全文获取类型
收费全文 | 1076篇 |
免费 | 57篇 |
国内免费 | 365篇 |
专业分类
化学 | 1362篇 |
晶体学 | 24篇 |
力学 | 13篇 |
综合类 | 5篇 |
物理学 | 94篇 |
出版年
2024年 | 1篇 |
2023年 | 19篇 |
2022年 | 33篇 |
2021年 | 47篇 |
2020年 | 48篇 |
2019年 | 46篇 |
2018年 | 49篇 |
2017年 | 58篇 |
2016年 | 53篇 |
2015年 | 46篇 |
2014年 | 47篇 |
2013年 | 108篇 |
2012年 | 67篇 |
2011年 | 67篇 |
2010年 | 66篇 |
2009年 | 80篇 |
2008年 | 65篇 |
2007年 | 62篇 |
2006年 | 55篇 |
2005年 | 55篇 |
2004年 | 55篇 |
2003年 | 62篇 |
2002年 | 40篇 |
2001年 | 30篇 |
2000年 | 33篇 |
1999年 | 26篇 |
1998年 | 35篇 |
1997年 | 19篇 |
1996年 | 26篇 |
1995年 | 19篇 |
1994年 | 13篇 |
1993年 | 9篇 |
1992年 | 11篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有1498条查询结果,搜索用时 15 毫秒
51.
Irene Carpani Mario Berrettoni Massimo Gazzano 《Journal of solid state chemistry》2006,179(12):3981-3988
A Ni, Al hydrotalcite-like compound (Htlc) has been proven an useful host material for an alternative synthesis of a K+-free mixed hexacyanoferrate Ni1.5FeIII(CN)6, which is very difficult to obtain in bulk. The first stage of the procedure consists in the intercalation of hexacyanoferrate(III) inside the Htlc structure. The intercalated Htlc has been treated with a NiNO3 solution. The obtained material has been characterized by XRD, XAS Raman and FT-IR spectroscopy. The voltammetric response of the compound obtained after the complete solubilization of the Htlc host shows a typical fingerprint of nickel hexacyanoferrate material with a very low level of potassium. Elemental analysis confirmed the absence of K+ and thus the occurrence of K+-free nickel hexacyanoferrate (14% yield). 相似文献
52.
P. C. Schulz M. A. Morini M. E. Gschaider de Ferreira 《Colloid and polymer science》1998,276(3):232-238
The system dodecyltrimethylammonium hydroxide (DTAOH)–water was studied by surface tension, ion-selective electrodes and
evaporation in an electrobalance. Results confirmed earlier conclusions about a stepwise aggregation mechanism in DTAOH solutions.
The aggregation process started at a total concentration C
T=(2.51±0.10)×10-4 mol dm-3) which probably corresponds to the formation of dimers. At C
T= (1.300±0.041)×10-3 mol dm-3 there was a change in the surface and evaporation behavior, corresponding to the formation of small, fully ionized aggregates
which grew with increasing concentration. At C
T= (1.108±0.010)×10-2 mol dm-3 the formation of true micelles with hydroxide counterions in the Stern layer did not change significantly the evaporation
and adsorption behavior. This means that between this concentration and C
T=(3.02±0.28)× M28.8n10-2 mol dm-3, the changes in structure were gradual. At the latter concentration there was a sudden change in the monolayer state at the
air/water interface, with a strong surfactant desorption, and a major change in evaporation behavior. The changes are compatible
with the formation of few, large aggregates reducing the total concentration of kinetically independent solute units, which
in turn increased the activity of the solvent. This phenomenon is in agreement with literature information. The reduction
in the evaporation rate of water was mainly due to the reduction of the water activity, caused by colligative effects. The
reduction of the effective area available for evaporation had only a slight effect in water evaporation.
Received: 9 January 1997 Accepted: 19 October 1997 相似文献
53.
A new method for the determination of triphenyltin hydroxide using capillary column gas chromatography with a tin-selective flame photometric detector has been developed. Triphenyltin hydroxide and its potential metabolites are converted to methyl derivatives and separated on glass capillary columns coated with OV-101. Derivatization of triphenyltin hydroxide, triphenyltin chloride, diphenyltin dichloride, phenyltin trichloride, and bis-triphenyltin oxide is nearly quantitative with a minimum of redistribution products. The selectivity of the flame photometric detector is cearly demonstrated by the comparison of chromatographic profiles obtained from using both the flame photometric and flame ionization detectors. The use of this chromatographic system in the analysis of triphenyltin hydroxide in a fortified water sample demonstrates the potential use of this system in organotin residue chemistry. 相似文献
54.
The crucial factor of the reaction of 2,6-di-tert-butylphenol with alkali hydroxides is temperature, depending on which two types of potassium or sodium 2,6-di-tert-butylphenoxides are formed. These types exhibit different catalytic activity in the alkylation of 2,6-di-tert-butylphenol with methyl acrylate. More active forms of 2,6-But
2C6H3OK or 2,6-But
2C6H3ONa are synthesized at temperatures higher than 160 °C and are predominantly the monomers, which dimerize on cooling. The
data of 1H NMR, electronic, and IR spectra for the corresponding forms of 2,6-But
2C6H3OK and 2,6-But
2C6H3ONa isolated in the individual state are in agreement with cyclohexadienone structure. In DMSO or DMF, the dimeric forms of
2,6-di-tert-butylphenoxides react with methyl acrylate to form methyl 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate in 64–92% yield.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2138–2143, December, 2006. 相似文献
55.
A two-stage, no-mix anaerobic digester of 145 L capacity was used to investigate the effect of controlling the pH of the methanogenic
stage on the biogas production and the pollution potential reduction of acid cheese whey. The digester was operated at a 15-d
hydraulic retention time, and a temperature of 35°C. Controlling the pH of the methanogenic stage increased the biogas production
rate and methane yield by 77.77 and 289.00%, respectively. Reductions of up to 32.19, 44.44, and 35.86% in the COD, solids
and nitrogen were achieved. 相似文献
56.
Chenmou Zheng Xinmin Zhang Shan He Qun Fu Deming Lei 《Journal of solid state chemistry》2003,170(2):221-226
V2O3 nanopowder with spherical particles was prepared by reducing pyrolysis of the precursor, (NH4)5[(VO)6(CO3)4(OH)9]·10H2O, in H2 atmosphere. The thermolysis process of the precursor in a H2 flow was investigated by thermogravimetric analysis and differential thermal analysis. The results indicate that pure V2O3 forms at 620°C and crystallizes at 730°C. The effects of various reductive pyrolysis conditions on compositions of V2O3 products were studied. Scanning electron micrographs show that the particles of the V2O3 powder obtained at 650°C for 1 h are spherical about 30 nm in size with more homogeneous distribution. Experiments show that nanopowder has larger adsorption capacity to gases and is more easily reoxidized by air at room temperature than micropowder. Differential scanning calorimetry experiment indicates that the temperature of phase transition of nano-V2O3 powder is −119.5°C on cooling or −99.2°C on heating. The transition heats are −12.55 J g−1 on cooling and 11.42 J g−1 on heating, respectively. 相似文献
57.
Fe2O3/Al2O3催化氧化苯偶姻制备苯偶酰 总被引:13,自引:1,他引:13
考察了几种常用载体负载金属氧化物催化分子氧氧化苯偶姻制备苯偶酰的性能 ,发现氧化铁、三氧化二铝催化活性较高,稳定性较好。以吡啶为溶剂,用483K下 活化的含铁14.8%的氧化铁/三氧化二铝作催化剂,当其用量为苯偶姻用量20% (质量分数),253K下反应1h,苯偶酰平均产率98.1%。用IR,MS,和^1H NMR光 谱对其结构进行了表征。 相似文献
58.
All methionine aminopeptidases exhibit the same conserved metal binding site. The structure of this site with either Co2+ions or Zn2+ions was investigated using density functional theory. The calculations showed that the structure of the site was not influenced by the identity of the metal ions. This was the case for both of the systems studied; one based on the X-ray structure of the human methionine aminopeptidase type 2 (hMetAP-2) and the other based on the X-ray structure of the E. colimethionine aminopeptidase type 1 (eMetAP-1). Another important structural issue is the identity of the bridging oxygen, which is part of either a water molecule or a hydroxide ion. Within the site of hMetAP-2 the results strongly indicate that a hydroxide ion bridges the metal ions. By contrast, the nature of the oxygen bridging the metal ions within the metal binding site of eMetAP-1 cannot be determined based on the results here, due to the similar structural results obtained with a bridging water molecule and a bridging hydroxide ion. 相似文献
59.
Dietrich Mootz Reinhard Seidel 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(1-2):139-157
The tetramethylammonium hydroxide-water system has been studied by low-temperature differential thermal analysis and X-ray powder diffraction. The melting diagram was constructed for concentrations between 66.7 and 100 mol% H2O. It shows the existence and stability ranges of as many as eight crystalline hydrate phases:- and-Me4NOH·2H2O (phase transition at –85°C, decomposition atca. 105°C), Me4NOH·4 H2O (melting point 44°C, incongruent), and-Me4NOH·5 H2O (phase transition at 42°C, melting point 68°C, congruent),- and-Me4NOH·7.5 H2O (phase transition at 6°C, melting point 16°C, incongruent), and Me4NOH·10 H2O (melting point –20°C, incongruent). The structures of all these phases, except the already known one of-Me4NOH·5 H2O, were determined from single-crystal MoK diffractometer data. The decahydrate and the high-temperature forms of the 7.5-hydrate and the pentahydrate are genuinepolyhedral clathrate hydrates, the first ones reported of a strong base. Their mostly novel three-dimensional anionic host structures, formed by the hydrogen-bonded OH– ions and H2O molecules, arefour-connected throughout, in spite of their proton deficiency which is apparently leveled by disorder. Disorder also affects the enclosed cationic Me4N+ guest species. Like the low-temperature form of the pentahydrate, that of the 7.5-hydrate has a clathrate-related, but not fully polyhedral structure, some of the oxygen atoms being three-connected only. The tetrahydrate presents the rare case of both a hydrogen bond of the type OH–...OH2 and a (deprotonated) water-channel structure. This is fully ordered and apart from that can be derived from the polyhedral one of the-pentahydrate just by removing the appropriate number of water molecules from certain positions. The structures of- and-Me4NOH·2 H2O contain identical one-dimensionalspiro chains [HO–(HOH)/42] with the hydroxide protonnot participating in the hydrogen bonding. The Me4N+ ion is ordered in the and disordered in the phase.Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82076 (66 pages).Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena. 相似文献
60.
The triangular phase diagram of the system dodecyltri-methylammonium hydroxide (DTAOH)–dodecanephosphonic acid (H2DP)–water was studied by several techniques. The DTAOH-rich zone could not be studied because DTAOH decomposed when it was
dried. Pure H2DP only forms lamellar mesophases with water. The inclusion of DTAOH in the system produces the appearance of cubic and hexagonal
mesophases. The gradual increase in DTAOH proportion lead to the gradual reduction in the existence of the lamellar mesophase
domain, and increase of the hexagonal liquid crystal domain. At high DTAOH content, the lamellar mesophase disappeared. This
behavior was explained by the gradual destruction of the hydrogen-bonded structure in the polar headgroup layer of liquid
crystal aggregates. H2DP-rich anhydrous crystals were triclinic.
Received: 8 September 1997 Accepted: 17 February 1998 相似文献