全文获取类型
收费全文 | 101505篇 |
免费 | 3296篇 |
国内免费 | 2648篇 |
专业分类
化学 | 33196篇 |
晶体学 | 945篇 |
力学 | 7433篇 |
综合类 | 134篇 |
数学 | 33461篇 |
物理学 | 19537篇 |
综合类 | 12743篇 |
出版年
2024年 | 59篇 |
2023年 | 262篇 |
2022年 | 441篇 |
2021年 | 555篇 |
2020年 | 554篇 |
2019年 | 550篇 |
2018年 | 11048篇 |
2017年 | 10894篇 |
2016年 | 6879篇 |
2015年 | 1678篇 |
2014年 | 1426篇 |
2013年 | 1633篇 |
2012年 | 5524篇 |
2011年 | 12738篇 |
2010年 | 7554篇 |
2009年 | 7793篇 |
2008年 | 8527篇 |
2007年 | 10677篇 |
2006年 | 1464篇 |
2005年 | 2352篇 |
2004年 | 2369篇 |
2003年 | 2644篇 |
2002年 | 1745篇 |
2001年 | 859篇 |
2000年 | 873篇 |
1999年 | 717篇 |
1998年 | 646篇 |
1997年 | 544篇 |
1996年 | 601篇 |
1995年 | 466篇 |
1994年 | 345篇 |
1993年 | 332篇 |
1992年 | 258篇 |
1991年 | 266篇 |
1990年 | 214篇 |
1989年 | 187篇 |
1988年 | 164篇 |
1987年 | 141篇 |
1986年 | 122篇 |
1985年 | 78篇 |
1984年 | 62篇 |
1983年 | 59篇 |
1982年 | 55篇 |
1981年 | 48篇 |
1980年 | 52篇 |
1979年 | 48篇 |
1914年 | 45篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
951.
标题化合物C24H29NO4?1/2C2H5OH稨2O)由香兰素、5,5-二甲基-1,3-环己二酮、醋酸铵在微波辐射下干反应并经95%乙醇重结晶而得C24H29NO4穀2(C2H5OH稨2O)晶体。结构通过单晶X-射线衍射法确定,其晶体属单斜晶系,空间群P21/n, a = 9.810(2), b = 14.516(3), c = 17.008(3) ? b = 101.03(2), V = 2377.2(8) ?, Z = 4, Mr = 427.52, Dc = 1.195 g/cm3 , m(MoKa) = 0.082 mm-1, F(000) = 920。晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子为R = 0.0406, wR = 0.0892。X-射线衍射分析结果表明,吡啶环和与之稠合的2个六员环均为信封式构象。 相似文献
952.
The equilibrium constants, K
2, have been determined for the proton-transfer reactions of 1-phenacylquinolinium ion, PHQ+, with several amines {triethylamine (TEA), N,N,N′,N′-tetramethylethylenediamine (ED), N,N,N′, N′-tetramethylpropanediamine (PD), N,N,N′,N′-tetramethylbutanediamine (BD), and 1,8-bis(dimethylamino-naphthalene (DMAN)} in acetonitrile (AN), AN-tetrahydrofuran (THF)
and AN-ethanol (EtOH) mixtures. The reaction was followed spectrophotometrically using a stopped-flow technique. The K
2 value decreased for DMAN and increased for TEA with increasing vol-% of THF in AN-THF mixtures. The changes in the K
2 value for ED, PD and BD changed in the order: ED, PD and BD from a pattern similar to TEA to a pattern similar to DMAN. The
change in the K
2 value for DMAN with increasing vol-% of THF in AN-THF mixtures was explained by the effect of polarity on the stability of
P−Q+ (the deprotonated product of PHQ+). The effect of THF on the K
2 value is consistent with that of the peak wavelength of the absorption spectrum of P−Q+. The change in the K
2 value for TEA, ED, PD and BD depended on the structures of the protonated bases, one of the products for this reaction. The
effect of EtOH on the K
2 value for DMAN was examined in ternary EtOH-THF-AN mixtures that contain different amounts of EtOH and whose relative permittivities
were adjusted to that of EtOH. The K
2 value increased with increasing vol-% of EtOH because of the stabilization of P−Q+ upon the formation of the hydrogen-bonded complex with EtOH. The absorption spectrum of P−Q+ demonstrated a blue shift as the vol-% of EtOH increased. 相似文献
953.
The total energy of all π-electrons in a conjugated hydrocarbon (within the framework of HMO approximation) is the sum of the absolute value of all
the eigenvalues of its corresponding graph. In this paper, we consider “double hexagonal chains” as benzenoids constructed
by successive fusions of successive naphthalenes along a zig–zag sequence of triples of edges as appear on opposite sides
of each naphthalene unit. It is shown that if the fusions are such as to give a polyaceacene then the total π-electron energy
is the minimum from among all the double hexagonal chains with the same number of naphthalene units.
相似文献
954.
A reversed-phase liquid chromatographic (RPLC) method has been developed for determination of arabinosylcytosin (Ara-C) and
its metabolite 1-β-D-arabinofuranosyluracil (Ara-U) on a 250 mm × 4.6 mm i.d., 5 μm particle, Diamonsil C18 column. The mobile phase was a mixture of 5% methanol and 95% 10 mmol L−1 phosphate buffer adjusted to pH 5.5. The flow-rate was 1.0 mL min−1 and the injection volume 20 μL. Eluting compounds were detected at 270 nm by use of an ultraviolet detector. Under these
LC conditions cyclophosphamide (CTX) and pirarubicin (THP), two other medicines given with Ara-C in clinical treatment, do
not interfere with measurement of Ara-C and Ara-U. Individual calibration plots of peak area against concentration generated
from analysis of standard solutions were used to calculate the concentrations of Ara-C and Ara-U in sample solutions. The
calibration plot was linear in the range 2.5–100 μg mL−1, the average recovery of Ara-C and Ara-U was more than 98% (RSD < 2.5%), and between-day and within-day precision, expressed as relative standard deviation (RSD), were below 4.0%. LOQ for both Ara-C and Ara-U was 2 μg mL−1. The method is rapid, simple, accurate and reproducible, and especially useful for application to patient samples. 相似文献
955.
The ring closing metathesis on appropriate vinyl or allyl aminoboranes (1 or 2) gives azaboracycloalkenes (3 or 4) which can be converted to azaborolides (5) or azaborines (6). 相似文献
956.
Yao Zhu Siyuan Fang Shaoqin Chen Youjie Tong Chunling Wang Yun Hang Hu 《Chemical science》2021,12(16):5825
Photocatalytic ethane conversion into value-added chemicals is a great challenge especially under visible light irradiation. The production of ethyl hydroperoxide (CH3CH2OOH), which is a promising radical reservoir for regulating the oxidative stress in cells, is even more challenging due to its facile decomposition. Here, we demonstrated a design of a highly efficient visible-light-responsive photocatalyst, Au/WO3, for ethane oxidation into CH3CH2OOH, achieving an impressive yield of 1887 μmol gcat−1 in two hours under visible light irradiation at room temperature for the first time. Furthermore, thermal energy was introduced into the photocatalytic system to increase the driving force for ethane oxidation, enhancing CH3CH2OOH production by six times to 11 233 μmol gcat−1 at 100 °C and achieving a significant apparent quantum efficiency of 17.9% at 450 nm. In addition, trapping active species and isotope-labeling reactants revealed the reaction pathway. These findings pave the way for scalable ethane conversion into CH3CH2OOH as a potential anticancer drug.Highly efficient visible-light driven photocatalytic oxidation of ethane into ethyl hydroperoxide was realized for the first time over Au/WO3. 相似文献
957.
Grażyna Janowska Teresa Mikołajczyk Dorota Wołowska-Czapnik M. Boguń 《Journal of Thermal Analysis and Calorimetry》2005,82(1):129-135
The paper discusses the thermal properties of alginate fibres made from alginic acid or sodium alginate and from alginates
substituted with divalent metal ions during the fibre-forming stage. Alginate fibres with an addition of silica nanoparticles
have also been examined. The selection of fibre-forming parameters was intended to obtain the best either sorption or strength
properties depending on the specific fibre application. Thermal curves of the fibres under investigations obtained by under
air atmosphere and differential scanning calorimetry (DSC) under neutral gas atmosphere have been interpreted from the view
of physical and chemical changes in the fibre-forming material. Based on thermogravimetric curves, the fibre thermal stability
indices have been determined. It has been found that the addition of silica nanoparticles exerts a positive influence on the
thermal properties of the examined fibres. 相似文献
958.
Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy
Concepción López Rosa M. Claramunt M. Ángeles García José Elguero 《Central European Journal of Chemistry》2004,2(4):660-671
Equimolar mixtures of 3,5-dimethylpyrazole (1) with four NH-imidazoles (2–5) have been studied by13C and 15N CPMAS NMR and by DSC. In three cases, the solid mixture behaves as the sum of the individual components [imidazole (2), 2-methylimidazole (3) and 2,4(5)-dimethylimidazole (5)]. In one case [4,5-dimethylimidazole (4)], the mixture corresponds to a new species in which the dynamic behavior of1 no longer exists. 相似文献
959.
Summary. Phenoxyacetic acid distribution in two-phase systems n-aliphatic hydrocarbon (C5–C8) – water and its dimerization in organic phase were investigated. The values of distribution coefficient (D
HR), distribution constant (K
D), and dimerization constant (K
dim) of acid were obtained. The empirical correlations of these quantities with Hildebrand solubility parameter of organic solvents were established. The influence of pH of the aqueous phase as well as the polarity of the applied organic solvents on phenoxyacetic acid physical chemistry in
the two-phase systems was described. 相似文献
960.
Ronaldo Santos da Silva Maria Inês Basso Bernardi Antonio Carlos Hernandes 《Journal of Sol-Gel Science and Technology》2007,42(2):173-179
In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba0.77Ca0.23TiO3 nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis,
morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through
thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy.
In summary, Ba0.77Ca0.23TiO3 nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity
and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions
with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution
(30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the
chelation in higher pHs. 相似文献