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91.
The effects of atomic multipole moments obtained by the potential-derived method on hydrogen bonding
A potential-derived atomic multipole method called the cumulative potential-derived atomic multipole method is developed, with which electrostatic atomic multipole moments are derived by fitting the molecular electric potential in a cumulative way. It is applied to the hydrides of N , O , F , S , Cl , and methanol and the hydrogen-bonded dimers formed between them. The relationship between atomic multipole moments and molecular charge distributions is found. The structures calculated with Buckingham's electrostatic model are in good agreement with experiments. The phenomena of nonlinear structures of most H -bonded complexes—the deviations of symmetry axes of electron donors from H bonds—and correct distinguishing between two alternative structures are attributed to atomic dipole and quadrupole moments. Compared with other methods, this method has a quantitative and qualitative advantage and simple algorithm. The main conclusion is that the atomic multipole moments play a substantial role, although a potential-derived charge model was deemed sufficient previously. © 1993 John Wiley & Sons, Inc. 相似文献
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Qi Zhang Yunlong Shao Boye Li Yuanyuan Wu Jingying Dong Dongtang Zhang Yanan Wang Yong Yan Xiayan Wang Qiaosheng Pu Guangsheng Guo 《Chemical science》2021,12(11):4111
The analysis of single living cells, including intracellular delivery and extraction, is essential for monitoring their dynamic biochemical processes and exploring intracellular heterogeneity. However, owing to the 2D view in bright-field microscopy and optical distortions caused by the cell shape and the variation in the refractive index both inside and around the cells, achieving spatially undistorted imaging for high-precision manipulation within a cell is challenging. Here, an accurate and visual system is developed for single-cell spatial manipulation by correcting the aberration for simultaneous bright-field triple-view imaging. Stereo information from the triple view enables higher spatial resolution that facilitates the precise manipulation of single cells. In the bright field, we resolved the spatial locations of subcellular structures of a single cell suspended in a medium and measured the random spatial rotation angle of the cell with a precision of ±5°. Furthermore, we demonstrated the visual manipulation of a probe to an arbitrary spatial point of a cell with an accuracy of <1 pixel. This novel system is more accurate and less destructive for subcellular content extraction and drug delivery.We achieved the low-damage spatial puncture of single cells at specific visual points with an accuracy of <65 nm. 相似文献
95.
8—氮鸟嘌呤的极谱伏安行为 总被引:4,自引:0,他引:4
用循环伏安法(CV)、电流采样极诸法(SCP,即TAST)、常规脉冲极谱法(NPP)、微分脉冲极谱法(DPP)、线性扫描伏安法(LSV)、Osteryoung方波伏安法(OSWV)和计时库仑法(CC)等电化学技术研究了抗癌药物8-氮鸟嘌呤(8-azaguanine,guanazolo,简称8-AG)的极谱伏安行为.在 0. 1mol/L H2SO4底液中,8-AG有一良好的还原峰,峰电位(Ep)在-0. 95V(vs.Ag/AgCl,下同)附近,8-AG浓度在4×10-6~8×10-4mol/L范围内.峰高与浓度有良好的线性关系,线性相关系数r=0.9999~0.9910,检出限为1× 10-6mol/L.实验证明了该峰具有吸附性.本文提出了电极反应机理,它包括:酸性介质中8-AG的质子化、质子化的8-AG在汞电极上吸附以及完全不可逆的两电子还原过程.同时用量子化学计算方法(全略微分重叠法即CNDO/2)对8-AG和鸟嘌呤的各原子的净电荷以及Wiberg键级进行了计算,从理论上解释了8-AG的电化学还原机理。 相似文献
96.
1—酰基—4—氯环己烷与取代芳烃的区域与立体选择性反应 总被引:2,自引:0,他引:2
从环己烯合成了1-酰基-4-氯环己烷,发现在其在AlCl3催化与苯,氯苯,溴苯等优先生成反式1-芳基-4-酰基环己烷,与联苯反应时选择性较差。 相似文献
97.
Yechen Hu Zhongcheng Wang Liang Liu Jianhua Zhu Dongxue Zhang Mengying Xu Yuanyuan Zhang Feifei Xu Yun Chen 《Chemical science》2021,12(23):7993
Precision medicine has been strongly promoted in recent years. It is used in clinical management for classifying diseases at the molecular level and for selecting the most appropriate drugs or treatments to maximize efficacy and minimize adverse effects. In precision medicine, an in-depth molecular understanding of diseases is of great importance. Therefore, in the last few years, much attention has been given to translating data generated at the molecular level into clinically relevant information. However, current developments in this field lack orderly implementation. For example, high-quality chemical research is not well integrated into clinical practice, especially in the early phase, leading to a lack of understanding in the clinic of the chemistry underlying diseases. In recent years, mass spectrometry (MS) has enabled significant innovations and advances in chemical research. As reported, this technique has shown promise in chemical mapping and profiling for answering “what”, “where”, “how many” and “whose” chemicals underlie the clinical phenotypes, which are assessed by biochemical profiling, MS imaging, molecular targeting and probing, biomarker grading disease classification, etc. These features can potentially enhance the precision of disease diagnosis, monitoring and treatment and thus further transform medicine. For instance, comprehensive MS-based biochemical profiling of ovarian tumors was performed, and the results revealed a number of molecular insights into the pathways and processes that drive ovarian cancer biology and the ways that these pathways are altered in correspondence with clinical phenotypes. Another study demonstrated that quantitative biomarker mapping can be predictive of responses to immunotherapy and of survival in the supposedly homogeneous group of breast cancer patients, allowing for stratification of patients. In this context, our article attempts to provide an overview of MS-based chemical mapping and profiling, and a perspective on their clinical utility to improve the molecular understanding of diseases for advancing precision medicine.An overview of MS-based chemical mapping and profiling, indicating its contributions to the molecular understanding of diseases in precision medicine by answering "what", "where", "how many" and "whose” chemicals underlying clinical phenotypes. 相似文献
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99.
ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE 总被引:1,自引:0,他引:1
The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here. 相似文献
100.
Jianjun ZhangFanzuo Kong 《Tetrahedron letters》2003,44(9):1839-1842
A general method for the synthesis of 2-xylose or glucuronic acid branched (1→3)-linked mannose oligosaccharides has been developed. As a typical example, the synthesis of the methyl glycoside of β-d-GlcpA-(1→2)-α-d-Manp-(1→3)-[β-d-Xylp-(1→2)-]α-d-Manp-(1→3)-[β-d-Xylp-(1→2)-]α-d-Manp, the repeating unit of the exopolysaccharide from Cryptococcus neoformans serovar A, was achieved in a regio- and stereoselective manner. 相似文献