全文获取类型
收费全文 | 3381篇 |
免费 | 131篇 |
国内免费 | 11篇 |
专业分类
化学 | 2317篇 |
晶体学 | 35篇 |
力学 | 101篇 |
数学 | 463篇 |
物理学 | 607篇 |
出版年
2022年 | 20篇 |
2021年 | 36篇 |
2020年 | 37篇 |
2019年 | 44篇 |
2018年 | 33篇 |
2017年 | 20篇 |
2016年 | 76篇 |
2015年 | 76篇 |
2014年 | 115篇 |
2013年 | 196篇 |
2012年 | 180篇 |
2011年 | 228篇 |
2010年 | 120篇 |
2009年 | 104篇 |
2008年 | 197篇 |
2007年 | 193篇 |
2006年 | 206篇 |
2005年 | 170篇 |
2004年 | 167篇 |
2003年 | 124篇 |
2002年 | 116篇 |
2001年 | 36篇 |
2000年 | 52篇 |
1999年 | 35篇 |
1998年 | 35篇 |
1997年 | 37篇 |
1996年 | 45篇 |
1995年 | 33篇 |
1994年 | 34篇 |
1993年 | 36篇 |
1992年 | 20篇 |
1991年 | 25篇 |
1990年 | 25篇 |
1989年 | 35篇 |
1988年 | 29篇 |
1987年 | 21篇 |
1986年 | 23篇 |
1985年 | 44篇 |
1984年 | 43篇 |
1983年 | 31篇 |
1982年 | 33篇 |
1981年 | 41篇 |
1980年 | 46篇 |
1979年 | 36篇 |
1978年 | 28篇 |
1977年 | 38篇 |
1976年 | 22篇 |
1975年 | 28篇 |
1974年 | 31篇 |
1973年 | 32篇 |
排序方式: 共有3523条查询结果,搜索用时 140 毫秒
61.
During electrolysis of molten KF-2HF, strongly adherent fluorine bubbles are generated at the surface of carbon anode. The current was passing even if the horizontal anode was fully covered with gas film. The formation and growth of gas bubbles were studied by transient electrochemical techniques. It was observed that the fluorine bubbles do not have the spherical cap shape predicted by the classical theory. The curvature radius of the interface profile is not constant, the edge of the bubble being flat with a contact angle close to zero. The results are interpreted in the frame of a model which takes into account the predominant role of the interfacial properties. 相似文献
62.
Baber RA Charmant JP Cook AJ Farthing NE Haddow MF Norman NC Orpen AG Russell CA Slattery JM 《Dalton transactions (Cambridge, England : 2003)》2005,(19):3137-3139
Treatment of the diborane(4) compound B(2)(NMe(2))(4) with aniline or 2,6-dimethylaniline results in the primary amido compounds B(2)(NHR)(4)(R = Ph, 2,6-Me(2)C(6)H(3)); subsequent treatment with n-BuLi in toluene in each case affords the first examples of anionic imidodiborates namely Li(4)(thf)(6)B(2)(NPh)(4) and Li(4)(thf)(4)B(2)(N-2,6-Me(2)C(6)H(3))(4); all complexes have been characterised crystallographically. 相似文献
63.
Edmond Amouyal Bertrand Zidler Patrick Keller Alec Moradpour 《Chemical physics letters》1980,74(2):314-317
Rate constants kq for the quenching of the excited state of Ru(bipy)32+ by a series of viologen salts having different redox potential E have been determined in deaerated aqueous solutions at pH = 5 by laser flash photolysis. The kq values are found to decrease with increasing —E and to correlate with the reaction free-energy change ΔG. Such a correlation is shown to be consistent with the Rehm—Weller model for electron-transfer reactions. 相似文献
64.
In order to find support for the validity of the hypothesis proposed by one of us regarding the different natures of the bonds in the four successive complexes formed between Ag+ and thiourea, the corresponding enthalpies are verified by direct calorimetry.Furthermore, because the influence of substituent groups on the nitrogen atoms may help to characterize the donor atom. the calorimetric enthalpies and potentiometric free energies of complexation between Ag+ and N-methylthiourea, N,N′- dimethylthiourea and N,N′-diethylthiourea have also been determined at 25°C, in aqueous medium of ionic strength μ = 0.5 M KNO3. 相似文献
65.
Cosper MM Jameson GN Davydov R Eidsness MK Hoffman BM Huynh BH Johnson MK 《Journal of the American Chemical Society》2002,124(47):14006-14007
The combination of resonance Raman, electron paramagnetic resonance and M?ssbauer spectroscopies has been used to investigate the effect of S-adenosyl-l-methionine (SAM) on the spectroscopic properties of the [4Fe-4S]2+ cluster in biotin synthase. The results indicate that SAM interacts directly at a unique iron site of the [4Fe-4S]2+ cluster in BioB and support the hypothesis of a common inner-sphere mechanism for the reductive cleavage of SAM in the radical SAM family of Fe-S enzymes. 相似文献
66.
Guy Guelachvili K. Narahari Rao Richard H. Tipping Brenda P. Winnewisser Manfred Winnewisser 《Mikrochimica acta》1988,95(1-6):339-343
This paper reports the observation of the far infrared absorption spectrum of a single crystal of N2, measured over absorption paths of 4 cm (lengthwise) and 2 cm (across the crystal). The crystal chamber, with quartz windows, was immersed in a flow of cold helium gas. The spectrum from 20 to 120 cm–1 was recorded in the liquid phase, the-phase, and over the full temperature range of the-phase (35.6–2.0 K) with a Fourier transform spectrometer. The spectral resolution, which was not instrument-limited, and the large path allowed the observation of more detailed multiphonon-transition structure in the spectrum of the-phase than has previously been observed. 相似文献
67.
Loferer MJ Webb BM Grant GH Liedl KR 《Journal of the American Chemical Society》2003,125(4):1072-1078
QM/MM methods were used to study the isomerization step from (2R)-methylmalonyl-CoA to succinyl-CoA. A pathway via a "fragmentation-recombination" mechanism is ruled out on energetic grounds. For the other radicalic pathway, involving an addition recombination step, geometries and vibrational contributions have been determined, and a barrier height of 11.70 kcal/mol was found. The effect of adjacent hydrogen-donating groups was found to reduce the energy barrier by 1-2 kcal/mol each and thus to provide a significant catalytic effect for this reaction. By means of molecular dynamics studies, the stereochemistry of the methylmalonyl-CoA mutase catalyzed reaction was examined. It is shown that TYR89 is essential for maintaining stereoselectivity of the abstraction of a hydrogen in the backreaction. The subsequent selective formation of one isomer of methylmalonyl-CoA is probably due to the presence of a bulky side chain. 相似文献
68.
Lithium diisopropylamide reacts with 2-fluoropyridine at low temperature: regioselectivity is excellent and metallation occurs without side reactions such as nucleophilic attack. 2-Fluoro-3-lithiopyridine is formed and with aldehydes it gives the corresponding fluorinated alcohols which are then selectively oxidized. Halogen substitution using amines leads to various 3-oxoalkyl- or 3-aroyl-2-aminopyridines. 相似文献
69.
A series of 2-substituted 4H-3,1-benzoxazinones and 2,3-disubstituted 4-(3H)quinazolinones have been synthesized in mild conditions by the use of triphenyl phosphite and pyridine as cyclising medium. Benzox-azinones are produced either by ring closure of 2-(acylamino)benzoic acids or in the reaction of benzoic acid with anthranilic acids. In the presence of aniline, the reaction leads to quinazolinones. 相似文献
70.
Musangu Mbuyi Michel Evers Guy Tihange Andr Luxen Lon Christiaens 《Tetrahedron letters》1983,24(52):5873-5876
We describe the synthesis of a new heterocyclic system : the 1,3-benzotellurazole, and some of its substituted derivatives. 相似文献