全文获取类型
收费全文 | 3896篇 |
免费 | 124篇 |
国内免费 | 10篇 |
专业分类
化学 | 3176篇 |
晶体学 | 99篇 |
力学 | 171篇 |
数学 | 106篇 |
物理学 | 478篇 |
出版年
2023年 | 23篇 |
2022年 | 36篇 |
2021年 | 53篇 |
2020年 | 72篇 |
2019年 | 95篇 |
2018年 | 97篇 |
2017年 | 74篇 |
2016年 | 126篇 |
2015年 | 90篇 |
2014年 | 173篇 |
2013年 | 431篇 |
2012年 | 268篇 |
2011年 | 234篇 |
2010年 | 146篇 |
2009年 | 138篇 |
2008年 | 224篇 |
2007年 | 218篇 |
2006年 | 159篇 |
2005年 | 162篇 |
2004年 | 151篇 |
2003年 | 131篇 |
2002年 | 112篇 |
2001年 | 41篇 |
2000年 | 43篇 |
1999年 | 34篇 |
1998年 | 21篇 |
1997年 | 24篇 |
1996年 | 41篇 |
1995年 | 25篇 |
1994年 | 30篇 |
1993年 | 30篇 |
1992年 | 27篇 |
1991年 | 24篇 |
1990年 | 38篇 |
1989年 | 30篇 |
1988年 | 25篇 |
1987年 | 29篇 |
1986年 | 29篇 |
1985年 | 37篇 |
1984年 | 42篇 |
1983年 | 30篇 |
1982年 | 28篇 |
1981年 | 25篇 |
1980年 | 23篇 |
1979年 | 18篇 |
1978年 | 14篇 |
1977年 | 21篇 |
1976年 | 16篇 |
1975年 | 18篇 |
1974年 | 9篇 |
排序方式: 共有4030条查询结果,搜索用时 46 毫秒
981.
Attempts to synthesise iso-cladospolide-B, cladospolide-B and cladospolide-C resulted in macrolides 1, 2 and 4 along with butenolide 3. Of the three stereogenic centres, the C-4/C-5 vic-diol was obtained from tartaric acid and d-glucose, while the C-11 stereocentre was created by Jacobsen’s method. 相似文献
982.
983.
Lakshmi VV Reddy TJ Murty MR Prabhakar S Vairamani M 《Rapid communications in mass spectrometry : RCM》2006,20(14):2209-2214
The detection and identification of degradation products of scheduled chemicals, which are characteristic markers of Chemical Warfare agents (CWAs), plays a key role in verification analysis. Identification of such non-scheduled but specific markers of CWAs helps in deciphering the kind of agent that was present in the sample submitted for off-site analysis. This paper describes the stability of N,N-dialkylaminoethyl-2-chlorides, which are precursors for highly toxic chemicals like VX, in different solvents. These compounds are stable in chloroform, acetonitrile, hexane and dichloromethane but tend to undergo in situ nucleophilic substitution reaction in the presence of alcohols giving the corresponding alkyl ether. The study shows that N,N-dialkylaminoethyl alkyl ethers can be used as markers of N,N-dialkylaminoethyl-2-chlorides. A detailed degradation study of these compounds in the presence of alcohols was carried out and it was found that the reaction follows pseudo-first order kinetics. Electron ionization mass spectral data for the methyl ethers of all the compounds are briefly discussed. 相似文献
984.
Reddy PN Srikanth R Srinivas R Sharma VU Sharma GV Nagendar P 《Rapid communications in mass spectrometry : RCM》2006,20(22):3351-3360
Dissociation pathways of a series of alkali-cationized hybrid peptides, viz., Boc-alpha,beta- and -beta,alpha-carbopeptides, synthesized from C-linked carbo-beta3-amino acids [Caa (S)] and alpha-alanine (L-Ala), have been investigated by electrospray ionization tandem mass spectrometry. The positional isomers (six pairs) of the cationized alpha,beta- and beta,alpha-peptides can be differentiated by the collision-induced dissociation (CID) spectra of their [M + Cat-Boc + H]+ ions which give characteristic series of alkali-cationized C- (x(n)+, y(n)+, z(n)+) and N-terminal (a(n)+, b(n)+, c(n)+) ions. Another noteworthy difference is cationized beta,alpha-peptides eliminate a molecule of ammonia whereas this pathway is absent for alpha,beta-peptides. This is useful for identifying the presence of a beta-amino acid at the N-terminus. The CID spectra of [M + Cat-Boc + H]+ ions of these peptide acids show abundant rearrangement [b(n) + 17 + Cat]+ (n = 1 to n-1) ions which is diagnostic for distinguishing between alpha- and beta-amino acid at the C-terminus. MS(n) experiments of [b(n) + Li-H]+ ions from these hybrid peptides showed the loss of CO and 72 u giving rise to [a(n) + Li-H]+ and cationized nitrile product ions which render support to earlier proposals that b(n)+ or [b(n) + Cat-H]+ ions have protonated or cationized oxazolinone structures, respectively. 相似文献
985.
Reddy TJ Prabhakar S Ravi Kumar M Saradhi UV Vairamani M 《Journal of mass spectrometry : JMS》2006,41(1):59-70
The electron impact (EI) mass spectra of a series of N,N-dialkyl-aminoethyl-2-chlorides, N(R(1))(R(2))-CH(2)-CH(2)Cl and trimethylsilyl ethers of N,N-dialkyl aminoethane-2-ols, N(R(1))(R(2))-CH(2)-CH(2)-O-Si(CH(3))(3), where R(1) and R(2) = methyl, ethyl, propyl and isopropyl, which are precursors of VX type of compounds, are studied. All the compounds (1-20) show abundant molecular ions, in addition to a weak [M - H](+) ion, except the N,N-diisopropyl group containing compounds (8 and 18). A general EI fragmentation pattern for the above two series of compounds is discussed. The observed fragment ions are due to simple homolytic cleavages, and they are distinct to allow the identification of the compounds unequivocally including those of isomeric compounds. The primary fragmentation of compounds 1-20 is beta-cleavage, i.e. homolytic cleavage of C-C bond, which is linked to the nitrogen atom. Three types of beta-cleavages are possible for these compounds, in which the abundance of beta-cleavage product ions is found to depend on the size and structure of the alkyl group attached to nitrogen. The alpha-cleavage fragment ions are found only for N,N-dialkyl aminoethyl-2-chlorides but are absent in the corresponding trimethylsilyl ethers of N,N-dialkyl aminoethane-2-ols. The retention indices are calculated for all the studied compounds (1-20) and are in the ranges of 750.38-1079.24 for 1-10 and 905.23-1190.25 for 11-20. 相似文献
986.
R. Venkateswarlu C. Kamakshi S.G.A. Moinuddin D. Rama Sekhara Reddy A. Pelter M.B. Hursthouse M.E. Light 《Tetrahedron》2006,62(18):4463-4473
Treatment of diphyllin 4 with phenyliodonium diacetate (PIDA) in methanol affords a 1-methoxy-1-aryl-4-oxonaphthalene lactone 6. Reduction of 6 with lithium aluminium hydride yields, inter alia, 3,4-dihydrodiphyllin 13, while reaction with sodium in ethanol yields 8 as a major product. These reactions illustrate that selective oxidation followed by reduction provides a facile route for the conversion of a 1-arylnaphthalene lactone to novel functionalised naphthalene and dihydronaphthalene derivatives. Of particular interest is that the oxidation indirectly activates the methylene position (C-10) of the γ-lactone, which may then potentially be substituted to give a new series of lignans. Reaction of 6 with hydroxylamine and benzyloxyamine also proceeds by way of initial attack at C-10. 相似文献
987.
Reddy AR Krishnamurthy NV Bhudevi B 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,63(3):700-708
Electron donor-acceptor molecular complexes of a few phenolic donors with some quinonoid and tetracyanoethylene acceptors have been prepared by two different methods, i.e., by simple grinding of the respective component pair in the solid-state and in solution. Both the methods yielded identical dark colored 1:1 stoichiometric complexes. Spectral studies revealed that the complexes are ionic in nature. The g values obtained in ESR spectral studies for all these molecular adducts vary between 2.000 and 2.022, confirming the free radical nature of the adducts. The electronic absorption spectral studies proved that the donor-acceptor complexes formed initially, exhibit new electronic transitions at longer wavelengths, are less stable and disassociate readily into ionic type of adducts. The absorption maximum at longer wavelengths, i.e. >or=550 nm, are assigned to the charge transfer complexes, while the new transition at around 410 +/- 5 nm is attributed to the anion radical of the adducts. The ease of complexation not only depends on the ionization potential and electron affinities of the phenolic donors and the acceptors but is also structure sensitive. Complexation is confirmed by the shift in IR absorption of the phenolic hydroxyl group and the carbonyl group of quinone acceptors and the cyano group of tetracyanoethylene. Proton magnetic resonance studies indicate an interaction between the phenolic donors and acceptors on basis of the altered chemical shifts. Further, IR and NMR studies show that the stability of the adducts is governed not only by the charge transfer interaction but also by hydrogen bonding. 相似文献
988.
Reddy SL Reddy NC Reddy GS Reddy BJ Frost RL 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,65(3-4):684-688
Clinohumite, a humite group mineral, originated from Pamir Mountains, USSR, is used in the present work. Optical absorption, electron paramagnetic resonance (EPR), near infrared (NIR) and M?ssbauer techniques are used in the characterization of the mineral sample. The optical absorption spectrum indicates that Fe(II) impurity is present in two sites with distorted octahedral structure. NIR results are attributed to water fundamentals. EPR studies on powder sample confirm the presence of Mn(II) in three different sites and also an iron impurity. M?ssbauer studies confirm the presence of iron impurity in two different sites. 相似文献
989.
2-(o-Hydroxyphenyl)-1,8-naphthyridine (HN), 2-(4-hydroxy-6-methylpyran-2-one-3-yl)-1,8-naphthyridine (HMPN) and 2-(benzimidazol-2-yl)-1,8-naphthyridine(BN) react with acetates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) to yield metal ion complexes of definite composition. These compounds were characterized by elemental analyses, molar conductivity, magnetic susceptibility measurements, thermal studies, IR, UV-visible, NMR and mass spectral investigations. The complexes are found to have the formulae [M(HN)2(H2O)2], [M(HMPN)2(H2O)2] and [M(BN)2(OAc)2], respectively. 相似文献
990.