全文获取类型
收费全文 | 1177篇 |
免费 | 41篇 |
国内免费 | 8篇 |
专业分类
化学 | 647篇 |
晶体学 | 8篇 |
力学 | 68篇 |
数学 | 114篇 |
物理学 | 389篇 |
出版年
2023年 | 9篇 |
2021年 | 5篇 |
2019年 | 19篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 23篇 |
2015年 | 25篇 |
2014年 | 35篇 |
2013年 | 40篇 |
2012年 | 82篇 |
2011年 | 91篇 |
2010年 | 53篇 |
2009年 | 56篇 |
2008年 | 68篇 |
2007年 | 71篇 |
2006年 | 64篇 |
2005年 | 57篇 |
2004年 | 38篇 |
2003年 | 35篇 |
2002年 | 30篇 |
2001年 | 26篇 |
2000年 | 26篇 |
1999年 | 10篇 |
1998年 | 9篇 |
1997年 | 14篇 |
1996年 | 16篇 |
1995年 | 9篇 |
1994年 | 14篇 |
1993年 | 28篇 |
1992年 | 19篇 |
1991年 | 23篇 |
1990年 | 20篇 |
1989年 | 10篇 |
1988年 | 11篇 |
1987年 | 12篇 |
1986年 | 5篇 |
1985年 | 9篇 |
1984年 | 9篇 |
1983年 | 7篇 |
1982年 | 13篇 |
1981年 | 11篇 |
1980年 | 12篇 |
1979年 | 15篇 |
1978年 | 11篇 |
1977年 | 9篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1972年 | 5篇 |
1970年 | 7篇 |
1969年 | 8篇 |
排序方式: 共有1226条查询结果,搜索用时 359 毫秒
1.
2.
Redox Communication within Multinuclear Iron–Sulfur Complexes Related to Electronic Interplay in the Active Site of [FeFe]Hydrogenase 下载免费PDF全文
Kai‐Ti Chu Dr. Yu‐Chiao Liu Yi‐Lan Huang Dr. Gene‐Hsiang Lee Dr. Mei‐Chun Tseng Prof. Ming‐Hsi Chiang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6852-6861
The one‐electron oxidations of a Fe2 complex lead to the formation of a persistent metal‐stabilized thiyl radical Fe2 species, mixed‐valent Fe4, and Fe8 complexes. The unpaired spin in the Fe2 radical species delocalizes over the Fe2 and the aromatic dithiolate, mostly on the terminal sulfur. The subsequent dimerization of the singly oxidized Fe2 to the Fe4 retains the partial thiyl radical character. For an analogue with less steric hindrance, the π–π stacking interaction between the dithiolato aromatic rings induces generation of the Fe8, in which process electronic structures of the species are modulated through reducing the thiyl radical to the thiolate. Electronic reorganization repeats when the Fe8 is converted to Fe4. Electronic interplay in the complexes decreases the energy gap of frontier MOs and buffers electronic impacts upon redox events. Easier accessible redox potentials and increased stability of the species are facilitated. The results demonstrate that electronic versatility of the benzenedithiolate exerts pronounced influences on electronic and coordination structure of the metal complexes. 相似文献
3.
Emily J. Hopkins Dr. Yurii Prots Dr. Ulrich Burkhardt Dr. Yves Watier Dr. Zhiwei Hu Dr. Chang‐Yang Kuo Dr. Jen‐Che Chiang Dr. Tun‐Wen Pi Dr. Arata Tanaka Prof. Liu Hao Tjeng Dr. Martin Valldor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(21):7938-7943
Through a solid‐state reaction, a practically phase pure powder of Ba3V2S4O3 was obtained. The crystal structure was confirmed by X‐ray single‐crystal and synchrotron X‐ray powder diffraction (P63, a=10.1620(2), c=5.93212(1) Å). X‐ray absorption spectroscopy, in conjunction with multiplet calculations, clearly describes the vanadium in charge‐disproportionated VIIIS6 and VVSO3 coordinations. The compound is shown to be a strongly correlated Mott insulator, which contradicts previous predictions. Magnetic and specific heat measurements suggest dominant antiferromagnetic spin interactions concomitant with a weak residual ferromagnetic component, and that intrinsic geometric frustration prevents long‐range order from evolving. 相似文献
4.
Yae Eun Chong Manting Chiang Kiran Deshpande Simon Haroutounian Leonid Kagan Jong Bong Lee 《Biomedical chromatography : BMC》2019,33(11)
Ondansetron, a widely used antiemetic agent, is a P‐glycoprotein (P‐gp) substrate and therefore expression of P‐gp at the blood–brain barrier limits its distribution to the central nervous system (CNS), which was observed to be reversed by coadministration with P‐gp inhibitors. Tariquidar is a potent and selective third‐generation P‐gp inhibitor, and coadministration with ondansetron has shown improved ondansetron distribution to the CNS. There is currently no reported bioanalytical method for simultaneously quantifying ondansetron with a third‐generation P‐gp inhibitor. Therefore, we aimed to develop and validate a method for ondansetron and tariquidar in rat and human plasma samples. A full validation was performed for both ondansetron and tariquidar, and sample stability was tested under various storage conditions. To demonstrate its utility, the method was applied to a preclinical pharmacokinetic study following coadministration of ondansetron and tariquidar in rats. The presented method will be valuable in pharmacokinetic studies of ondansetron and tariquidar in which simultaneous determination may be required. In addition, this is the first report of a bioanalytical method validated for quantification of tariquidar in plasma samples. 相似文献
5.
Dr. Wenyan Hao Yuchen Sha Dr. Yi Deng Yi Luo Li Zeng Shan Tang Dr. Yue Weng Prof. Dr. Chien-Wei Chiang Prof. Dr. Aiwen Lei 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(19):4931-4934
An in situ generated oxidation species of nickel quinolinylpropioamide intermediate was produced. Characterization by X-ray absorption near edge structure (XANES) and EPR provides complementary insights into this oxidized nickel species. With aliphatic amides and isocyanides as substrates, a nickel-catalyzed facile synthesis of structurally diverse five-membered lactams could be achieved. 相似文献
6.
ZnO‐Coated Carbon Nanotubes: Inter‐Diffusion of Carboxyl Groups and Enhanced Photocurrent Generation 下载免费PDF全文
Chia‐I Hung Dr. Hua‐Chiang Wen Yao‐Cheng Lai Dr. Shih‐Hsin Chang Prof. Dr. Wu‐Ching Chou Prof. Dr. Wen‐Kuang Hsu 《Chemphyschem》2015,16(4):812-816
ZnO is a defect‐governed oxide and emits light at both visible and UV regimes. This work employs atomic layer deposition to produce oxide particles on oxygenated carbon nanotubes, and the composites only show emission profiles at short wavelengths. The quenching of defect‐related emissions at long wavelengths is verified, owing to carboxyl diffusion into oxygen vacancies, and doping is supported by ZnCO3 formation in oxide lattice. Fully coated tubes display an increased photocurrent and the quantum efficiency increases by 22 % relative to the bare nanotubes. 相似文献
7.
Efrem Braun Dr. Joseph J. Chen Dr. Sondre K. Schnell Dr. Li‐Chiang Lin Dr. Jeffrey A. Reimer Dr. Berend Smit 《Angewandte Chemie (International ed. in English)》2015,54(48):14349-14352
Molecular simulations and NMR relaxometry experiments demonstrate that pure benzene or xylene confined in isoreticular metal–organic frameworks (IRMOFs) exhibit true vapor–liquid phase equilibria where the effective critical point may be reduced by tuning the structure of the MOF. Our results are consistent with vapor and liquid phases extending over many MOF unit cells. These results are counterintuitive since the MOF pore diameters are approximately the same length scale as the adsorbate molecules. As applications of these materials in catalysis, separations, and gas storage rely on the ability to tune the properties of adsorbed molecules, we anticipate that the ability to systematically control the critical point, thereby preparing spatially inhomogeneous local adsorbate densities, could add a new design tool for MOF applications. 相似文献
8.
Bo-Hao Chen Jun-Jia Xu Wei-Ren Lai Chung-Kai Chang Jeng-Lung Chen Jyh-Fu Lee Jin-Ming Chen Hwo-Shuenn Sheu Jey-Jau Lee Yoshiki Kubota Ming-Hsi Chiang Yasutaka Kitagawa Yu-Chun Chuang I-Jui Hsu 《中国化学会会志》2023,70(5):1187-1199
Two cobalt(II) halide complexes with 1,2,4-triazole as a ligand were synthesized. Their structures were determined by extended x-ray absorption fine structure (EXAFS) and powder x-ray diffraction (XRD). Both complexes [Co(Htrz)Cl2]n ( 1 ) and {[Co(Htrz)2(trz)]BF4}n ( 2 ) form one-dimensional polymeric chain and the distances of Co⋯Co are 3.3521(2) Å and 3.8629(2) Å, respectively. The Htrz and Cl− are bridging ligands to connect two Co(II) ions in 1 , and the local environment of Co site is in a distorted octahedron with {CoN2Cl4} core. In complex 2 , two Htrz and one trz are bridging ligands to connect two Co(II) ions, and the local geometry of Co is in a pseudo octahedron with {CoN6} core. The analysis of Co LII,III-edge XAS indicates that the Co(II) of both complexes are at high spin state with t2g5eg2 configuration and the crystal field strength (10Dq) is about 1.2 eV. The broken-symmetry DFT calculations indicate that antiferromagnetic coupling state of Co⋯Co is the most stable state in both complexes; and the coupling constants of 1 and 2 are −0.32 cm−1 and −3.70 cm−1, respectively. Based on the distances of Co⋯Co and coupling constants, such antiferromagnetic interaction is achieved through triazole ligands. 相似文献
9.
A biosensor was fabricated to detect pesticides in food samples. Acetylcholinesterase was immobilized in a novel fenugreek hydrogel–agarose matrix with gold nanoparticles. Transparent thin films with superior mechanical strength and stability were obtained with 2% fenugreek hydrogel and 2% agarose. Immobilization of acetylcholinesterase on the membrane resulted in high enzyme retention efficiency (92%) and a significantly prolonged shelf life of the enzyme (half-life, 55 days). Transmission electron microscopy revealed that, gold nanoparticles (10–20 nm in diameter) were uniformly dispersed in the fenugreek hydrogel–agarose–acetylcholinesterase membrane. This immobilized enzyme-gold nanoparticle dip-strip system detected various carbamates, including carbofuran, oxamyl, methomyl, and carbaryl, with limits of detection of 2, 21, 113, and 236 nM (S/N = 3), respectively. Furthermore, the fabricated biosensor exhibited good testing capabilities when used to detect carbamates added to various fruit and vegetable samples. 相似文献
10.
Wee‐Kee Tan Yiqian Ang Teck‐Kwang Lim Tit‐Meng Lim Prakash Kumar Chiang‐Shiong Loh Qingsong Lin 《Electrophoresis》2015,36(19):2473-2481
Preparation of proteins from salt‐gland‐rich tissues of mangrove plant is necessary for a systematic study of proteins involved in the plant's unique desalination mechanism. Extraction of high‐quality proteins from the leaves of mangrove tree species, however, is difficult due to the presence of high levels of endogenous phenolic compounds. In our study, preparation of proteins from only a part of the leaf tissues (i.e. salt gland‐rich epidermal layers) was required, rendering extraction even more challenging. By comparing several extraction methods, we developed a reliable procedure for obtaining proteins from salt gland‐rich tissues of the mangrove species Avicennia officinalis. Protein extraction was markedly improved using a phenol‐based extraction method. Greater resolution 1D protein gel profiles could be obtained. More promising proteome profiles could be obtained through 1D‐LC‐MS/MS. The number of proteins detected was twice as much as compared to TUTS extraction method. Focusing on proteins that were solely present in each extraction method, phenol‐based extracts contained nearly ten times more proteins than those in the extracts without using phenol. The approach could thus be applied for downstream high‐throughput proteomic analyses involving LC‐MS/MS or equivalent. The proteomics data presented herein are available via ProteomeXchange with identifier PXD001691. 相似文献