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151.
The fragmentation patterns of a novel series of dithiocarbamate derivatives with pharmaceutical activity were investigated by positive ion electrospray ionization mass spectrometry in conjunction with tandem mass spectrometry (ESI-MS(n)). In the gas phase, the dithiocarbamate protonated molecules containing the piperazinium moiety undergo losses of bromide to form the piperazinium cation by ionization, followed by subsequent losses of methyl bromide, ring opening and rearrangement of piperazinium. Furthermore, the dithiocarbamate derivatives and their intermediates both undergo cleavage of the C-S bond to produce two common fragment ions. The different fragmentation observed for these compounds facilitated their identification and could be valuable in the further study of their metabolic pathways as prodrugs. 相似文献
152.
采用碘化N,N,N-三甲基-8-氨基-三环[5.2.1.02.6]癸烷为结构导向剂, 通过过程控制方法, 经3-4 d成功合成了高性价比的B-SSZ-33分子筛. 以B-SSZ-33为母体, 经过Al(NO3)3溶液后处理制得了Al-SSZ-33分子筛. 采用X射线衍射(XRD), 傅里叶变换红外(FT-IR)光谱, 扫描电子显微镜(SEM), 热重(TG)分析, 电感耦合等离子体原子发射光谱(ICP-AES), N2吸附/脱附, 27Al核磁共振(27Al NMR)和NH3程序升温脱附(NH3-TPD)等手段对合成的B-SSZ-33、Al-SSZ-33样品进行了物理化学性能表征. 并以甲苯作为汽车尾气中碳氢化合物的探针分子, 通过甲苯程序升温脱附测试来考察样品的碳氢捕集性能. 结果表明: 后处理过程中Al同晶取代B, 从而制得了含骨架Al的Al-SSZ-33; 在甲苯的程序升温脱附测试中, 由于Al-SSZ-33相对于B-SSZ-33具有较强的酸性位, 且表面孔口由于骨架外硅铝物种的修饰, 限制了甲苯的扩散, 致使脱附速率最大时的温度(Tmax)和脱附最终的温度(Tend)均升高, 从而形成了新型汽车尾气捕集催化剂的雏形. 相似文献
153.
采用基于密度泛函理论(DFT)的Dmol3程序系统研究了O原子与O2在 Au19与Au20团簇上的吸附反应行为. 结果表明: O在Au19团簇顶端洞位上的吸附较Au20强; 在侧桥位吸附强度相近. O与O2在带负电Au团簇上吸附较强, 在正电团簇吸附较弱. 从O―O键长看, 当金团簇带负电时, O―O键长较长, 中性团簇次之, 正电团簇中O―O键长较短, 因而O2活化程度依次减弱. 电荷布居分析表明, Au团簇带负电时, O与O2得电子数较中性团簇多, 而团簇带正电时, 得电子数较少. 差分电荷密度(CDD)表明, O2与Au团簇作用时, 金团簇失电子, O2的π*轨道得电子, 使O―O键活化. O2在Au19-团簇上解离反应活化能为1.33 eV, 较中性团簇低0.53 eV; 而在Au19+上活化能为2.27 eV, 较中性团簇高0.41 eV, 这与O2在不同电性Au19团簇O―O键活化规律相一致. 相似文献
154.
CHEN WenWen LI TangSong HE Sha LIU DingBin WANG Zhuo ZHANG Wei & JIANG XingYu CAS Key Laboratory for Biological Effects of Nanomaterials Nanosafety National Center for Nanoscience Technology Beijing China Graduate Schoold of the Chinese Academy of Sciences Beijing China Key Laboratory of Microsystems Microstructures Manufacturing Ministry of Education Harbin Institute of Technology Harbin College of Bioengineering Chongqing Universit... 《中国科学B辑(英文版)》2011,(8)
Immunoassays are useful for many bioassays. Many new techniques and materials are introduced into the immunoassay to improve the efficiency. This paper reviews recent progress in the application of microfluidic systems and gold nanoparticles in immunoassay. The micro/nano technologies and materials can offer good sensitivity, fast detection, cost-effectiveness and easy signal readout. In particular, the miniaturization of microfluidics and colorimetric assays based on gold nanoparticles have dramatically im... 相似文献
155.
Sha Zhao Guoquan Zhang Lei Fu Lifen Liu Xiaohong Fang Fenglin Yang 《Electroanalysis》2011,23(2):355-363
To analyze the specific roles of anthraquinone‐2‐sulfonate (AQS) and polypyrrole (PPy) layer on oxygen reduction reaction (ORR), the electrocatalytic reduction of oxygen was investigated on the AQS/PPy composite modified graphite electrode. Results show that the enhanced electrocatalytic performance is attributed to the excellent electrocatalytic activity of the immobilized AQS functional groups to mediate two‐electron reduction of O2 to H2O2. The PPy layer may not participate in ORR, but it can further catalyze the two‐electron reduction of H2O2 to produce H2O in the potential range more negative than that the two‐electron reduction of oxygen proceeds efficiently on the AQS sites. 相似文献
156.
The asymmetric α-amination of 4-substituted pyrazolones with azodicarboxylates was investigated for the first time, employing an N,N'-dioxide gadolinium(III) complex as the catalyst. The novel transformations exhibited high yield, and 4-amino-5-pyrazolone derivatives bearing a chiral quaternary center were obtained in excellent yields (up to 99%) and enantioselectivities (90%-97% ee) for a broad scope of 5-pyrazolones by using 1 mol % or only 0.05 mol % of catalyst. 相似文献
157.
本文研究了求解单调变分不等式问题的一个投影收缩算法.利用何炳生教授的分析手法,给出了新步长,并且证明了在该步长下算法的全局收敛性.初步的数值试验表明了新步长的实用性. 相似文献
158.
Yu TH Sha Y Liu WG Merinov BV Shirvanian P Goddard WA 《Journal of the American Chemical Society》2011,133(49):19857-19863
We report results of quantum mechanics (QM) mechanistic studies of Nafion membrane degradation in a polymer electrolyte membrane (PEM) fuel cell. Experiments suggest that Nafion degradation is caused by generation of trace radical species (such as OH(●), H(●)) only when in the presence of H(2), O(2), and Pt. We use density functional theory (DFT) to construct the potential energy surfaces for various plausible reactions involving intermediates that might be formed when Nafion is exposed to H(2) (or H(+)) and O(2) in the presence of the Pt catalyst. We find a barrier of 0.53 eV for OH radical formation from HOOH chemisorbed on Pt(111) and of 0.76 eV from chemisorbed OOH(ad), suggesting that OH might be present during the ORR, particularly when the fuel cell is turned on and off. Based on the QM, we propose two chemical mechanisms for OH radical attack on the Nafion polymer: (1) OH attack on the S-C bond to form H(2)SO(4) plus a carbon radical (barrier: 0.96 eV) followed by decomposition of the carbon radical to form an epoxide (barrier: 1.40 eV). (2) OH attack on H(2) crossover gas to form hydrogen radical (barrier: 0.04 eV), which subsequently attacks a C-F bond to form HF plus carbon radicals (barrier as low as 1.00 eV). This carbon radical can then decompose to form a ketone plus a carbon radical with a barrier of 0.86 eV. The products (HF, OCF(2), SCF(2)) of these proposed mechanisms have all been observed by F NMR in the fuel cell exit gases along with the decrease in pH expected from our mechanism. 相似文献
159.
Xin XL Deng S Zhang BJ Huang SS Tian Y Ma XC An L Shu XH Yao JH Cui X 《Natural product communications》2011,6(6):781-784
Biotransformation of deoxyandrographolide (1) by Alternaria alternata AS 3.4578 gave five derivatives identified by spectral methods including 2D NMR as the known dehydroandrographolide (2) and 9beta-hydroxy-dehydroandrographolide (3) and the new compounds 9beta-hydroxy-deoxyandrographolide (4), 3alpha,17,19-trihydroxy-8,13-ent-labdadien-15,16-olide (5) and 3-oxo-9beta-hydroxy-deoxyandrographolide (6). 相似文献
160.
The simplified model for 4f-5d transitions is applied to obtain the line strengths for emission, ground-state absorption and excited states absorption involving 4f-5d transitions of Nd3+ in crystals. The results are host independent for the usual case where 5d crystal-field interaction can be considered as strong, in the sense that the calculated 5d-4f emission relative line strengths will be the same for Nd3+ in any host. Also the calculated 4f-5d absorption line strengths can be grouped by the 5d crystal-field components. For each 5d crystal-field component, the group of absorption line strengths for different 4f25d transition final states forms a pattern independent of the 5d crystal-field component and the host. For practical cases, due to strong but still limited 5d crystal-field splitting, the transitions to different 5d crystal-field components may overlap each other. The theoretical results are used to interpret available experimental data. 相似文献