全文获取类型
收费全文 | 17526篇 |
免费 | 3146篇 |
国内免费 | 2117篇 |
专业分类
化学 | 12714篇 |
晶体学 | 184篇 |
力学 | 1027篇 |
综合类 | 103篇 |
数学 | 1817篇 |
物理学 | 6944篇 |
出版年
2024年 | 48篇 |
2023年 | 399篇 |
2022年 | 472篇 |
2021年 | 647篇 |
2020年 | 741篇 |
2019年 | 718篇 |
2018年 | 630篇 |
2017年 | 574篇 |
2016年 | 858篇 |
2015年 | 827篇 |
2014年 | 1002篇 |
2013年 | 1277篇 |
2012年 | 1596篇 |
2011年 | 1530篇 |
2010年 | 1072篇 |
2009年 | 993篇 |
2008年 | 1095篇 |
2007年 | 1034篇 |
2006年 | 947篇 |
2005年 | 853篇 |
2004年 | 612篇 |
2003年 | 521篇 |
2002年 | 510篇 |
2001年 | 397篇 |
2000年 | 358篇 |
1999年 | 425篇 |
1998年 | 346篇 |
1997年 | 340篇 |
1996年 | 318篇 |
1995年 | 275篇 |
1994年 | 225篇 |
1993年 | 198篇 |
1992年 | 156篇 |
1991年 | 135篇 |
1990年 | 157篇 |
1989年 | 111篇 |
1988年 | 76篇 |
1987年 | 54篇 |
1986年 | 59篇 |
1985年 | 59篇 |
1984年 | 30篇 |
1983年 | 30篇 |
1982年 | 30篇 |
1981年 | 19篇 |
1980年 | 10篇 |
1977年 | 3篇 |
1957年 | 2篇 |
1942年 | 2篇 |
1930年 | 2篇 |
1916年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
971.
Scott B. Ficarro Jessica M. Biagi Jinhua Wang Jenna Scotcher Rositsa I. Koleva Joseph D. Card Guillaume Adelmant Huan He Manor Askenazi Alan G. Marshall Nicolas L. Young Nathanael S. Gray Jarrod A. Marto 《Journal of the American Society for Mass Spectrometry》2014,25(4):636-650
We assemble a versatile molecular scaffold from simple building blocks to create binary and multiplexed stable isotope reagents for quantitative mass spectrometry. Termed Protected Amine Labels (PAL), these reagents offer multiple analytical figures of merit including, (1) robust targeting of peptide N-termini and lysyl side chains, (2) optimal mass spectrometry ionization efficiency through regeneration of primary amines on labeled peptides, (3) an amino acid-based mass tag that incorporates heavy isotopes of carbon, nitrogen, and oxygen to ensure matched physicochemical and MS/MS fragmentation behavior among labeled peptides, and (4) a molecularly efficient architecture, in which the majority of hetero-atom centers can be used to synthesize a variety of nominal mass and sub-Da isotopologue stable isotope reagents. We demonstrate the performance of these reagents in well-established strategies whereby up to four channels of peptide isotopomers, each separated by 4 Da, are quantified in MS-level scans with accuracies comparable to current commercial reagents. In addition, we utilize the PAL scaffold to create isotopologue reagents in which labeled peptide analogs differ in mass based on the binding energy in carbon and nitrogen nuclei, thereby allowing quantification based on MS or MS/MS spectra. We demonstrate accurate quantification for reagents that support 6-plex labeling and propose extension of this scheme to 9-channels based on a similar PAL scaffold. Finally, we provide exemplar data that extend the application of isotopologe-based quantification reagents to medium resolution, quadrupole time-of-flight mass spectrometers. Figure
115F 相似文献
972.
Yu He Sen Liao Zhipeng Chen Yu Li Yao Xia Wenwei Wu Bin Li 《Journal of Thermal Analysis and Calorimetry》2014,115(1):237-245
The precursor of LiNiPO4 was synthesized by solid-state reaction at low-heating temperature using LiOH·H2O and NH4NiPO4·H2O as raw materials. LiNiPO4 was obtained by calcining the precursor. Based on the advanced isoconversional procedure and the distributed activation energy model (DAEM), the activation energies calculated indicated that the thermal process involved two stages which stage II was a kinetically complex process, but stage I was single-step process. The most probable mechanism for the stage I is random nucleation and subsequent growth. DAEM and nonlinear model-fitting method were applied to study the stage II of decomposition process of the precursor. The distributions of activation energy, f(E a) and values of preexponential factor A of the stage II of the thermal decomposition of precursor were obtained on the basis of DAEM. The results of nonlinear model-fitting method showed the most probable mechanisms of the parallel reactions for stage II are chemical reaction and nucleation. 相似文献
973.
He Xu Ye Wu Shi-xiao Jin Ye Wang Jin Han Xiao-lin Meng Hai-long Yuan 《Journal of Thermal Analysis and Calorimetry》2014,115(3):2463-2470
The antibacterial activities of a kind of novel peptide from Plutella xylostella (pxCECA1) on methicillin-resistant staphylococcus aureus (MRSA) and Escherichia coli (E. coli) growth were investigated by microcalorimetry. The heat flow power–time curves of MRSA and E. coli growth in the presence of pxCECA1 were recorded using the 3114/3115 Thermal Activity Monitor Air Isothermal Calorimeter based on ampoule mode at 37 °C. Some parameters including growth rate constant k, maximum power output P max, total heat output Qt, generation time t g, growth inhibitory ratio I, and half-inhibitory concentration of the drugs IC50 were obtained to elucidate the antibacterial activity of pxCECA1. The results showed that k, P max, and Q t decreased, but I and t g increased or delayed with the increase in pxCECA1 concentration. The IC50 of pxCECA1 on E. coli was 6.122 μg mL?1 and MRSA was 7.809 μg mL?1. It could be concluded that pxCECA1 had stronger inhibitory effect on E. coli than MRSA. In vivo test was simultaneously performed using an E. coli and MRSA infection model to validate the antibacterial activity of pxCECA1. The results revealed that pxCECA1 with broad spectrum antimicrobial activities hopefully represented a class of promising substitute of antimicrobial agents. 相似文献
974.
Chunxiang Hu Yunyun He Shuiliang Chen Yongmei Zhu Muddasir Hanif Haoqing Hou 《Journal of Solid State Electrochemistry》2014,18(10):2797-2802
A binder-free activated carbon paper (ACP) was simply prepared for electric double-layer capacitors by the carbonization of filter paper, followed by heat-air activation at a lower temperature. The electrochemical cells assembled using the as-prepared ACP-470 provides a high specific capacitance of 296.4 F g?1 at current density of 0.5 A g?1 and a high rate performance at a current density of 150 A g?1 with a capacitance of 191.2 F g?1 and a high cycle ability at 10,000 recycles with 100 % capacitance retention. In addition, the ACP has a lower electrical resistivity and provides an effective energy storage performance with a maximum energy density of 41.2 Wh kg?1 and a maximum power density of 138.0 kW kg?1 in a voltage range of 1 V. 相似文献
975.
Biao Xu Peilei He Huiling Liu Pengpeng Wang Prof. Dr. Gang Zhou Prof. Dr. Xun Wang 《Angewandte Chemie (International ed. in English)》2014,53(9):2339-2343
Multidimensional nano‐heterostructures (NHSs) that have unique dimensionality‐dependent integrative and synergic effects are intriguing but still underdeveloped. Here, we report the first helical 1D/2D epitaxial NHS between CdS and ZnIn2S4. Experimental and theoretical studies reveal that the mismatches in lattice and dangling bonds between 1D and 2D units govern the growth procedure. The resulting well‐defined interface induces the delocalized interface states, thus facilitate the charge transfer and enhance the performance in the photoelectrochemical cells. We foresee that the mechanistic insights gained and the electronic structures revealed would inspire the design of more complex 1D/2D NHSs with outstanding functionalities. 相似文献
976.
Pumping through Porous Hydrophobic/Oleophilic Materials: An Alternative Technology for Oil Spill Remediation
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Jin Ge Yin‐Dong Ye Hong‐Bin Yao Xi Zhu Xu Wang Liang Wu Jin‐Long Wang Prof. Hang Ding Prof. Ni Yong Prof. Ling‐Hui He Prof. Dr. Shu‐Hong Yu 《Angewandte Chemie (International ed. in English)》2014,53(14):3612-3616
Recently, porous hydrophobic/oleophilic materials (PHOMs) have been shown to be the most promising candidates for cleaning up oil spills; however, due to their limited absorption capacity, a large quantity of PHOMs would be consumed in oil spill remediation, causing serious economic problems. In addition, the complicated and time‐consuming process of oil recovery from these sorbents is also an obstacle to their practical application. To solve the above problems, we apply external pumping on PHOMs to realize the continuous collection of oil spills in situ from the water surface with high speed and efficiency. Based on this novel design, oil/water separation and oil collection can be simultaneously achieved in the remediation of oil spills, and the oil sorption capacity is no longer limited to the volume and weight of the sorption material. This novel external pumping technique may bring PHOMs a step closer to practical application in oil spill remediation. 相似文献
977.
Alkyl Ammonium Cation Stabilized Biocidal Polyiodides with Adaptable High Density and Low Pressure
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Chunlin He Dr. Damon A. Parrish Prof. Dr. Jean'ne M. Shreeve 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6699-6706
The effective application of biocidal species requires building the active moiety into a molecular back bone that can be delivered and decomposed on demand under conditions of low pressure and prolonged high‐temperature detonation. The goal is to destroy storage facilities and their contents while utilizing the biocidal products arising from the released energy to destroy any remaining harmful airborne agents. Decomposition of carefully selected iodine‐rich compounds can produce large amounts of the very active biocides, hydroiodic acid (HI) and iodine (I2). Polyiodide anions, namely, I3?, I5?, which are excellent sources of such biocides, can be stabilized through interactions with large, symmetric cations, such as alkyl ammonium salts. We have designed and synthesized suitable compounds of adaptable high density up to 3.33 g cm?3 that are low‐pressure polyiodides with various alkyl ammonium cations, deliverable iodine contents of which range between 58.0–90.9 %. 相似文献
978.
979.
Yong‐Gang Zhang Xiang‐Lei Liu Zeng‐Yang He Xi‐Ming Li Hong‐Jian Kang Prof. Dr. Shi‐Kai Tian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(10):2765-2769
An unprecedented oxidative arylation reaction of terminal alkenes with simple aroyl hydrazides has been developed under aerobic conditions for the stereoselective synthesis of 1,2‐disubstituted alkenes. A range of aroyl hydrazides underwent palladium/copper‐catalyzed oxidative Mizoroki–Heck reaction with terminal alkenes open to air in a 1:1 mixture of dimethyl sulfoxide and acetonitrile to give structurally diverse 1,2‐disubstituted alkenes in moderate to excellent yields with excellent regio‐ and E‐selectivity. The reaction tolerated a wide variety of functional groups, such as alkoxy, hydroxy, amino, fluoro, chloro, bromo, cyano, nitro, ester, amide, imide, phosphine oxide, and sulfone groups, and, moreover, molecular oxygen and dimethyl sulfoxide were demonstrated to serve as terminal oxidants. This study provides a useful method for the stereoselective synthesis of 1,2‐disubstituted alkenes through direct transformation of the vinylic C?H bonds in terminal alkenes. 相似文献
980.
Reactivity of Oxygen Radical Anions Bound to Scandia Nanoparticles in the Gas Phase: CH Bond Activation
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Li‐Hua Tian Jing‐Heng Meng Dr. Xiao‐Nan Wu Dr. Yan‐Xia Zhao Dr. Xun‐Lei Ding Prof. Dr. Sheng‐Gui He Dr. Tong‐Mei Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):1167-1175
The activation of C?H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O?.) is an important species in C?H activation. The mechanistic details of C?H activation by O?. radicals can be well understood by studying the reactions between O?. containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n‐butane was studied by using a high‐resolution time‐of‐flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n‐butane by (Sc2O3)NO? (N=1–18) clusters was observed. The reactivity of (Sc2O3)NO? (N=1–18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc8O13?) and 12 (Sc24O37?). Larger (Sc2O3)NO? clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc2O3)NO? (N=1–5) clusters, which were found to contain the O?. radicals as the active sites. The local charge environment around the O?. radicals was demonstrated to control the experimentally observed size‐dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O?. containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C?H bond activation. 相似文献