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961.
SAPO-11分子筛晶化过程研究 总被引:1,自引:0,他引:1
采用X射线衍射、X射线荧光光谱、扫描电镜和固体核磁等方法研究了SAPO-11分子筛的水热晶化过程.结果表明,晶化初期,SAPO-11和一种具有磷硅铝组成的未知晶相同时生成;随着晶化的进行,中间相溶解,SAPO-11的生成速率大大增加,呈现快速晶化的特征;至2.33h后,SAPO-11的结晶度接近100%,并保持至晶化结束.硅从晶化初期即参与了SAPO-11的形成,它在晶体中的含量随晶化时间的延长而逐渐增加.硅原子主要以硅岛的形式分布于SAPO-11分子筛骨架中,从而导致多种硅配位环境的存在.分析显示,SAPO-11分子筛呈现外表面富硅的特点,结合晶化过程的分析可推测,硅在SAPO-11分子筛晶体中的分布不均匀,其含量从内向外递增. 相似文献
962.
Kinetic features of the photo- and thermo-chromic behaviour of new cholesteric triple copolymers with photosensitive spiropyran-containing side groups are considered. The kinetics of the back thermal process at different temperatures have been studied; activation energies for this process for the copolymers with different contents of the dye units have been obtained. The photochromic homopolymer and copolymers with a low content of dye units are shown to possess maximum values of the activation energy. 相似文献
963.
Adrian Adamski Andrzej Biadasz Krzysztof Domieracki Marek Andrzej Kojdecki Dominik Paukszta Dominika Uryzaj 《Liquid crystals》2013,40(4):456-462
Liquid-crystalline perylene-3,4,9,10-tetra-(n-hexylester) forms characteristic dendritic or flower-like structures at room temperature when it is deposited on a hydrophilic glass substrate using the zone-casting technique. It was found that such unique structures were not possible to be created simply by recrystallisation of this dye from a liquid-crystalline columnar phase. On the basis of the observations using a confocal microscope and the study of wide angle X-ray scattering (WAXS) as well as the analysis of the absorption and fluorescence spectra, some conclusions, concerning the molecular organisation in the dendritic structure, are drawn. Based on the research, one can assume that the dendrites are formed by columnar molecular aggregates with the column axes parallel to the substrate. Such an organisation of the molecules can be interesting from the point of view of organic electronics. 相似文献
964.
Remko Achten Arie Koudijs Marcel Giesbers Antonius T. M. Marcelis Corresponding author Ernst J. R. Sudhölter 《Liquid crystals》2013,40(3):277-285
Two series of non‐symmetric banana‐shaped compounds, both with one alkyl and one alkenyl terminal tail, have been synthesized and studied. Both series were compared with the corresponding series with two saturated terminal alkyl tails. All the compounds have a bent central 1,3‐phenylene bis(4‐benzoyloxy)benzoate core; their mesophases were characterized by polarizing optical microscopy, differential scanning calorimetry, X‐ray diffraction and switching current response experiments. In all four series one of the terminal tails is varied from OC8H17 to OC16H33. The other terminal tails are OC11H23, O(CH2)9CH?=?CH2, OC10H21 and O(CH2)8CH?=?CH2. The short‐tailed compounds show monotropic or enantiotropic B1 phases and the long‐tailed compounds the B2 phase. The introduction of one terminal vinyl group slightly lowers the transition temperatures. The introduction of a second terminal vinyl group further suppresses the liquid crystalline properties. All compounds with B2 phases have layer spacings that suggest a tilt of ~45° of the bent molecules in the layers, and their switching behaviour is antiferroelectric. 相似文献
965.
Céline Guéguen Chad W. Cuss Weibin Chen 《International journal of environmental analytical chemistry》2013,93(13):1428-1440
Asymmetrical flow field-flow fractionation (AF4) with sequential on-line UV/visible and fluorescence detectors was used to investigate the composition of dissolved organic matter (DOM) in permeate and retentate fractions isolated by tangential flow ultrafiltration (TFF) at various concentration factors (i.e. ratio of initial volume to the retentate volume; CF). The permeation coefficient model, which defines the log-log relationship between DOM in the permeate fractions and CFs, described the permeation behaviour of DOM with regression coefficients r 2 > 0.99. The dominance of higher-molecular weight retentate chromophoric DOM (CDOM) observed in TFF was consistent with the results of AF4. The weight-averaged molecular weights (M w) of the integral permeate and retentate at CF = 20 were determined to be 1160 and 2320 by AF4, respectively, while their molecular weight distributions (MWD) were centered at 1120 and 1600 Da. M w, MWD, and aromaticity (i.e. ratio of absorbance at 250 and 365 nm; E2/E3) in permeate fractions were altered significantly during the early stages of TFF (CF < 9). These changes, however, were not evident in excitation-emission matrix fluorescence properties as determined using the parallel factor analysis model. The application of AF4 to TFF fractions suggests that the choice of CF may have an important impact on the size distribution and aromaticity of permeate fractions, whereas fluorescence properties appear insensitive to concentration factor. These results suggest that the choice of CF is crucial only in the study of the permeate fraction where similar CF (i.e. > 9) should be used to obtain meaningful comparison among samples. 相似文献
966.
Mario Ulises Delgado‐Jaime Prof. Serena DeBeer Prof. Matthias Bauer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(47):15888-15897
Valence‐to‐core X‐ray emission spectroscopy (V2C XES) has been applied to a series of compounds relevant to both homogeneous catalysts and intermediates in heterogeneous reactions, namely [Fe(CO)5], [Fe2(CO)9], [Fe3(CO)12], [Fe(CO)3(cod)] (cod=cyclo‐octadienyl), [Fe2Cp2(CO)4] (Cp=cyclo‐pentadienyl), [Fe2Cp*2(CO)4] (Cp*=tetramethylcyclopentadienyl), and [FeCp(CO)2(thf)][B(ArF)4] (ArF=pentafluorophenyl). DFT calculations of the V2C XES spectra show very good agreement with experiment, which allows for an in depth analysis of the origins of the observed spectral signatures. It is demonstrated that the observed spectral features can be broken down into specific ligand and metal fragment contributions. The relative intensities of the observed features are further explained through a quantitative investigation of the metal 3p and 4p contributions to the spectra. The ability to use V2C XES to separate carbonyl, hydrocarbon, and solvent contributions is highlighted. 相似文献
967.
Dr. Chih‐Kai Liang Dr. Galina V. Dubacheva Dr. Thierry Buffeteau Dr. Dominique Cavagnat Dr. Philippe Hapiot Dr. Bruno Fabre Prof. James H. R. Tucker Dr. Dario M. Bassani 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12748-12758
The synthesis of an anthracene‐bearing photoactive barbituric acid receptor and its subsequent grafting onto azide‐terminated alkanethiol/Au self‐assembled monolayers by using an CuI‐catalyzed azide–alkyne reaction is reported. Monolayer characterization using contact‐angle measurements, electrochemistry, and spectroscopic ellipsometry indicate that the monolayer conversion is fast and complete. Irradiation of the receptor leads to photodimerization of the anthracenes, which induces the open‐to‐closed gating of the receptor by blocking access to the binding site. The process is thermally reversible, and polarization‐modulated IR reflection–absorption spectroscopy indicates that photochemical closure and thermal opening of the surface‐bound receptors occur in 70 and 100 % conversion, respectively. Affinity of the open and closed surface‐bound receptor was characterized by using force spectroscopy with a barbituric‐acid‐modified atomic force microscope tip. 相似文献
968.
Vânia F. Pais Dr. Hamdy S. El‐Sheshtawy Prof. Dr. Rosario Fernández Prof. Dr. José M. Lassaletta Dr. Abel Ros Prof. Dr. Uwe Pischel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6650-6661
A series of nine borylated arylisoquinolines has been prepared with systematic variation in their electronic properties and their photophysical properties were investigated. The color of their fluorescence can be finely tuned by changing the properties of the aryl moiety, which is involved in internal‐charge‐transfer processes. For example, methoxy‐substituted compound 5 showed an intense green emission, whereas dimethylamino‐substituted compound 6 showed an orange‐red emission. These new fluorophores were tested for their potential as molecular switches with external ionic stimuli, such as protons and fluoride ions. On the one hand, protonation of the isoquinoline moiety led to fluorescence enhancement for compounds that showed weak charge transfer and fluorescence quenching for compounds that showed strong charge transfer. On the other hand, the formation of ate complexes with fluoride led to strong fluorescence quenching in all of the investigated cases. 相似文献
969.
Prof. Giuseppe Alibrandi Dr. Valeria Amendola Dr. Greta Bergamaschi Dr. Riccardo Dollenz Prof. Luigi Fabbrizzi Prof. Maurizio Licchelli Dr. Carmelo Lo Vecchio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(11):3729-3734
The combined activity of the 1.1.1‐cryptand and of a dicopper(II) bistren cryptate complex including chloride makes the Cl? ion be continuously and slowly delivered to the solution, without any external intervention. The 1.1.1‐cryptand slowly releases OH? ions, according to a defined kinetics, and each OH? ion displaces a Cl? ion from the cryptate. Chloride displacement induces a sharp colour change from bright yellow to aquamarine and can be conveniently monitored spectrophotometrically, even in diluted solutions. The 1.1.1‐cryptand is the motor of a molecular dispenser (the dicopper(II) cryptate) delivering chloride ion automatically, from the inside of the solution. 相似文献
970.
Dr. Yu Nakagawa Takashi Doi Takara Taketani Prof. K. Takegoshi Prof. Yasuhiro Igarashi Dr. Yukishige Ito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(32):10516-10525
Pradimicins (PRMs) and benanomicins are the only family of non‐peptidic natural products with lectin‐like properties, that is, they recognize D ‐mannopyranoside (Man) in the presence of Ca2+ ions. Coupled with their unique Man binding ability, they exhibit antifungal and anti‐HIV activities through binding to Man‐containing glycans of pathogens. Notwithstanding the great potential of PRMs as the lectin mimics and therapeutic leads, their molecular basis of Man recognition has yet to be established. Their aggregate‐forming propensity has impeded conventional interaction analysis in solution, and the analytical difficulty is exacerbated by the existence of two Man binding sites in PRMs. In this work, we investigated the geometry of the primary Man binding of PRM‐A, an original member of PRMs, by the recently developed analytical strategy using the solid aggregate composed of the 1:1 complex of PRM‐A and Man. Evaluation of intermolecular distances by solid‐state NMR spectroscopy revealed that the C2–C4 region of Man is in close contact with the primary binding site of PRM‐A, while the C1 and C6 positions of Man are relatively distant. The binding geometry was further validated by co‐precipitation experiments using deoxy‐Man derivatives, leading to the proposal that PRM‐A binds not only to terminal Man residues at the non‐reducing end of glycans, but also to internal 6‐substituted Man residues. The present study provides new insights into the molecular basis of Man recognition and glycan specificity of PRM‐A. 相似文献