全文获取类型
收费全文 | 19826篇 |
免费 | 1805篇 |
国内免费 | 1105篇 |
专业分类
化学 | 14103篇 |
晶体学 | 215篇 |
力学 | 805篇 |
综合类 | 110篇 |
数学 | 2081篇 |
物理学 | 5422篇 |
出版年
2024年 | 19篇 |
2023年 | 222篇 |
2022年 | 336篇 |
2021年 | 531篇 |
2020年 | 533篇 |
2019年 | 531篇 |
2018年 | 448篇 |
2017年 | 433篇 |
2016年 | 780篇 |
2015年 | 716篇 |
2014年 | 952篇 |
2013年 | 1394篇 |
2012年 | 1730篇 |
2011年 | 1817篇 |
2010年 | 1159篇 |
2009年 | 1000篇 |
2008年 | 1331篇 |
2007年 | 1191篇 |
2006年 | 1051篇 |
2005年 | 932篇 |
2004年 | 819篇 |
2003年 | 699篇 |
2002年 | 726篇 |
2001年 | 508篇 |
2000年 | 360篇 |
1999年 | 350篇 |
1998年 | 211篇 |
1997年 | 192篇 |
1996年 | 228篇 |
1995年 | 185篇 |
1994年 | 177篇 |
1993年 | 153篇 |
1992年 | 138篇 |
1991年 | 129篇 |
1990年 | 100篇 |
1989年 | 89篇 |
1988年 | 58篇 |
1987年 | 45篇 |
1986年 | 46篇 |
1985年 | 60篇 |
1984年 | 31篇 |
1983年 | 26篇 |
1982年 | 27篇 |
1981年 | 26篇 |
1980年 | 19篇 |
1979年 | 19篇 |
1978年 | 21篇 |
1977年 | 15篇 |
1976年 | 18篇 |
1957年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
The reaction of propanedioic acid, 2-diazo-1,3-bis(1,1-dimethylethyl) ester (di-tert-butyl diazomalonate) with a series of cyclopenta[b]thiophenes in the presence of catalytic rhodium acetate was studied. The resulting S—C ylides underwent a rearrangement to form a heterocycle with different topology; thialene, in very low yields. Experimental and spectral data for all compounds are provided. 相似文献
992.
Sojung Park Junhong Min 《International journal of environmental analytical chemistry》2013,93(6):655-664
A fast and sensitive chemiluminescent enzyme-linked immunosorbent assay method to measure pathogenic bacteria, Escherichia coli O157:H7, on immuno-chromatographic membrane was studied. Non-specific binding of proteins on membrane strip was controlled to attain the best performance of immunosensor by optimising the composition of a running buffer. The specificity of the proposed immunostrip was confirmed by conducting experiments for four different micro-organisms. A chemiluminescent signal could be successfully generated from a proposed immunostrip sensing system, and a significant change in the chemiluminescent light intensity with the concentration of target microbes was obtained. E. coli O157:H7 could be quantitatively measured in the range of 1.1?×?103?–1.1?×?107 CFU (colony forming units) mL?1 within 16?min by using the developed chemiluminescent immunostrip. 相似文献
993.
Kristýna Urbánková Martin Moos Jiří Machát 《International journal of environmental analytical chemistry》2013,93(11):1077-1087
This paper deals with a simplified multi-element profiling of inorganic arsenic, antimony, selenium and tellurium in the form of 75As, 82Se, 121Sb and 125Te by ICP-MS for amounts less than 10?µg?L?1. Internal standards such as 72Ge and 209Bi were successfully used for the suppression of both influence of macro elements Na+, K+, Ca2+, Mg2+ or Al3+, and interference of limited concentrations of heavy metal ions. Modified silica sorbents Separon? SGX C18, C8, CN, NH2, RPS and Phenyl were tested for the preconcentration of As, Sb, Se and Te (0.25–5?µg?L?1) in the form of ion associates with cationic surfactants from 50–250?mL sample volume. 1-etoxycarbonyl-pentadecyltrimethylammonium bromide (Septonex®, 0.005?mol?L?1) was suitable for this purpose in the presence of 4-(2-pyridylazo) resorcinol, 2-pyrrolidinecarbodithioate and 8-hydroxyquinoline-5-sulphonic acid. The quantitative retention occurred at pH 7?±?0.2 and the mixture of acetone with ethanol in ratio 1?:?1 in the presence of 0.1?mol?L?1 HCl was used for the quantitative elution. Organic solvents and the excess of acid were removed by evaporation prior to the determination by ICP-MS. The determination of the above trace metalloids in various kinds of water with enrichment factor till 50 times on silica Separon? SGX C18 and the above reagents were compared with the standard addition method. 相似文献
994.
Wei-Bin Huang Cai-Yan Du Jian-An Jiang Ya-Fei Ji 《Research on Chemical Intermediates》2013,39(6):2849-2856
A method for concurrent synthesis of vanillin and isovanillin has been developed by a nonregioselective Vilsmeier–Haack reaction of O-alkyl guaiacols. O-Alkylation of guaiacol provided the corresponding O-alkyl guaiacol (1), which was then formylated with N-methylformanilide/phosphorus oxychloride to give a mixture of 4-alkoxy-3-methoxy-benzaldehyde (2) and 3-alkoxy-4-methoxybenzaldehyde (3). Finally, the obtained mixture underwent a selective dealkylation by anhydrous aluminium trichloride, while leaving methyl groups intact to simultaneously achieve the significant fine chemicals vanillin and isovanillin. 相似文献
995.
Jin-Qiang Liu Xin-Zhi Chen Baoming Ji Bang-Tun Zhao 《Research on Chemical Intermediates》2013,39(3):1143-1152
(S)-Indoline-2-carboxylic acid was synthesized by use of a nitro amination approach with l-phenylalanine as chiral pool. The first step of the synthesis was nitration of l-phenylalanine, with urea nitrate (UN)/H2SO4 as nitrating reagent, to give 2,4-dinitro-l-phenylalanine in 75.7 % yield in one-pot synthesis and 69.1 % yield by step-wise nitration. Intramolecular nitro amination of 2,4-dinitro-l-phenylalanine gave (S)-6-nitro-indoline-2-carboxylic acid in 65.7 % yield and more than 99.5 % enantiomeric excess (ee). The title compound, (S)-indoline-2-carboxylic acid, was obtained in 85.9 % yield and high ee by one-pot transformation of (S)-6-nitroindoline-2-carboxylic acid. The total synthesis consisted of three operations and gave the title compound in 42 % yield and more than 99.5 % ee. 相似文献
996.
A series of BaDyxFe12?xO19 ferrite microfibres have been synthesized from metal nitrates and citric acid by the sol–gel method. TG-DSC, XRD, FTIR, FESEM, TEM and VSM were employed to characterize the thermal decomposition process, crystallite sizes, structure and magnetic properties of ferrite microfibres. The effect of calcined temperature, holding time, ion substitution on structure, magnetic properties of barium ferrite microfibres was investigated. The nanoparticle growth mechanism of ferrite microfibres was discussed. The results indicated that the hexaferrite phase was formed at 750 °C and Dy3+ ions entered the magnetoplumbite lattice. However, the reflections shift to a lower angle and the characteristic peaks of ferrite microfibres in FTIR shift to the lower wavenumber with the Dy content increasing. The VSM results shown that saturation magnetization (M s ) gradually increased with calcined temperature increasing and holding time prolonging, while coercive force (H c ) revealed an increase at first and then decreases. With the Dy content increasing, the M s achieved values of M s = 50 emu?g?1 (297 K) and 70 emu?g?1 (77 K) and the H c value shown a continuous reduction from 515 kA??m?1 (297 K) and 435 kA?m?1 (77 K) (x = 0.0) to 242 and 215 kA?m?1 (x = 0.4). 相似文献
997.
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
998.
Soaram Kim Hyunggil Park Giwoong Nam Hyunsik Yoon Jae-Young Leem 《Journal of Sol-Gel Science and Technology》2013,67(3):580-591
Sol–gel spin-coating was used to grow zinc oxide (ZnO) thin films doped with 0–2.5 at.% B on quartz substrates. The structural, optical, and electrical properties of the thin films were investigated using field-emission scanning electron microscopy, X-ray diffraction (XRD), photoluminescence (PL), ultraviolet–visible spectroscopy, and van der Pauw Hall-effect measurements. All the thin films had deposited well onto the quartz substrates and exhibited granular morphology. The average crystallite size, lattice constants, residual stress, and lengths of the bonds in the crystal lattice of the thin films were calculated from the XRD data. The PL spectra showed near-band-edge (NBE) and deep-level emissions, and B doping varied the PL properties and increased the efficiency of the NBE emission. The optical transmittance spectra for the undoped ZnO and boron-doped zinc oxide (BZO) thin films show that the optical transmittance of the BZO thin films was significantly higher than that of the undoped ZnO thin films in the visible region of the spectra and that the absorption edge of the BZO thin films was blue-shifted. In addition, doping the ZnO thin films with B significantly varied the absorption coefficient, optical band gap, Urbach energy, refractive index, extinction coefficient, single-oscillator energy, dispersion energy, average oscillator strength, average oscillator wavelength, dielectric constant, and optical conductivity of the BZO thin films. The Hall-effect data suggested that B doping also improved the electrical properties such as the carrier concentration, mobility, and resistivity of the thin films. 相似文献
999.
Nature and population of Li+ cationic sites in MCM-22 zeolite and its pillared form (MCM-36) were investigated by means of adsorption of CO as a probe molecule. CO stretching frequency and adsorption heat were measured by FTIR spectroscopy and adsorption microcalorimetry. Intrazeolitic carbonyl complexes on Li+ cations in MCM-22 and MCM-36 are characterized by two main vibrational bands at 2,195 and 2,188 cm?1. Band at higher wavenumbers is ascribed to carbonyls on Li+ ions coordinated only to two oxygen atoms at the intersection of 10-ring channels and interacting with CO molecule by energy around 45 kJ mol?1. Band at 2,188 cm?1 was assigned to the carbonyls on Li+ cations located on top of 5 or 6-rings on the channel walls and coordinated to three or four oxygen atoms, interacting with CO molecule by energy 33–36 kJ mol?1. Effect of pillaring and layered form of zeolite on nature and population of Li+ cationic sites is also discussed, as well as the formation of dicarbonyl complexes. 相似文献
1000.
Hyun Ook Seo Dae Han Kim Kwang-Dae Kim Eun Ji Park Chae Won Sim Young Dok Kim 《Adsorption》2013,19(6):1181-1187
Adsorption and desorption of toluene on bare and TiO2-coated silica with a mean pore size of 15 nm under dry and humid conditions were studied using toluene breakthrough curves and temperature programmed desorption (TPD) of toluene and CO2. Two TiO2/silica samples (either partially or fully covered with TiO2) were prepared with 50 and 200 cycles of TiO2 atomic layer deposition (ALD), respectively. The capacity of silica to adsorb toluene improved significantly with TiO2-thin film coating under dry conditions. However, toluene desorption from the surface due to displacement by water was more pronounced for TiO2-coated samples than bare samples under humid conditions. In TPD experiments, silica with a thinner TiO2 film (50-ALD cycled) had the highest reactivity for toluene oxidation to CO2 both in the absence and presence of water. Toluene adsorption and oxidation reactivity of silica can be controlled by modifying the silica surface with small amount of TiO2 using ALD. 相似文献