全文获取类型
收费全文 | 59909篇 |
免费 | 5324篇 |
国内免费 | 4804篇 |
专业分类
化学 | 26036篇 |
晶体学 | 579篇 |
力学 | 4295篇 |
综合类 | 577篇 |
数学 | 11862篇 |
物理学 | 26688篇 |
出版年
2024年 | 91篇 |
2023年 | 611篇 |
2022年 | 1427篇 |
2021年 | 1448篇 |
2020年 | 1626篇 |
2019年 | 1605篇 |
2018年 | 1426篇 |
2017年 | 1641篇 |
2016年 | 1834篇 |
2015年 | 1496篇 |
2014年 | 2185篇 |
2013年 | 3970篇 |
2012年 | 2649篇 |
2011年 | 2930篇 |
2010年 | 2410篇 |
2009年 | 3454篇 |
2008年 | 3698篇 |
2007年 | 4063篇 |
2006年 | 3490篇 |
2005年 | 2807篇 |
2004年 | 2428篇 |
2003年 | 2609篇 |
2002年 | 3048篇 |
2001年 | 2275篇 |
2000年 | 2139篇 |
1999年 | 1778篇 |
1998年 | 1718篇 |
1997年 | 1038篇 |
1996年 | 985篇 |
1995年 | 827篇 |
1994年 | 878篇 |
1993年 | 633篇 |
1992年 | 720篇 |
1991年 | 486篇 |
1990年 | 453篇 |
1989年 | 352篇 |
1988年 | 316篇 |
1987年 | 304篇 |
1986年 | 270篇 |
1985年 | 264篇 |
1984年 | 261篇 |
1983年 | 155篇 |
1982年 | 211篇 |
1981年 | 192篇 |
1980年 | 129篇 |
1979年 | 154篇 |
1978年 | 144篇 |
1977年 | 124篇 |
1976年 | 80篇 |
1973年 | 64篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
A.?González-PérezEmail author J.?Czapkiewicz J.?M.?Ruso J.?R.?Rodríguez 《Colloid and polymer science》2004,282(10):1169-1173
The specific conductivity of dodecyldimethylbenzylammonium bromide (C12BBr) in aqueous solutions, in the temperature range of 15 to 40 °C, has been measured as a function of molality. The two breaks which were found on the conductivity against molality plots were attributed to the critical micelle concentration, cmc, and second critical micelle concentration, 2nd cmc, respectively. The ratio of the slopes, S, of the three linear fragments on the plots, S2/S1 and S3/S1, was attributed to the degree of ionization of the micelles at cmc and 2nd cmc respectively. It was shown that the values of the 2nd cmc estimated above 27 °C are only apparent due to thermal disintegration of the micelles. In the temperature range of 15 to 27 °C, the values of the 2nd cmc increase gradually and the plot of the 2nd cmc against temperature is concave. The ratio of 2nd cmc/cmc for C12BBr at 25 °C amounts to 15 and appears to be high compared to the literature values for other surfactants. For comparative purposes the cmc and 2nd cmc values were also estimated conductometrically for decyldimethylbenzylammonium bromide (C10BBr) at 25 °C. The 2nd cmc value for this surfactant is higher compared to the value for the C12 homologue by a factor of 2.6.The standard Gibbs free energies of micellization at cmc and at the 2nd cmc were estimated from the experimental data for both surfactants at 25 °C. 相似文献
942.
Luisa Fernanda Rojas Paola Zapata Laura Ruiz-Tirado 《Current Opinion in Green and Sustainable Chemistry》2022
According to the Food and Agriculture Organization of the United Nations, approximately 1.3 billion tons of food is wasted each year, equivalent to approximately one-third of world production. Agri-food wastes are the source of proteins, carbohydrates, lipids, and other essential minerals that have been exploited for value-added products by the development of biorefineries and sustainable business as important elements of circular economies. The innovation and materialization of these types of processes, including the use of disruptive technologies on microbial bioconversion and enzyme technology, such as nanotechnology, metabolic engineering, and multi-omics platforms, increase the perspectives on the waste valorization process. Lignocellulolytic enzymes, pectinases, and proteases are mainly used as catalyzers on agri-food waste treatment, and their production in house might be the trend in near future for agro-industrial countries. Another way to transform the agri-food wastes is via aerobic or anaerobic microbial process from fungal or bacterial cultures; these processes are the key to produce waste enzymes. 相似文献
943.
在乙腈溶液中, 由混合价三核锰配合物[Mn3O(ClCH2COO)6(py)2]•(H2O) (py为吡啶)与2,2′-联吡啶(bipy)反应合成了混合价(Mn3IIIMnII)四核锰配合物[Mn4O2(ClCH2COO)7(bipy)2]•H2O. 采用元素分析、红外光谱、热分析和X射线单晶衍射法确定了其组成和结构. 标题化合物晶体属于三斜晶系, 空间群P-1, 晶胞参数: a=0.89854(13) nm, b=1.4027(2) nm, c=1.9037(3) nm, α=93.518(3)°, β=96.736(3)°, γ=94.875(3)°, V=2.3680(6) nm3, Z=2, Dc=1.734 g/cm3, F(000)=1238, GOF=1.036, R1=0.0592, wR2=0.1162 [I>2σ(I)]. 在标题化合物中, 配位结构单元中心为一蝶型[Mn4(μ3-O)2]7+多核簇, 含有2个Mn3(μ3-O)单元, 具有近似C2对称轴. 4个Mn离子均为六配位, 外围配体为7个氯乙酸根和2个2,2′-联吡啶, 处于变形的八面体环境. 变温磁化率研究表明标题化合物在整体上表现为反铁磁性耦合作用, 但在低温下的磁相互作用较为复杂. 相似文献
944.
Summary Packings and stationary phases applied to high resolution separations of proteins, enzymes, and nucleic acids must satisfy
a series of distinct criteria that are different from those usually required by HPLC of low molecular weight non-biologically
active analytes. These requirements have been met through substantial improvements in classical gel media together with novel
developments in silica supports, and have led to a family of products with tailor-made and reproducible properties. Supports
consisting of cross-linked organic gels, and inorganic materials (mostly silicas) are now available with graduated particle
sizes, pore sizes, porosities and surface areas as well as non-porous beads. A whole range of stationary phases, such as reversed
phase, hydrophobic interaction, ion exchanger and affinity packings, were designed for application as chemical sensors for
biopolymer recognition in adsorptive chromatography. The phase systems are operated in the gradient mode, giving high resolution
and high peak capacities. In addition, aqueous liquid-liquid partitioning systems have been developed for the fractionation
of proteins and nucleic acids. Size exclusion media complete the set of HPLC variants enabling a discrimination of proteins
according to their size and shape in an isocratic elution mode. Basically, protein purification and isolation is a multistage
process where-by the HPLC variants are combined in a logistic sequence, utilizing the different selectivities of the phase
systems and thus maximising resolution, speed and throughput. 相似文献
945.
Sourav Pal 《Theoretical chemistry accounts》1985,68(5):379-388
In this paper, we analyse the algebraic structure of the equations for calculating the first order static properties using several approximate versions of Coupled Cluster (CC) methods. In particular, the non-variational and the variational method using a CC wavefunction corresponding to an appropriately defined perturbed Hamiltonian as well as the simple expectation value expression using a CC stationary state are studied under different approximations. Two different models are proposed: (a) use of maximum overlap orbitals where the pertinent approximations are TT
2, T
(1) T
2
(1), (b) use of Hartree-Fock orbitals and T(T
1+T
2), T
(1)(T
1
(1)
+T
2
(1)
) approximations. It is analytically shown that in both these models certain approximate versions of the methods under purview yield identical results for first order static properties.NCL Communication No. 3725 相似文献
946.
Low-dimensional systems are formed by planar metal dithiolene complexes which stack as columnar structures in the solid state.
Stronger interactions among units within a chain leads to highly anisotropic magnetic properties. The magnetic effects are
a manifestation of exchange interaction,J and can be studied through detailedepr techniques in conjunction with magnetic susceptibility and x-ray crystal structure. A brief review of such studies carried
out mostly in our laboratory is presented along with the relevant background materials. 相似文献
947.
N. T. Ul'chenko N. P. Bekker T. V. Chernenko N. K. Yuldasheva A. I. Glushenkova 《Chemistry of Natural Compounds》2003,39(3):249-252
Seed characteristics and the lipid and fatty-acid compositions were determined for the new cotton varieties ASh-25, Omad, 9771-I, Termez-43, and Bukhara-6. 相似文献
948.
The reaction of 1-alkynylcyclobutanols with aryl iodides in the presence of Pd(OAc)2 and Et3N in acetonitrile at 80°C for 24 h gives 2-disubstituted methylenecyclopentan-1-ones in modest to good yields. The tandem insertion-ring expansion process proceeds via the formation of an alkynyl π-complex, followed by migration of a carbon-carbon bond of the tert-alkanol to form the cyclopentanones stereoselectively. 相似文献
949.
A sensitive and selective method using liquid chromatography with electrospray ionization mass spectrometric detection was
developed for the quantification of bilobalide and ginkgolides in canine plasma. The analytes were extracted with diethyl
ether-dichloromethane-isopropanol (6:3:1, v/v) after spiking the samples with daidzein (internal standard). The lower limit
of quantification (LLOQ) of the method was 2.5 μg L−1 for ginkgolide B and 10.0 μg L−1 for bilabolide, ginkgolide A and ginkgolide C. The accuracy of the method was within 15% of the actual values over a wide
range of plasma concentrations. The intra-day and inter-day precision was better than 15% (R.S.D.). Finally, the LC-ESI-MS
method was successfully applied to study the pharmacokinetics of ginkgolides and bilabolide after administration of Ginkgo biloba extracts to dogs. 相似文献
950.
Chelsea N. Widener Alexandria N. Bone Mykhaylo Ozerov Rachael Richardson 路正光 Komalavalli Thirunavukkuarasu Dmitry Smirnov 陈学太 薛子陵 《无机化学学报》2020,36(6):1149-1156
最近Ruamps和同事发现三角双锥构型的Ni(Ⅱ)配合物[Ni(Me6tren)Cl]ClO4(1,Me6tren=tris(2-(dimethylamino)ethyl)amine)具有大的单轴磁各向异性(J.Am.Chem.Soc.,2013,135:3017-3026)。他们利用HF-EPR研究获得横向零场分裂(ZFS)参数E=1.56(5)cm-1但未能确定轴向零场分裂参数D。在本工作中,我们利用0~17.5 T和5 K的变磁场远红外光谱(FIRMS)来检测自旋基态S=1中的MS=±1和MS=0态之间的磁跃迁。在FIRMS中直接观察到Zeeman分裂态之间的跃迁,得出轴向ZFS参数D=-110.7(3)cm-1。我们对1的晶体结构进行了Hirshfeld表面分析,揭示了1分子中的阳离子与阴离子之间以及分子之间的相互作用。 相似文献