全文获取类型
收费全文 | 6236篇 |
免费 | 201篇 |
国内免费 | 15篇 |
专业分类
化学 | 4896篇 |
晶体学 | 70篇 |
力学 | 58篇 |
数学 | 314篇 |
物理学 | 1114篇 |
出版年
2023年 | 36篇 |
2022年 | 33篇 |
2021年 | 64篇 |
2020年 | 104篇 |
2019年 | 93篇 |
2018年 | 75篇 |
2017年 | 48篇 |
2016年 | 129篇 |
2015年 | 103篇 |
2014年 | 160篇 |
2013年 | 288篇 |
2012年 | 323篇 |
2011年 | 441篇 |
2010年 | 192篇 |
2009年 | 208篇 |
2008年 | 368篇 |
2007年 | 369篇 |
2006年 | 366篇 |
2005年 | 394篇 |
2004年 | 322篇 |
2003年 | 256篇 |
2002年 | 267篇 |
2001年 | 153篇 |
2000年 | 169篇 |
1999年 | 67篇 |
1998年 | 64篇 |
1997年 | 56篇 |
1996年 | 84篇 |
1995年 | 48篇 |
1994年 | 65篇 |
1993年 | 47篇 |
1992年 | 65篇 |
1991年 | 53篇 |
1990年 | 51篇 |
1989年 | 46篇 |
1988年 | 57篇 |
1987年 | 46篇 |
1986年 | 62篇 |
1985年 | 68篇 |
1984年 | 71篇 |
1983年 | 46篇 |
1982年 | 52篇 |
1981年 | 43篇 |
1980年 | 47篇 |
1979年 | 42篇 |
1978年 | 36篇 |
1977年 | 33篇 |
1976年 | 25篇 |
1975年 | 40篇 |
1974年 | 32篇 |
排序方式: 共有6452条查询结果,搜索用时 31 毫秒
991.
Within the framework of the complex basis function method, the photoionization cross sections of H(2)(+) and H(2) were calculated based on the variational principle for the frequency-dependent polarizabilities. In these calculations, complex orbital exponents of Gaussian-type basis functions for the final state continuum wavefunctions were fully optimized for each photon energy with the numerical Newton-Raphson method. In most cases, the use of only one or two complex Gaussian-type basis functions was enough to obtain excellent agreement with previous high precision calculations and available experimental results. However, there were a few cases, in which the use of complex basis functions having various angular momentum quantum numbers was crucial to obtain the accurate results. The behavior of the complex orbital exponents as a function of photon energy was discussed in relation to the scaling relation and the effective charge for photoelectron. The success of this method implies the effectiveness of the optimization of orbital exponents to reduce the number of basis functions and shows the possibility to calculate photoionization cross sections of general molecules using only Gaussian-type basis functions. 相似文献
992.
Kawaguchi M Ito R Honda H Endo N Okanouchi N Saito K Seto Y Nakazawa H 《Journal of chromatography. A》2008,1206(2):196-199
A simple and highly sensitive method called stir bar sorptive extraction (SBSE) and thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS), which is used for the determination of trace amounts of 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan) in river water samples, is described. A stir bar coated with polydimethylsiloxane (PDMS) is added to a 10mL water sample and stirring is carried out for 120min at room temperature (25 degrees C) in a vial. Then, the PDMS stir bar is subjected to TD-GC-MS. The detection limit of triclosan is 5ngL(-1) (ppt). The method shows linearity over the calibration range (0.02-20mugL(-1)) and the correlation coefficient is higher than 0.997 for triclosan standard solution. The recovery of triclosan in river water samples ranges from 91.9 to 108.3% (RSD: 4.0-7.0%). This simple, accurate, sensitive, and selective analytical method may be used in the determination of trace amounts of triclosan in river water samples. 相似文献
993.
Ito R Kawaguchi M Sakui N Honda H Okanouchi N Saito K Nakazawa H 《Journal of chromatography. A》2008,1209(1-2):267-270
A method for mercury analysis and speciation in drinking water was developed, which involved stir bar sorptive extraction (SBSE) with in situ propyl derivatization and thermal desorption (TD)-GC-MS. Ten millilitre of tap water or bottled water was used. After a stir bar, pH adjustment agent and derivatization reagent were added, SBSE was performed. Then, the stir bar was subjected to TD-GC-MS. The detection limits were 0.01 ng mL(-1) (ethylmercury; EtHg), 0.02 ng mL(-1) (methylmercury; MeHg), and 0.2 ng mL(-1) (Hg(II) and diethylmercury (DiEtHg)). The method showed good linearity and correlation coefficients. The average recoveries of mercury species (n=5) in water samples spiked with 0.5, 2.0, and 6.0 ng mL(-1) mercury species were 93.1-131.1% (RSD<11.5%), 90.1-106.4% (RSD<7.8%), and 94.2-109.6% (RSD<8.8%), respectively. The method enables the precise determination of standards and can be applied to the determination of mercury species in water samples. 相似文献
994.
The living radical photocopolymerization of 2-(N,N-diethyldithiocarbamyl)ethyl methacrylate (DCEM) as inimer and stearyl methacrylate (STM) as comonomer was carried out under UV irradiation. According to this method, we synthesized hyperbranched polymers (HP) consisting of a STM sequence having a long alkyl side chain. The gel permeation chromatography distribution of hyperbranched polymers had a unimodal pattern. The reactivity ratios (r(1)=0.79 and r(2)=0.81) were estimated by the Kelen-Tüd?s method (DCEM: [M](1) and STM: [M](2)). These values indicated that the two monomers showed almost equal reactivity toward propagating radical species. The radius of gyration (R(g)) and the hydrodynamic radius (R(h)) of copolymers were determined by static and dynamic light scattering (SLS and DLS), and the values of R(g)/R(h) changed from 0.79 to 1.59 with an increment of the feed amount of STM. These results indicated that the copolymer structures changed from hard spheres to loose branched molecules in solution. 相似文献
995.
Kawaguchi M Ito R Honda H Endo N Okanouchi N Saito K Seto Y Nakazawa H 《Journal of chromatography. A》2008,1200(2):260-263
A method for the simultaneous measurement of benzophenone (BP) sunscreen compounds, its derivatives 2,4-dihydroxybenzophenone (BP-1), 2-hydroxy-4-methoxybenzophenone (BP-3), 2-hydroxy-4-methoxy-4'-methylbenzophenone (BP-10), 2-hydroxybenzophenone (2OH-BP), 3-hydroxybenzophenone (3OH-BP) and 4-hydroxybenzophenone (4OH-BP), in water samples was developed using stir bar sorptive extraction (SBSE) with in situ derivatization followed by thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS). The detection limit is 0.5-2 ng L(-1) (ppt) for the seven BPs. The method shows good linearity and the correlation coefficients are equal to or higher than 0.990 for all the analyte. The average recoveries of BPs range from 102.0 to 128.1% (RSD<15.4%, n=6). Trace amounts of BPs in river water samples were determined by the present method. 相似文献
996.
Tsue H Matsui K Ishibashi K Takahashi H Tokita S Ono K Tamura R 《The Journal of organic chemistry》2008,73(19):7748-7755
To investigate the solid-state complexation of nitrogen-bridged calixarene analogues, azacalix[7]arene heptamethyl ether 1 has been prepared by applying a "5 + 2"-fragment coupling approach using Buchwald-Hartwig aryl amination reaction aided by our previously devised temporal N-silylation protocol. X-ray crystallographic analysis revealed that azacalix[7]arene 1 adopted a highly distorted 1,2-alternate conformation in the solid state as a result of intramolecular NH/O hydrogen bonding interactions and steric repulsion between the methoxy groups. In the crystal, molecules of 1 are mutually interacted by intermolecular NH/O and CH/pi interactions to establish one-dimensional (1D) hexane-filled nanochannel crystal architecture. Similarly to our recently reported azacalix[6]arene 2, the desolvated crystalline powder material of 1 was capable of selectively and rapidly adsorbing CO2 among the four main components of the atmosphere. The adsorption capacity of 1 for CO2 nearly doubled as compared to that of 2 because of the formation of the 1D nanochannel with almost twice the volume of the latter. 相似文献
997.
998.
Synthesis of palmitoyl caprazol 7, which possesses a simple fatty acyl side chain at the 3' '-position of the diazepanone moiety, was carried out and their antibacterial activity was evaluated. The key elements of our approach include the improved synthesis of the key 5'-beta-O-aminoribosyl-glycyluridine derivative, installation of the palmitoyl side chain to the cyclization precursor, and the construction of the diazepanone by an intramolecular reductive amination. The second generation synthesis of (+)-caprazol was also established. Palmitoyl caprazol 7 exhibited antibacterial activity against Mycobacterium smegmatis ATCC607 (MIC = 6.25 microg/mL) with potency similar to that of the caprazamycins (CPZs). Palmitoyl caprazol 7 and N6'-desmethyl palmitoyl caprazol 28 also exhibited antibacterial activity against drug-resistant bacteria including methyciline-resistant Staphylococcus aureus (MRSA) and vancomycin-resistant Enterococcus (VRE) strains (MIC = 3.13-12.5 microg/mL). 相似文献
999.
Chiral trianglamine-Cu(OAc)2 complex was found to be an efficient catalyst for enantioselective Henry reaction between nitromethane and various aldehydes to provide β-hydroxynitoroalkanes with high enantiomeric excesses under solvent-free conditions. 相似文献
1000.
Dr. Ziqian Xue Dr. Jia-Jia Zheng Dr. Yusuke Nishiyama Dr. Ming-Shui Yao Dr. Yoshitaka Aoyama Zeyu Fan Dr. Ping Wang Prof. Takashi Kajiwara Prof. Yoshiki Kubota Prof. Satoshi Horike Prof. Ken-ichi Otake Prof. Susumu Kitagawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(2):e202215234
Exploring new porous coordination polymers (PCPs) that have tunable structure and conductivity is attractive but remains challenging. Herein, fine pore structure engineering by ligand conformation control of naphthalene diimide (NDI)-based semiconducting PCPs with π stacking-dependent conductivity tunability is achieved. The π stacking distances and ligand conformation in these isoreticular PCPs were modulated by employing metal centers with different coordination geometries. As a result, three conjugated PCPs (Co−pyNDI, Ni−pyNDI, and Zn−pyNDI) with varying pore structure and conductivity were obtained. Their crystal structures were determined by three-dimensional electron diffraction. The through-space charge transfer and tunable pore structure in these PCPs result in modulated selectivity and sensitivity in gas sensing. Zn−pyNDI can serve as a room-temperature operable chemiresistive sensor selective to acetone. 相似文献