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951.
The scope of the Suzuki‐cross‐coupling reaction of 6‐haloimidazo[1,2‐a]pyridines is dependent on the availability of the (hetero)arylboronic acids. Thus, with the aim to develop expanded applications of (hetero)arylations of imidazo[1,2‐a]pyridines, we investigated the Negishi‐ and Stille‐cross‐coupling reactions at the 6‐position. Remarkably, attempts to apply the Negishi‐cross‐coupling conditions to the organozinc derivative prepared from 6‐haloimidazo[1,2‐a]pyridine via a lithium? zinc exchange led to the 5‐phenyl compound 3 in 54% yield instead of the desired 6‐phenyl isomer (Scheme 1). In contrast, various commercially available halogenated five‐ or six‐membered‐ring heterocycles were efficiently coupled to the 6‐(trialkylstannyl)imidazo[1,2‐a]pyridine under Stille conditions (Table 2).  相似文献   
952.
The reaction of 2-amino-2-oxazolines with ethoxycarbonyl isocyanate was investigated in order to access to fused 1,3,5-triazine-2,4-diones with a potential 5-HT2 antagonist activity. The reaction leads to 2,3,6,7-tetrahydro-4H-oxazolo[3,2-a]-1,3,5-triazine-2,4-diones and to 1-carbethoxy-3-(2-iminooxazolidine)ureas. During the carbamoylation the regioselectivity seems to be related to the strong nucleophilic character of the endo nitrogen atom of 2-amino-2-oxazolines. The structures of two compounds were studied by X-ray crystallography. N-Substituted compounds have been prepared by alkylation of the 2,3,6,7-tetrahydro-7-phenoxymethyl-4H-oxazolo[3,2-a]-1,3,5-triazine-2,4-dione.  相似文献   
953.
The conformation of phenyl-substituted monosaccharides (mannose, galactose, and glucose) and their singly hydrated complexes has been investigated in the gas phase by means of a combination of mass selected, conformer specific ultraviolet and infrared double resonance hole burning spectroscopy experiments, and ab initio quantum chemistry calculations. In each case, the water molecule inserts into the carbohydrate at a position where it can replace a weak intramolecular interaction by two stronger intermolecular hydrogen bonds. The insertion can produce significant changes in the conformational preferences of the carbohydrates, and there is a clear preference for structures where cooperative effects enhance the stability of the monosaccharide conformers to which the water molecule chooses to bind. The conclusions drawn from the study of monosaccharide-water complexes are extended to the disaccharide lactose and discussed in the light of the underlying mechanisms that may be involved in the binding of carbohydrate assemblies to proteins and the involvement, or not, of key structural water molecules.  相似文献   
954.
The issue of the influence of the side chain/backbone interaction on the local conformational preferences of a phenylalanine residue in a peptide chain is addressed. A synergetic approach is used, which combines gas-phase UV spectroscopy as well as gas-phase IR/UV double-resonance experiments with DFT and post Hartree-Fock calculations. N-Acetyl-Phe-amide was chosen as a model system for which three different conformers were observed. The most stable conformer has been identified as an extended beta(L) conformation of the peptide backbone. It is stabilized by a weak but significant NH-pi interaction bridging the aromatic ring on the residue (i) with the NH group on residue (i+1), with the aromatic side chain being in an anti conformation. This stable conformation corresponds to the common NH(i+1)-aromatic(i) interaction encountered in proteins for the three aromatic residues (phenylalanine, tyrosine, and tryptophan), which illustrates the relevance of gas-phase investigations to structural biology issues. The two other less abundant conformers have been assigned to two gamma-folded backbone conformations that differ by the orientation of the side chain. In all cases, the IR data provided spectroscopic fingerprints of these interactions. Finally, the strong conformational dependence of the fluorescence yield found for N-acetyl-Phe-amide illustrates the role of the environment on the excited-state dynamics of these species, which is often exploited by biochemists to monitor protein structural changes from tryptophan lifetime measurements.  相似文献   
955.
The relative nonlinear efficiency of some conjugated ester, thioester and dithioester molecules was investigated by quantum chemical semi-empirical methods. The results of calculations on ground and excited states properties and on finite-field hyperpolarizabilities allowed to select the best compounds for quadratic nonlinear optics. Some of these molecules were synthesized and the theoretical results were confronted with the experimental NLO response obtained by EFISH measurements. It was concluded from this analysis that the dithioester substituent represents an interesting electron-accepting group for applications in nonlinear optics and can be used instead of the nitro group. Correspondence to: A. Botrel  相似文献   
956.
Let A be a set, and let E be the Banach space of bounded functions : A R, equipped with its natural order. With a rectangle R = (a,b) × (0,T] let F(x,t,) : R × E E be a bounded, continuous function satisfying a local Hölder condition and being quasimonotone increasing with respect to . Then there exists a solution u: [a,b] × [0,T] E of the problem ut(x,t) – uxx(x,t) = F(x,t,u(x,t)) ((x,t) R), u(x,t) = 0 ((x,t) R R).  相似文献   
957.
The plant sterols sitosterol and stigmasterol exert very different effects on plant model membranes, the first one being a "reinforcer" like cholesterol, the second one not. 25-(2)H-Stigmasterol has been synthesized by coupling of the 22-aldehyde derived from stigmasterol by ozonolysis, with the proper sulfone labeled in position 25. The configuration of the ethyl side chain at C-24 was controlled by separation of the diastereomers introduced via a chiral sulfoxide. This synthetic scheme allowed the introduction of a labeled side chain in plant sterols in eight steps for stigmasterol and nine for sitosterol (overall yield ca. 15%). Using both diastereomers, the 24-epimers of sitosterol (clionasterol) and stigmasterol (poriferasterol) have also been synthesized. Deuterium NMR on oriented lipid bilayers made of soybean phosphatidylcholine and containing these four labeled plant sterols clearly reveals the difference of orientation and mobility of the four side chains.  相似文献   
958.
An unprecedented methodology was developed to simultaneously assign the relative percentages of the major chiral compounds and their prevailing enantiomeric form in crude essential oils (EOs). In a first step the infrared (IR) and vibrational circular dichroism (VCD) spectra of the crude essential oils were recorded and in a second step they were modelized as a linear weighted combination of the IR and VCD spectra of the individual spectra of pure enantiomer of the major chiral compounds present in the EOs. The VCD spectra of enantiomer of known enantiomeric excess shall be recorded if they are not yet available in a library of VCD spectra. For IR, the spectra of pure enantiomer or racemic mixture can be used. The full spectra modelizations were performed using a well known and powerful mathematical model (least square estimation: LSE) which resulted in a weighting of each contributing compound. For VCD modelization, the absolute value of each weighting represented the percentage of the associate compound while the attached sign addressed the correctness of the enantiomeric form used to build the model. As an example, a model built with the non-prevailing enantiomer will show a negative sign of the weighting value. For IR spectra modelization, the absolute value of each weighting represented the percentage of the compounds without of course accounting for the chirality of the prevailing enantiomers. Comparison of the weighting values issuing from IR and VCD spectra modelizations is a valuable source of information: if they are identical, the EOs are composed of nearly pure enantiomers, if they are different the chiral compounds of the EOs are not in an optically pure form. The method was applied on four samples of essential oil of Artemisia herba-alba in which the three major compounds namely (−)-α-thujone, (+)-β-thujone and (−)-camphor were found in different proportions as determined by GC–MS and chiral HPLC using polarimetric detector. In order to validate the methodology, the modelization of the VCD spectra was performed on purpose using the individual VCD spectra of (−)-α-thujone, (+)-β-thujone and (+)-camphor instead of (−)-camphor. During this work, the absolute configurations of (−)-α-thujone and (+)-β-thujone were confirmed by comparison of experimental and calculated VCD spectra as being (1S,4R,5R) and (1S,4S,5R) respectively.  相似文献   
959.
Polymerization‐induced self‐assembly (PISA) was employed to compare the self‐assembly of different amphiphilic block copolymers. They were obtained by emulsion polymerization of styrene in water using hydrophilic poly(N‐acryloylmorpholine) (PNAM)‐based macromolecular RAFT agents with different structures. An average of three poly (ethylene glycol acrylate) (PEGA) units were introduced either at the beginning, statistically, or at the end of a PNAM backbone, resulting in formation of nanometric vesicles and spheres from the two former macroRAFT architectures, and large vesicles from the latter. Compared to the spheres obtained with a pure PNAM macroRAFT agent, composite macroRAFT architectures promoted a dramatic morphological change. The change was induced by the presence of PEGA hydrophilic side‐chains close to the hydrophobic polystyrene segment.  相似文献   
960.
A series of melamine-formaldehyde microcapsules as an intrinsic intumescent system was prepared by an in situ polymerization. The structural and thermal properties of the resultant microcapsules were studied. The surface morphology and chemical structure of microcapsules were investigated using scanning electron microscope (SEM), and Fourier-transform infrared spectroscope (FT-IR), respectively. The thermal properties of samples were investigated by thermogravimetric analysis (TGA) and by differential scanning calorimetry (DSC). The results showed that the thermo-physical properties are strongly dependant on the nature core content and the synthesis conditions. From the thermal analysis, it was concluded that microcapsules containing di-ammonium hydrogen phosphate exhibits characteristics of an intumescent system during their thermal degradation and could be interpreted due to the interaction between phosphate and melamine.  相似文献   
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