全文获取类型
收费全文 | 21648篇 |
免费 | 1350篇 |
国内免费 | 1947篇 |
专业分类
化学 | 20859篇 |
晶体学 | 407篇 |
力学 | 692篇 |
综合类 | 89篇 |
数学 | 151篇 |
物理学 | 2747篇 |
出版年
2024年 | 21篇 |
2023年 | 203篇 |
2022年 | 368篇 |
2021年 | 393篇 |
2020年 | 635篇 |
2019年 | 662篇 |
2018年 | 705篇 |
2017年 | 955篇 |
2016年 | 1085篇 |
2015年 | 831篇 |
2014年 | 850篇 |
2013年 | 2180篇 |
2012年 | 1366篇 |
2011年 | 1166篇 |
2010年 | 1067篇 |
2009年 | 1299篇 |
2008年 | 1112篇 |
2007年 | 1181篇 |
2006年 | 1037篇 |
2005年 | 878篇 |
2004年 | 792篇 |
2003年 | 674篇 |
2002年 | 577篇 |
2001年 | 510篇 |
2000年 | 525篇 |
1999年 | 454篇 |
1998年 | 416篇 |
1997年 | 370篇 |
1996年 | 364篇 |
1995年 | 358篇 |
1994年 | 283篇 |
1993年 | 227篇 |
1992年 | 185篇 |
1991年 | 157篇 |
1990年 | 154篇 |
1989年 | 132篇 |
1988年 | 161篇 |
1987年 | 168篇 |
1986年 | 101篇 |
1985年 | 79篇 |
1984年 | 90篇 |
1983年 | 24篇 |
1982年 | 58篇 |
1981年 | 26篇 |
1980年 | 20篇 |
1979年 | 17篇 |
1978年 | 7篇 |
1977年 | 5篇 |
1973年 | 6篇 |
1959年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 203 毫秒
991.
A rapid and inexpensive method for simultaneous quantification of terbumeton (TER), and its major potential metabolites (TED;
terbumeton-desethyl, TOH; terbumeton-2-hydroxy and TID; terbumeton-deisopropyl) in soil bulk water (SBW) samples is proposed.
The analytical method involves extraction–concentration from SBW samples using a graphitized carbon black (GCB) cartridge
followed by their separation–detection by reversed-phase high-performance liquid chromatography analysis using a C18 column and a diode array detector. A mobile phase of acetonitrile−0.005 mol L−1 phosphate buffer (pH 7.0) (35:65, v/v) at a flow rate of 0.8 mL min−1 in isocratic elution mode has been used. After optimization of the extraction and separation conditions, this method can be
used for the simultaneous determination of investigated compounds in the range of the international limits of 0.1 μg L−1. For TER the detection limit was 0.009 μg L−1 and it was 0.100, 0.550, and 0.480 μg L−1 for TED, TOH, and TID, respectively. The recoveries of TER, TED, TOH, and TID from SBW samples, measured at three levels of
concentration range, were found to be between 48.0 and 102.0%. The intra-day precision measured by relative standard deviation
(RSD) was always lower than 9.0%. 相似文献
992.
993.
Verónica Iguarbe 《Liquid crystals》2020,47(2):301-308
ABSTRACT Novel liquid crystalline Janus dendrimers that combine a mesogenic block and an electroactive block have been synthesised. The mesogenic block is based on two third-generation Percec-type dendrons bearing six or eight terminal dodecyloxy alkyl chains, whereas the electroactive blocks are formed by one or two carbazole units. The liquid crystal behaviour was investigated by polarised-light optical microscopy, differential scanning microscopy and X-ray diffraction. The Janus dendrimers with one electroactive unit exhibited cubic or columnar liquid crystal phases, whereas the Janus dendrimers with two electroactive units did not show liquid crystalline behaviour. The UV-vis absorption and emission properties of the Janus dendrimers were investigated. The spectra suggested the existence of π-π stacking and the formation of aggregates in the solid state. Electrodeposition of the carbazole-containing dendrimers afforded semi-globular particles in which the number of electropolymerizable units and the flexible or rigid character of the linker have a decisive influence in the particle size. 相似文献
994.
A supported liquid membrane (SLM) method for the speciation of chromium has been developed. The method is based on selective extraction and enrichment of anionic Cr(VI) and cationic Cr(III) species in two serially connected SLM units. Methyltricaprylammonium chloride (Aliquat) and di-(2-ethylhexyl) phosphoric acid (DEHPA), respectively were used as the selective extractants in the membrane liquid. Graphite furnace atomic absorption spectrometry (GFAAS) was utilised for final determination. Optimised conditions for the DEHPA membrane were, sample solution at pH 3, acceptor solution 0.1 M HNO3 and 10% w/w carrier in kerosene. The corresponding values for the Aliquat membrane were pH 7, 0.75 M HNO3 and 6% w/w carrier in di-n-hexylether. This gave extraction efficiencies for Cr(III) and Cr(VI) of 90 and 40%, respectively. The method was used to measure the concentration of Cr III and Cr VI in surface water from an abandoned tannery site. Storage experiments at different pH showed that preservation at neutral pH gave almost constant values over a period of one month. At acidic pH (pH=3.0) the concentration of Cr(VI) decreased rapidly while the concentration of Cr(III) increased. The detection limit, expressed as three times the standard deviation of enriched blank samples was 0.01 μg l−1. 相似文献
995.
The Studies of the Heterogeneous Properties of Solid Surfaces by Means of the Derivatograph Q-1500 D
A simple method has been adopted to obtain an important information on the heterogeneous properties of materials studied,
adsorbed liquid films and liquid-solid interactions. The method utilizes Q-TG mass loss and the first derivative Q-DTG mass
loss curves with respect to temperature and time obtained during programmed liquid thermodesorption in quasi-isothermal conditions.
The values of the adsorption capacity, total porosity of material, the value of active centers, desorption energy distribution
and mesopore-size distribution functions obtained by this method are in good agreement with those estimated on the basis of
independent methods. The theoretical and experimental results provided novel and unique data on the heterogeneity of solid
surfaces, properties of liquid adsorbed films and thermal stability of the liquid/solid interfaces.
This paper presents the more important results obtained so far in the studies the liquid/solid systems by means of the Paulik's
classical and quasi-isothermal techniques.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
996.
Summary Two reversed-phase LC systems were investigated by frontal analysis for the determination of linear chromatographic conditions,
as defined according to the isotherm concept. The Partisil ODS-3 bonded silica and the PRP-1 polystyrene-divinylbenzene resin
were used as stationary phases together withtrans-2-hexen-al as test solute and methanol-water mixtures as mobile phases. Particular attention was paid to the respective influence
of the two main parameters which may cause sorbent overloading, that is, the capacity factor (k′) and the solute concentration
in the mobile phase (Cm). Provided that k′Cm≤10−2 M, linear chromatographic behaviour was observed for both sorbents, the maximum capacities of which were found greater than
1mmolg−1. 相似文献
997.
M. I. Volkova-Gugeshashvili A. G. Volkov V. S. Markin 《Russian Journal of Electrochemistry》2006,42(10):1073-1078
The thermodynamics of adsorption of amphiphilic surface-active compounds at the interface between two immiscible liquids is
considered. At the interface, these molecules are supposed to replace a few of the adsorbed molecules of both solvents. Classical
isotherms of adsorption (Frumkin, Frumkin-Damaskin, Langmuir, Henry) were based on the model of non-penetrable interface,
where an adsorbate can substitute only molecules of one solvent. At the interface between two immiscible electrolytes, nonpolar
oil/water interfaces, and liquid membranes amphiphilic molecules can substitute molecules of both solvent and classic isotherms
cannot be used. The generalization of Frumkin isotherm for permeable and non-permeable interfaces, known as the Markin-Volkov
isotherm, gives the possibility to analyze adsorption in a general case. The adsorption isotherms of pentafluorobenzoic acid
at the octane/water interface at different pHs were measured by the drop-weight method. The thermodynamic parameters of pentafluorobenzoic
acid (PFBA) adsorption at octane/water interface were determined. From the measurements of PFBA adsorption, the structure
of the octane/water interface was determined. Substitution of one adsorbed octane molecule requires approximately three adsorbed
PFBA molecules. This result shows that the orientation of solvent molecules at the interface is different from the bulk. Adsorbed
octane molecules have a lateral orientation with respect to the interface. Gibbs free energy of adsorption equilibrium and
thermodynamic parameters of PFBA adsorption show that the adsorption of PFBA at the octane/water interface is accompanied
by a reduction in the attraction between adsorbed PFBA molecules as the pH decreases to the acidic region.
Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 10, pp. 1194–1200.
The text was submitted by the authors in English. 相似文献
998.
Kosaka T Yoneyama-Takazawa T Kubota K Matsuoka T Sato I Sasaki T Tanaka Y 《Journal of mass spectrometry : JMS》2003,38(12):1281-1287
We have developed a method for protein identification with peptide mass fingerprinting and sequence tagging using nano liquid chromatography (LC)/Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). To achieve greater sensitivity, a nanoelectrospray (nano-ES) needle packed with reversed-phase medium was used and connected to the nano-ES ion source of the FTICR mass spectrometer. To obtain peptide sequence tag information, infrared multiphoton dissociation (IRMPD) was carried out in nano-LC/FTICR-MS analysis. The analysis involves alternating nano-ES/FTICR-MS and nano-ES/IRMPD-FTICR-MS scans during a single LC run, which provides sets of parent and fragment ion masses of the proteolytic digest. The utility of this alternating-scan nano-LC/IRMPD-FTICR-MS approach was evaluated by using bovine serum albumin as a standard protein. We applied this approach to the protein identification of rat liver diacetyl-reducing enzyme. It was demonstrated that this enzyme was correctly identified as 3-alpha-hydroxysteroid dehydrogenase by the alternating-scan nano-LC/IRMPD-FTICR-MS approach with accurate peptide mass fingerprinting and peptide sequence tagging. 相似文献
999.
E. Lachowicz B. R
a
ska F. Teixidor H. Meliani M. Barboiu N. Hovnanian 《Journal of membrane science》2002,210(2):279-290
The reactivity of new ligands described as S1, S5, S2O9 (in respect to character and amount of donors) towards metal ions was examined by extraction from HNO3 and HCl media. These ligands were next utilised as carriers for Ag and Pd transport through a supported liquid membrane (SLM). The effect of collecting a greater number of S donors in one molecule and the influence of type of donors (O–S versus S) on efficiency and selectivity of Ag and Pd(II) extraction and transport were examined.
The extraction of Ag from HNO3 solutions increased with increasing amount of S-donors in one molecule (S12O95). For palladium the sequence was different (S512O9). The transport of Ag through SLM impregnated with m-chlorotoluene solution of ionophore increased in the same order as in the case of extraction, whereas for Pd the row was different: S52O91. The highest fluxes of Ag and Pd transported from HNO3 equalled to 5.25×10−7 and 1.37×10−7 mol/m2 s, respectively. Palladium flux depended on stripping solution type (Na2S2O3
1000.
The incongruent solvation of M(I)4P6 species (M(I) = K, Rb, Cs) in liquid ammonia leads to a broad variety of polyphosphides such as P7(3-), P11(3-), and the putatively aromatic P4(2-) and P5(-), which we investigated by using NMR spectroscopy and single-crystal X-ray structure analysis. The structures of Cs2P4 x 2 NH3, (K@[18]crown-6)3K3(P7)2 x 10 NH3, Rb3P7 x 7 NH3, and (Rb@[18]crown-6)3P7 x 6 NH3 are discussed and compared. The electron localization function ELF is used in a comparison of the chemical bonding of various phosphorus species. The variances of the basin populations provide a well-established measure for electron delocalization and therefore aromaticity. While comparable variance is calculated for P4(2-) and P5(-) it is observed in the lone pairs rather than in the basin populations of the bonds as in the prototypical aromatic hydrocarbons such as benzene or the cyclopentadienide anion. For this behavior, the term "lone pair aromaticity" is proposed. 相似文献