthanide cations are different in the solid state and in solution, with the presence of one molecule of water bound to the lanthanide cation in solution. The presence of such a water molecule is a significant source of nonradiative deactivation of the excited states of the lanthanide cations, an unfavorable condition that leads to significant loss in fluorescence intensity of these lanthanide complexes. This exemplifies that such comparative analysis between the solid state and solution is important for the rationalization of the luminescence properties of the complexes. This analysis will aid us in optimizing ligand design for improved photophysical properties of the complex. 相似文献
995.
A new method for the non-specific determination of iron-porphyrin-like complexes in natural waters has been developed. It is based on the chemiluminescent oxidation of the luminol in the presence of dioxygen (O2) at pH 13. The method has been implemented in a FIA manifold that allowed the direct injection of seawater. The limit of detection is 0.11 nM of equivalent hemin (Fe-protoporphyrin IX). Fe2+, Fe3+, H2O2, siderophore (deferoxamin mesylate), humic acid and phytic acid did not interfere when they were present at the concentrations expected in seawater. Metal free porphyrin and Mg, Cu, Co porphyrin complexes did not induce a significant chemiluminescent signal. Poisoned unfiltered samples could be stored for several weeks before analyses. The new method was successfully applied to the determination of the Fe-porphyrin complexes contained in cultured phytoplankton and in natural samples. 相似文献
996.
In this study we present a rapid and simultaneous assay method using headspace (HS) solid-phase microextraction (SPME)/gas chromatography (GC)/electron impact (EI) mass spectrometry (MS) (selected ion monitoring) for contaminants causing the principal organoleptic defects of wine (2,4,6-trichloroanisole, 2,3,4,6-tetrachloroanisole, pentachloroanisole, 2,4,6-tribromoanisole, 1-octen-3-ol, geosmin, 2-methylisoborneol, 3-isopropyl-2-methoxypyrazine, fenchol, fenchone, 2-methoxy-3,5-dimethylpyrazine, 4-ethylphenol, 4-ethylguaiacol, 4-vinylphenol, 4-vinylguaiacol, 3-isobutyl-2-methoxypyrazine, guaiacol and ethyl acetate). The method was validated according to protocols NF ISO 5725-1, 2 and NF V03-110. Its characteristics (limit of detection (LOD), limit of quantification (LOQ), uncertainties) were determined after having optimised the SPME parameters. The target contaminants were quantified in the wines below their threshold of perception with a satisfactory relative standard deviation for all the analytes except ethyl acetate (RSD=36%); for that, the assay method permits clear differentiation of the wines that are at risk of presenting an acescent character, i.e. containing more than 120mgL(-1) ethyl acetate. The target volatile and odorous substances were determined at concentrations significantly below their threshold of perception in a hydroalcoholic context and their threshold of recovery in wines. 相似文献
997.
Kirsch S Widart J Louette J Focant JF De Pauw E 《Journal of chromatography. A》2007,1153(1-2):300-306
A method to perform absolute quantification of two biomarkers (IGF-1 and IGFBP-3) of growth hormone abuse has been developed. Isotope dilution is used with synthetically labelled peptides as internal standards. Peptide selection and multiple reaction monitoring design are discussed. A simple sample preparation based on the reduction and alkylation of cysteine residues followed by tryptic digestion provides a sufficient digestion of proteins. Serum samples fortified with increasing amounts of target proteins are analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) on a triple quadrupole mass spectrometer. Specificity is ensured by the selection of sequences with no homology in BLAST, as well as retention time deviation check, and ion ratio monitoring. Linearity is studied in terms of calibration curves. These curves for IGFBP-3 and IGF-1 are generated with mean slopes of 0.055 and 0.065, intercepts of 0.107 and -0.011, and with coefficients of correlation of 0.95 and 0.98, respectively. These curves result from the addition of proteins to the serum. Risks of variations related to potential matrix effects are therefore reduced, as well as probable variations related to the digestion steps. The working concentration ranges are 4-10 ng/microl for IGFBP-3 and 2-8 ng/microl for IGF-1. Preliminary data regarding repeatability show that relative standard deviations (RSDs) range between 13 and 32% for IGFBP-3 and between 7 and 29% for IGF-1. 相似文献
998.
A rational protocol for the synthesis of arylated bipyridine ligands via a cycloaddition pathway 总被引:1,自引:0,他引:1
A generic design principle for the preparation of a variety of substituted phenyl-polypyridine ligands is described. These ligands are readily prepared by a regioselective [4+2] cycloaddition between electron-deficient dienes, such as 2,6-disubstituted-1,3,4-triazines, and ethynyl-arenes or ethynyl-alkanes. Exceptional reactivity is found with electron-rich dienophiles bearing ethynylgallate or ethynylphenyldibutylamino groups. Two regioisomers are formed, the meta being preferred due to favorable pi-pi interactions in the transition state, while the para isomers are formed in low yields in most cases. The use of tert-butylacetylene or N,N-dimethylamino-2-propyne, however, drives the reaction exclusively to the para isomer. Di-N,N-dibutylaminophenyl or isoquinoline ligands can also be produced in a single step by reverse Diels-Alder reactions. Cross-coupling reactions of iodo-substituted ligands or their platinum(II) complexes under Pd(0) catalysis gives branched ligands and complexes bearing paraffin chains, electron-donor or electron-acceptor groups. The use of a chloro-Pt(II) complex of an iodo-functionalized ligand allows both halogens to be replaced by ethynyl groups by using different catalysts. This methodology readily accommodates various functional groups and has been successfully extended to systems containing a variety of donor/acceptor frameworks. All ligands strongly absorb in the near-UV and luminesce in solution at rt with quantum yields ranging from 0 to 66%. Excited state lifetimes are in the nanosecond range and the solvent effects are in keeping with singlet excited states mixed with charge-transfer character. As deduced from spectroscopic and electrochemical studies, the di-n-butylamino derivatives are strong reductants in the excited state. 相似文献
999.
AFM imaging of immobilized fibronectin: does the surface conjugation scheme affect the protein orientation/conformation? 总被引:1,自引:0,他引:1
Vallières K Chevallier P Sarra-Bournet C Turgeon S Laroche G 《Langmuir : the ACS journal of surfaces and colloids》2007,23(19):9745-9751
Covalent grafting of biomolecules could potentially improve the biocompatibility of materials. However, these molecules have to be grafted in an active conformation to play their biological roles. The present work aims at verifying if the surface conjugation scheme of fibronectin (FN) affects the protein orientation/conformation and activity. FN was grafted onto plasma-treated fused silica using two different crosslinkers, glutaric anhydride (GA) or sulfosuccinimidyl 4-(p-maleimidophenyl)butyrate (SMPB). Fused silica was chosen as a model surface material because it presents a roughness well below the dimensions of FN, therefore allowing AFM analyses with appropriate depth resolution. Cell adhesion assays were performed to evaluate the bioactivity of grafted FN. Cell adhesion was found to be higher on GA-FN than on SMPB-FN. Since FN-radiolabeling assays allowed us to rule out a surface concentration effect (approximately 80 ng/cm2 of FN on both crosslinkers), it was hypothesized that FN adopted a more active conformation when grafted via GA. In this context, the FN conformation on both crosslinkers was investigated through AFM and contact angle analyses. Before FN grafting, GA- and SMPB-modified surfaces had a similar water contact angle, topography, and roughness. However, water contact angles of GA-FN and SMPB-FN surfaces clearly show differences in surface hydrophilicity, therefore indicating a dependence of protein organization toward the conjugation strategy. Furthermore, AFM results demonstrated that surface topography and roughness of both FN-conjugated surfaces were significantly different. Distribution analysis of FN height and diameter confirmed this observation as the protein dimensions were significantly larger on GA than SMPB. This study confirmed that the covalent immobilization scheme of biomolecules influences their conformation and, hence, their activity. Consequently, selecting the appropriate conjugation strategy is of paramount importance in retaining molecule bioactivity. 相似文献
1000.
Artzner F Geiger S Olivier A Allais C Finet S Agnely F 《Langmuir : the ACS journal of surfaces and colloids》2007,23(9):5085-5092
Poloxamers F88 (EO97PO39EO97) and P85 (EO27PO39EO27) are triblock copolymers of ethylene oxide (EO) and propylene oxide (PO), which have the same hydrophobic PO block. We studied aqueous solutions of these two copolymers by the conjoint use of differential scanning calorimetry (DSC), rheology, and small-angle X-ray scattering (SAXS). The results showed that the temperature-induced micellization of aqueous solutions of F88 and P85 was a progressive process followed by gelation for sufficiently concentrated samples. Gelation was due to the ordered packing of micelles under a hexagonal compact (HC) structure for P85 and a body-centered cubic (BCC) phase for F88. Importantly, the phase diagram of F88/P85 mixtures in water was elucidated and showed the destabilization of the HC phase upon addition of small amounts of F88. 相似文献