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961.
The total energy of all π-electrons in a conjugated hydrocarbon (within the framework of HMO approximation) is the sum of the absolute value of all
the eigenvalues of its corresponding graph. In this paper, we consider “double hexagonal chains” as benzenoids constructed
by successive fusions of successive naphthalenes along a zig–zag sequence of triples of edges as appear on opposite sides
of each naphthalene unit. It is shown that if the fusions are such as to give a polyaceacene then the total π-electron energy
is the minimum from among all the double hexagonal chains with the same number of naphthalene units.
相似文献
962.
Bi HC Zhong GP Zhou S Chen X Huang M 《Rapid communications in mass spectrometry : RCM》2005,19(20):2911-2917
A liquid chromatography/tandem mass spectrometry (LC/MS/MS) method was developed and validated to determine the concentrations of adefovir [9-(2-phosphonylmethoxyethyl)adenine, PMEA] in human plasma. After one-step protein precipitation of plasma samples by methanol, adefovir was analyzed by LC/MS/MS using positive electrospray ionization. Chromatography was performed on a C18 column. The extraction recoveries of adefovir were found to be 85.1-89.3%. Adefovir was stable under routine laboratory conditions. A minimal matrix effect resulting in a slight ionization enhancement of adefovir (<10.9%) was observed, which did not markedly affect the behavior of the calibrations curves and accuracy and precision data. The method had a chromatographic run time of 7.8 min and a linear calibration curve over the concentration range 1.5-90 ng/mL for adefovir. The lower limit of quantification of the method was 1.5 ng/mL. The intra- and inter-day precision was less than 8.4%. These results indicated that this LC/MS/MS method has high selectivity and efficiency, and acceptable accuracy, precision and sensitivity. The validated LC/MS/MS method has been successfully used in a pharmacokinetic study in healthy volunteers treated with oral adefovir dipivoxil at 10 and 20 mg. 相似文献
963.
Vinayak Juvekar Chang Su Lim Dong Joon Lee Sang Jun Park Gyeong Ok Song Hyuk Kang Hwan Myung Kim 《Chemical science》2021,12(1):427
Two-photon photodynamic therapy (TP-PDT) is a promising approach for the treatment of cancer because of its better penetration depth and superior spatial selectivity. Here, we describe an azo group containing cyclized-cyanine derivatives (ACC1 and ACC2) as a two-photon activated, type I based photosensitizer (PS). These small-molecule and heavy atom-free organic dyes showed marked reactive oxygen species (ROS)-generating ability under physiological conditions, as well as fast loading ability into the cells and negligible dark toxicity. Live cell analyses with one- and two-photon microscopy revealed that these dyes showed higher ROS generation ability upon two-photon excitation than upon one-photon excitation via the type I process. The PSs have superior PDT properties compared to conventional Visudyne and 5-ALA under mild conditions. These characteristics allowed for precise PDT at the target region in mimic tumor spheroids, demonstrating that the developed TP PS could be useful in efficient PDT applications and in designing various PSs.Azo containing dyes as a two-photon selective and type I based photosensitizers (PSs) were developed that exhibit excellent photodynamic therapy properties under mild condition. 相似文献
964.
Dong-Dong Zhou Jun Wang Pin Chen Yangyong He Jun-Xi Wu Sen Gao Zhihao Zhong Yunfei Du Dingyong Zhong Jie-Peng Zhang 《Chemical science》2021,12(4):1272
Rational manipulation of supramolecular structures on surfaces is of great importance and challenging. We show that imidazole-based hydrogen-bonded networks on a metal surface can transform into an isostructural coordination network for facile tuning of the pore size and guest recognition behaviours. Deposition of triangular-shaped benzotrisimidazole (H3btim) molecules on Au(111)/Ag(111) surfaces gives honeycomb networks linked by double N–H⋯N hydrogen bonds. While the H3btim hydrogen-bonded networks on Au(111) evaporate above 453 K, those on Ag(111) transform into isostructural [Ag3(btim)] coordination networks based on double N–Ag–N bonds at 423 K, by virtue of the unconventional metal–acid replacement reaction (Ag reduces H+). The transformation expands the pore diameter of the honeycomb networks from 3.8 Å to 6.9 Å, giving remarkably different host–guest recognition behaviours for fullerene and ferrocene molecules based on the size compatibility mechanism.A hydrogen-bonded network on a Ag(111) surface can transform into an isostructural Ag(i) coordination network, giving drastically different host–guest recognition behaviours. 相似文献
965.
Gregory M. Su Han Wang Brandon R. Barnett Jeffrey R. Long David Prendergast Walter S. Drisdell 《Chemical science》2021,12(6):2156
Metal–organic frameworks are promising materials for applications such as gas capture, separation, and storage, due to their ability to selectively adsorb small molecules. The metal–organic framework CuI-MFU-4l, which contains coordinatively unsaturated copper(i) centers, can engage in backbonding interactions with various small molecule guests, motivating the design of frameworks that engage in backbonding and other electronic interactions for highly efficient and selective adsorption. Here, we examine several gases expected to bind to the open copper(i) sites in CuI-MFU-4l via different electronic interactions, including σ-donation, π-backbonding, and formal electron transfer. We show that in situ Cu L-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy can elucidate π-backbonding by directly probing excitations to unoccupied backbonding orbitals with Cu d-character, even for gases that participate in other dominant interactions, such as ligand-to-metal σ-donation. First-principles calculations based on density functional theory and time-dependent density functional theory additionally reveal the backbonding molecular orbitals associated with these spectroscopic transitions. The energies of the transitions correlate with the energy levels of the isolated small molecule adsorbates, and the transition intensities are proportional to the binding energies of the guest molecules within CuI-MFU-4l. By elucidating the molecular and electronic structure origins of backbonding interactions between electron rich metal centers in metal–organic frameworks and small molecule guests, it is possible to develop guidelines for further molecular-level design of solid-state adsorbents for energy-efficient separations of relevance to industry. In situ near edge X-ray absorption fine structure spectroscopy directly probes unoccupied states associated with backbonding interactions between the open metal site in a metal–organic framework and various small molecule guests. 相似文献
966.
Grażyna Janowska Teresa Mikołajczyk Dorota Wołowska-Czapnik M. Boguń 《Journal of Thermal Analysis and Calorimetry》2005,82(1):129-135
The paper discusses the thermal properties of alginate fibres made from alginic acid or sodium alginate and from alginates
substituted with divalent metal ions during the fibre-forming stage. Alginate fibres with an addition of silica nanoparticles
have also been examined. The selection of fibre-forming parameters was intended to obtain the best either sorption or strength
properties depending on the specific fibre application. Thermal curves of the fibres under investigations obtained by under
air atmosphere and differential scanning calorimetry (DSC) under neutral gas atmosphere have been interpreted from the view
of physical and chemical changes in the fibre-forming material. Based on thermogravimetric curves, the fibre thermal stability
indices have been determined. It has been found that the addition of silica nanoparticles exerts a positive influence on the
thermal properties of the examined fibres. 相似文献
967.
Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy
Concepción López Rosa M. Claramunt M. Ángeles García José Elguero 《Central European Journal of Chemistry》2004,2(4):660-671
Equimolar mixtures of 3,5-dimethylpyrazole (1) with four NH-imidazoles (2–5) have been studied by13C and 15N CPMAS NMR and by DSC. In three cases, the solid mixture behaves as the sum of the individual components [imidazole (2), 2-methylimidazole (3) and 2,4(5)-dimethylimidazole (5)]. In one case [4,5-dimethylimidazole (4)], the mixture corresponds to a new species in which the dynamic behavior of1 no longer exists. 相似文献
968.
Summary. Phenoxyacetic acid distribution in two-phase systems n-aliphatic hydrocarbon (C5–C8) – water and its dimerization in organic phase were investigated. The values of distribution coefficient (D
HR), distribution constant (K
D), and dimerization constant (K
dim) of acid were obtained. The empirical correlations of these quantities with Hildebrand solubility parameter of organic solvents were established. The influence of pH of the aqueous phase as well as the polarity of the applied organic solvents on phenoxyacetic acid physical chemistry in
the two-phase systems was described. 相似文献
969.
Ronaldo Santos da Silva Maria Inês Basso Bernardi Antonio Carlos Hernandes 《Journal of Sol-Gel Science and Technology》2007,42(2):173-179
In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba0.77Ca0.23TiO3 nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis,
morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through
thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy.
In summary, Ba0.77Ca0.23TiO3 nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity
and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions
with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution
(30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the
chelation in higher pHs. 相似文献
970.
Raquel Peña-Alonso Gian Domenico Sorarù 《Journal of Sol-Gel Science and Technology》2007,43(3):313-319
The sol–gel method has been used for the synthesis of borosilicate gels from mixtures of methyltriethoxysilane (MTES) and
dimethyldiethoxysilane (DMDES) and boric acid. The use of boric acid, B(OH)3 allows the hydrolysis and condensation of hybrid silicon alkoxides without further addition of water or catalyst. The use
of difunctional silicon units, –(CH3)2SiO– promote the formation, during the sol–gel process, of linear oligomers which facilitate fiber drawing before gelation.
Gel characterization performed by FT-IR, XRD, TG-DTA and DCS analysis indicates the formation of a mixed network with incorporation
of the boron units via =B-O-Si≡ bridges. The formation of borosiloxane bonds seems favored by the presence of DMDES. SiBOC
glasses were obtained after pyrolysis of the borosilicate gels in argon atmosphere at 1000 °C. TG-DTA study indicates that
the ceramic yield decreases by increasing the amount of DMDES. Gel fibers were successfully prepared from convenient partially-aged
solutions by hand drawing. Pyrolysis of the obtained gel fibers under argon atmosphere at 1000 °C open the possibility to
produce SiBOC homogeneous glass fibers with diameter as low as 10 μm. 相似文献