首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   2367篇
  免费   82篇
  国内免费   9篇
化学   1497篇
晶体学   57篇
力学   72篇
数学   240篇
物理学   592篇
  2023年   26篇
  2022年   59篇
  2021年   45篇
  2020年   61篇
  2019年   61篇
  2018年   41篇
  2017年   47篇
  2016年   74篇
  2015年   66篇
  2014年   97篇
  2013年   185篇
  2012年   133篇
  2011年   165篇
  2010年   91篇
  2009年   88篇
  2008年   135篇
  2007年   145篇
  2006年   79篇
  2005年   82篇
  2004年   69篇
  2003年   44篇
  2002年   37篇
  2001年   32篇
  2000年   20篇
  1999年   9篇
  1998年   13篇
  1997年   13篇
  1996年   21篇
  1995年   20篇
  1994年   27篇
  1993年   27篇
  1992年   20篇
  1991年   9篇
  1990年   11篇
  1989年   15篇
  1988年   22篇
  1987年   21篇
  1986年   20篇
  1985年   26篇
  1984年   24篇
  1983年   27篇
  1982年   20篇
  1981年   21篇
  1980年   22篇
  1979年   18篇
  1978年   28篇
  1977年   13篇
  1976年   22篇
  1974年   16篇
  1973年   12篇
排序方式: 共有2458条查询结果,搜索用时 15 毫秒
81.
The isolation of stable carbenes of the Arduengo and Wanzlick type has prompted us to look for stable nitrenium ions of the related structural type 1-Hydroxy-3-methyl benzotriazolium trifluromethane sulfonate. Nitrenium ions are azocations with structure and survive long enough under in vitro conditions to bind with biological nucleophiles, i.e. DNA bases, and play an important role in carcinogenic processes involving the metabolism of aromatic amines. The title compound (C15H16F3N6O5S) was isolated and crystallized in the monoclinic space group Cc with cell parameters a = 19.866(1) Å, b = 13.128(9) Å, c = 7.673(5) Å, and Z = 4. The structure has both intra- and intermolecular hydrogen bonds.  相似文献   
82.
83.
This review examines the most recent electrochemical developments for nitrate, nitrite and ammonium detection for on-site water monitoring. There remains a high demand for effective field-based detection of the dissolved inorganic nitrogen (DIN) analytes to aid in mitigating nitrogen loading. Electrochemical approaches show increasing potential to fill this role as advancements in nanotechnology continually improve analytical performance and on-site applicability. However, translating these improvements into the field still faces the resonating challenges of reaching analytical proficiency (selectivity, sensitivity, robustness, stability), practical end-user functionality, minimal matrix interferences and cost effectiveness. Herein, we elaborate on these challenges via a critical evaluation of current studies and examine how realistic the prospects of on-site nitrate, nitrite and ammonium are. We also present recommendations in addressing these gaps to conclude the review.  相似文献   
84.
In this work, the ternary hybrid structure VSe2/SWCNTs/rGO is reported for supercapacitor applications. The ternary composite exhibits a high specific capacitance of 450 F g−1 in a symmetric cell configuration, with maximum energy density of 131.4 Wh kg−1 and power density of 27.49 kW kg−1. The ternary hybrid also shows a cyclic stability of 91 % after 5000 cycles. Extensive density functional theory (DFT) simulations on the structure as well as on the electronic properties of the binary hybrid structure VSe2/SWCNTs and the ternary hybrid structure VSe2/SWCNTs/rGO have been carried out. Due to a synergic effect, there are enhanced density of states near the Fermi level and higher quantum capacitance for the hybrid ternary structure compared to VSe2/SWCNTs, leading to higher energy and power density for VSe2/SWCNTs/rGO, supporting our experimental observation. Computed diffusion energy barrier of electrolyte ions (K+) predicts that ions move faster in the ternary structure, providing higher charge storage performance.  相似文献   
85.
86.
The syntheses, structures, and chemotherapeutic activities of Ag(I)‐, Au(I)‐, and Ru(II)‐complexes ligated to a novel N‐heterocyclic carbene ligand, 2‐(4‐nitrophenyl)imidazo[1,5‐a]pyridin‐2‐ylidene ( 1 ), are described. The corresponding complexes, [Ag( 1 )2][PF6], [Au( 1 )2][PF6] ( 3 ), and [Ru( 1 )(p‐cymene)Cl][PF6] ( 4 ), were prepared using convenient transmetallation chemistry and characterized using a range of spectroscopic and analytical techniques. X‐ray crystallography revealed that complexes 2 and 3 adopted linear structures whereas 4 exhibited a prototypical “piano‐stool”‐like geometry; the structural assignments were further supported by DFT calculations. A series of in vitro studies revealed that while the aforementioned Ag(I), Au(I) and Ru(II) complexes exhibited significant cytotoxicities against the human colon adenocarcinoma (HCT 116), lung cancer (A549), and breast cancer (MCF7) cell lines, the Ru derivative was most prominent.  相似文献   
87.
Optics has already showed its potency over its electronic complements in case of superfast computing and communication systems. Semiconductor optical amplifier, (SOA) with its several nonlinear properties, plays a very crucial role in the development of high-speed all-optical processor. Multiplexer and demultiplexer are the extremely important element of the processor which takes part in utilizing different actions like encoding, decoding, routing, and the different process of data conversion and generation, etc. In this paper, the authors have proposed a scheme of phase encoded all-optical phase multiplexer using four wave mixing (FWM) property of semiconductor optical amplifier. Thus, the improved tolerance against fiber-nonlinearity and higher receiver sensitivity of phase encoding method with the fast occurring processes like FWM in SOA offers higher speed in this proposed scheme of multiplexing.  相似文献   
88.
High-rate and high-density gas separation adsorbents used in vacuum pressure swing adsorption (VPSA) processes are described. Agglomerated zeolite Li–LSX compositions made using colloidal silica binding agents and having improved nitrogen pore diffusivity compared to like compositions prepared with traditional clay binders, are also described. Preparation methods for the colloidal silica-bound adsorbents are described together with their characterization by mercury (Hg) porosimetry, scanning electron microscopy (SEM) and low dead-volume breakthrough testing, from which the pore diffusivity is obtained. In this article, we show how the location and dispersion of the colloidal silica binding agent within the agglomerated zeolite particle yields pore-architectures that resemble “state-of-the-art” binderless adsorbents. In addition, we use VPSA process simulations to show that the best process performance is achieved by the combination of high-rate and high-density adsorbent properties.  相似文献   
89.
Journal of Radioanalytical and Nuclear Chemistry - Uranium is carcinogenic ion and if present in water above its permissible limit, is very harmful to living beings. The main objective of this...  相似文献   
90.
4,4′-bipyridine bridged two Cu (II) complexes, [Cu2L12(4,4′-bipy)(H2O)2](ClO4)2 ( 1 ) and [Cu2L22(4,4′-bipy)]n·(2H2O)n ( 2 ) (where, HL1 = 2-[(3-methylamino-propylimino)-methyl]-phenol, H2L2 = 3-[(2-hydroxy-3-methoxy-benzylidene)-amino]-propionic acid, and 4,4′-bipy = 4,4′-bipyridine) have been synthesized and characterized by single crystal structure determination, mass spectrometry, FT-IR, electronic absorption, and emission spectroscopy. Complex 1 is dinuclear cationic compound and counter balanced by perchlorate anion, whereas complex 2 possesses 1D poly-nuclear structure. Both the complexes crystallize in monoclinic system with P21/c space group and the copper centers possess square pyramidal geometry. H-bonding, C-H···π, π···π interactions results the formation of two dimentional supramolecular structure for both the complexes. Interactions of complexes with bovine serum albumins (BSA) and human serum albumins (HSA) have been studied by using electronic absorption and emission spectroscopic technique. The calculated values of binding constants (Kb) are (9.22 ± 0.26) × 105 L mol−1 ( 1 -BSA), (7.19 ± 0.16) × 105 L mol−1 ( 1 -HSA), (5.05 ± 0.20) × 105 L mol−1 ( 2 -BSA) and (3.56 ± 0.25) × 105 L mol−1 ( 2 -HSA). The mechanism of serum albumins-complex interactions have been investigated by fluorescence lifetime measurement. Fluorescence spectroscopic studies indicate that both the complexes interact with calf thymas-DNA. Catecholase activity of the complexes has been studied in methanol using 3,5-di-tert-butylcatechol (3,5-DTBC) as substrate and the result show that both the complexes are active for catalytic oxidation of 3,5-DTBC to 3,5-di-tert-butylquinone (3,5-DTBQ) in presence of molecular oxygen. Calculated values of turnover numbers are 71.81 ± 1.04 h−1 and 69.45 ± 0.74 h−1 for 1 and 2 , respectively.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号