全文获取类型
收费全文 | 20811篇 |
免费 | 3594篇 |
国内免费 | 3459篇 |
专业分类
化学 | 15574篇 |
晶体学 | 390篇 |
力学 | 1254篇 |
综合类 | 301篇 |
数学 | 2682篇 |
物理学 | 7663篇 |
出版年
2024年 | 42篇 |
2023年 | 368篇 |
2022年 | 718篇 |
2021年 | 689篇 |
2020年 | 804篇 |
2019年 | 864篇 |
2018年 | 735篇 |
2017年 | 704篇 |
2016年 | 973篇 |
2015年 | 1062篇 |
2014年 | 1270篇 |
2013年 | 1586篇 |
2012年 | 1757篇 |
2011年 | 1893篇 |
2010年 | 1426篇 |
2009年 | 1476篇 |
2008年 | 1612篇 |
2007年 | 1460篇 |
2006年 | 1351篇 |
2005年 | 1194篇 |
2004年 | 921篇 |
2003年 | 771篇 |
2002年 | 904篇 |
2001年 | 667篇 |
2000年 | 566篇 |
1999年 | 411篇 |
1998年 | 273篇 |
1997年 | 215篇 |
1996年 | 217篇 |
1995年 | 150篇 |
1994年 | 132篇 |
1993年 | 108篇 |
1992年 | 95篇 |
1991年 | 72篇 |
1990年 | 68篇 |
1989年 | 59篇 |
1988年 | 50篇 |
1987年 | 32篇 |
1986年 | 27篇 |
1985年 | 29篇 |
1984年 | 17篇 |
1983年 | 21篇 |
1982年 | 9篇 |
1981年 | 4篇 |
1980年 | 9篇 |
1979年 | 9篇 |
1978年 | 16篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1973年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
982.
Shao-Song Qian Yue Zhao Miao-Miao Zhen Cheng-Lu Zhang Zhong-Lu You Hai-Liang Zhu 《Transition Metal Chemistry》2013,38(1):63-68
Two cubane-type tetranuclear nickel(II) and copper(II) complexes, [Ni4(L1)4(CH3OH)4] (1) and [Cu4(L2)4]·H2O (2), where L1 and L2 are the dianionic forms of the tridentate Schiff bases 4-nitro-2-[(2-hydroxyethylimino)methyl]phenol (H2L1) and 5-methoxy-2-[(2-hydroxyethylimino)methyl]phenol (H2L2), respectively, have been synthesized and characterized by physicochemical methods and single-crystal X-ray diffraction. The magnetic properties of the complexes show the presence of ferromagnetic interactions for complex 1 and antiferromagnetic interactions for complex 2, mediated by hydroxyl bridges. 相似文献
983.
Kongkai Zhu Junyan Lu Zhongjie Liang Xiangqian Kong Fei Ye Lu Jin Heji Geng Yong Chen Mingyue Zheng Hualiang Jiang Jun-Qian Li Cheng Luo 《Journal of computer-aided molecular design》2013,27(3):247-256
New Delhi metallo-β-lactamase-1 (NDM-1) has emerged as a major global threat to human health for its rapid rate of dissemination and ability to make pathogenic microbes resistant to almost all known β-lactam antibiotics. In addition, effective NDM-1 inhibitors have not been identified to date. In spite of the plethora of structural and kinetic data available, the accurate molecular characteristics of and details on the enzymatic reaction of NDM-1 hydrolyzing β-lactam antibiotics remain incompletely understood. In this study, a combined computational approach including molecular docking, molecular dynamics simulations and quantum mechanics/molecular mechanics calculations was performed to characterize the catalytic mechanism of meropenem catalyzed by NDM-1. The quantum mechanics/molecular mechanics results indicate that the ionized D124 is beneficial to the cleavage of the C–N bond within the β-lactam ring. Meanwhile, it is energetically favorable to form an intermediate if no water molecule coordinates to Zn2. Moreover, according to the molecular dynamics results, the conserved residue K211 plays a pivotal role in substrate binding and catalysis, which is quite consistent with previous mutagenesis data. Our study provides detailed insights into the catalytic mechanism of NDM-1 hydrolyzing meropenem β-lactam antibiotics and offers clues for the discovery of new antibiotics against NDM-1 positive strains in clinical studies. 相似文献
984.
Jian‐Nan Xiang Li‐Hui Jiang Chao‐Yue Chen Zhi‐ying Fu Jun‐Fei Duan Xiao‐Xiao He 《Journal of carbohydrate chemistry》2013,32(7):595-614
New retinoyl sugar derivatives of 13‐cis‐retinoic acid were synthesized in three ways in this paper in order to enhance pharmacal effects, especially antiproliferative activities of 13‐cis‐retinoic acid. Their structures were confirmed by IR, 1H‐NMR, 13C‐NMR, and MS spectra and their antiproliferative activities were determined in vitro using human cancer lines. Results showed that some compounds possessed potential antitumor activities. 相似文献
985.
Yuxia Sun Yong Zhou Hongri Liu Zhao Xia Man Luo Kai Wan Chengyan Wang 《Journal of Sol-Gel Science and Technology》2013,66(3):429-433
Highly preferentially oriented polycrystalline BiFeO3 thin film was grown on FTO/glass substrate by a sol–gel method annealed at 500 °C. XRD result showed that the film adopts highly (100) preferential orientation. SEM results indicate that the film is composed of large grains of 40–200 nm and the thickness is about 320 nm. Room temperature saturated polarization and large Pr ~55 μC/cm2 were obtained. Leakage current was substantially reduced by the controlling of ferroelectric polarization. Polarization-modulated conduction mechanism was studied. Moreover, substantial photovoltaic effect was observed. 相似文献
986.
Yong Li Xia Wen Lei Li Feng Wang Ning Zhao Fukui Xiao Wei Wei Yuhan Sun 《Journal of Sol-Gel Science and Technology》2013,66(3):353-362
A one-pot template-free route was developed for the synthesis of novel tetraethylenepentamine modified porous silica as CO2 adsorbents, the obtained materials were characterized by N2 adsorption/desorption, thermogravimetry, elemental analysis, Fourier transform infrared spectrometry,scanning electron microscopy and transmission electron microscopy. It was found that the amine species were inserted into the silica skeleton, which considerably enhanced their dispersion. Compared with similar materials derived from impregnation, the porous structure of the silica can be better reserved, leading to a promising CO2 adsorption capacity of 3.98 mmol CO2/g-adsorbent and a fast adsorption kinetic in simulated flue gas at 348 K. The resulted adsorbents could also be easily regenerated and showed a good durability in multiple adsorption–desorption cycles. All these features make this method a promising option for the preparation of CO2 adsorbents. 相似文献
987.
Yanlong Shi Xiaojuan Feng Yongsheng Wang Guoren Yue Wu Yang 《Journal of Sol-Gel Science and Technology》2013,67(2):251-255
A highly oriented ZnO nanorod array film was fabricated on glass substrate by combinations of Sol–Gel and hydrothermal. The film exhibits perfect superhydrophobicity with a contact angle of 155° and a glide angle of 4° after being surface modified by fluoroalkylsilane, which is similar with wings’ property and structures of large yellow spots mosquitoes. Interestingly, the ZnO nanorods film were converted from superhydrophobicity into superhydrophilicity under ultraviolet light for 2 h due to the decomposition of fluoroalkyl chain of fluoroalkylsilane and the photosensitivity of ZnO surface. The transition mechanisms of wettability are discussed on the basis of correlated theories. 相似文献
988.
Dr. Ke‐Rang Wang Yue‐Qing Wang Hong‐Wei An Jin‐Chao Zhang Prof. Dr. Xiao‐Liu Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(8):2903-2909
A new triazatruxene‐based fluorescent glycocluster has been designed, synthesized, and fully characterized by NMR spectroscopy and mass spectrometry. Furthermore, its specific and selective binding properties with concanavalin A (Con A) have been investigated by fluorescence spectroscopy, circular dichroism (CD) spectroscopy, and turbidity assay. The obtained results showed that the multivalent mannose‐modified triazatruxene exhibited specific binding with Con A, but no binding to peanut agglutinin (PNA) lectin or bovine serum albumin (BSA), corresponding to a two‐orders‐of‐magnitude higher affinity than that of monovalent mannose ligands. Most interestingly, a fluorescence enhancement of the triazatruxene‐based glycocluster was observed upon binding with Con A because of hydrophobic interactions involving sites close to the triazatruxene moiety. Furthermore, the inhibitory ability of the triazatruxene‐based glycocluster against ORN178‐ induced haemagglutination has been investigated by haemagglutination inhibition assay. The results indicated selective binding with ORN178. 相似文献
989.
Wangdong Zeng Dr. Masatoshi Ishida Sangsu Lee Young Mo Sung Dr. Zebing Zeng Yong Ni Prof. Chunyan Chi Prof. Dongho Kim Prof. Jishan Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16814-16824
A p‐quinodimethane (p‐QDM)‐bridged porphyrin dimer 1 has been prepared for the first time. An unexpected Michael addition reaction took place when we attempted to synthesize compound 1 by reaction of the cross‐conjugated keto‐linked porphyrin dimers 8 a and 8 b with alkynyl/aryl Grignard reagents. Alternatively, compound 1 could be successfully prepared by intramolecular Friedel–Crafts alkylation of the diol‐linked porphyrin dimer 14 with concomitant oxidation in air. Compound 1 shows intense one‐photon absorption (OPA, λmax=955 nm, ε=45400 M ?1 cm?1) and a large two‐photon absorption (TPA) cross‐section (σ(2)max=2080 GM at 1800 nm) in the near‐infrared (NIR) region due to its extended π‐conjugation and quinoidal character. It also exhibits a short singlet excited‐state lifetime of 25 ps. The cyclic voltammogram of 1 displays multiple redox waves with a small electrochemical energy gap of 0.86 eV. The ground‐state geometry, electronic structure, and optical properties of 1 have been further studied by density functional theory (DFT) calculations and compared with those of the keto‐linked dimer 8 b . This research has revealed that incorporation of a p‐QDM unit into the porphyrin framework had a significant impact on its optical and electronic properties, leading to a novel NIR OPA and TPA chromophore. 相似文献
990.
Ji Ha Lee Sunwoo Kang Prof. Dr. Jin Yong Lee Prof. Dr. Justyn Jaworski Prof. Dr. Jong Hwa Jung 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16665-16671
There is an ongoing need for explosive detection strategies to uncover threats to human security including illegal transport and terrorist activities. The widespread military use of the explosive trinitrotoluene (TNT) for landmines poses another particular threat to human health in the form of contamination of the surrounding environment and groundwater. The detection of explosives, particularly at low picogram levels, by using a molecular sensor is seen as an important challenge. Herein, we report on the use of a fluorescent metal–organic framework hydrogel that exhibits a higher detection capability for TNT in the gel state compared with that in the solution state. A portable sensor prepared from filter paper coated by the hydrogel was able to detect TNT at the picogram level with a detection limit of 1.82 ppt (parts per trillon). Our results present a simple and new means to provide selective detection of TNT on a surface or in aqueous solution, as afforded by the unique molecular packing through the metal–organic framework structure in the gel formation and the associated photophysical properties. Furthermore, the rheological properties of the MOF‐based gel were similar to those of a typical hydrogel. 相似文献