全文获取类型
收费全文 | 4611篇 |
免费 | 116篇 |
国内免费 | 18篇 |
专业分类
化学 | 2872篇 |
晶体学 | 17篇 |
力学 | 291篇 |
数学 | 919篇 |
物理学 | 646篇 |
出版年
2023年 | 24篇 |
2022年 | 87篇 |
2021年 | 116篇 |
2020年 | 92篇 |
2019年 | 80篇 |
2018年 | 61篇 |
2017年 | 57篇 |
2016年 | 137篇 |
2015年 | 132篇 |
2014年 | 133篇 |
2013年 | 235篇 |
2012年 | 253篇 |
2011年 | 279篇 |
2010年 | 188篇 |
2009年 | 173篇 |
2008年 | 248篇 |
2007年 | 245篇 |
2006年 | 245篇 |
2005年 | 231篇 |
2004年 | 194篇 |
2003年 | 134篇 |
2002年 | 172篇 |
2001年 | 45篇 |
2000年 | 49篇 |
1999年 | 50篇 |
1998年 | 41篇 |
1997年 | 48篇 |
1996年 | 54篇 |
1995年 | 44篇 |
1994年 | 38篇 |
1993年 | 45篇 |
1992年 | 48篇 |
1991年 | 35篇 |
1990年 | 16篇 |
1989年 | 22篇 |
1988年 | 23篇 |
1987年 | 35篇 |
1986年 | 21篇 |
1985年 | 37篇 |
1984年 | 40篇 |
1983年 | 41篇 |
1982年 | 34篇 |
1981年 | 50篇 |
1980年 | 52篇 |
1979年 | 43篇 |
1978年 | 29篇 |
1977年 | 29篇 |
1976年 | 24篇 |
1975年 | 20篇 |
1967年 | 13篇 |
排序方式: 共有4745条查询结果,搜索用时 0 毫秒
81.
A stereoselective total synthesis of (S)-Virol C and (S)-1-dehydroxyvirol A has been developed, based upon the selective and sequential substitution of the two trimethylsilyl groups of readily available 1,4-bis(trimethylsilyl)-1,3-butadiyne. 相似文献
82.
Capodaglio G Toscano G Barbante C Gambaro A Scarponi G Cescon P 《Annali di chimica》2002,92(3):163-176
The methodology for using DPASV to study cadmium complexation in seawater is evaluated using EDTA as a model ligand and by analysing natural samples. The results show that the methodology gives an accurate evaluation of metal complexation when inert complexes are studied, both as regards the ligand concentration and the conditional stability constant; the error for both the parameters is lower than 10% at a ligand concentration of about 10(-8) M and a conditional stability constant of 10(9) M-1. Cadmium complexes with ligands present in natural seawater show an evident kinetic lability that may lead to underestimation of the conditional stability constant when a working electrode characterised by a very thick diffusion layer is used. The conditional stability constant in one water sample of the Adriatic coast ranged between 0.14 and 1.4 l/nmol using a rotating disk electrode at rotation rates of 300 and 6000 rpm. The results of cadmium complexation obtained for samples collected in coastal seawater show that the ligands present low specificity for the metal. 相似文献
83.
Abstract— Enzyme-generated triplet species transfer energy very efficiently to thylakoid membrane fractions enriched in either photosystem-I or photosystem-II. Independent of the nature of the triplet donor, the emission is always more intense with photosystem-I. Since the fluorescence quantum yield of chlorophyll in PS-I is lower and the rate of energy transfer usually smaller than to chlorophyll in PS-II, the yield of 1 S chlorophylls in PS-I is substantially higher. This is tentatively attributed to more favorable reverse intersystem crossing from an upper triplet state in PS-I. 相似文献
84.
[RhCl(C8H14)2]2 together with the optically active amidines C6H5C(=NR)NHCH(CH3) (C6H5) I–V or their Li derivatives after activation with molecular hydrogen gives catalysts which at room temperature and 1.1 bar H2-pressure hydrogenate the prochiral substrates (Z)-[N-acetylamino]-cinnamic acid, itaconic acid, -methylcinnamic acid, -methylcinnamic aldehyde, and -methylcinnamic alcohol as well as cyclohexene, benzene and toluene. Good hydrogenation activity of the new catalysts is in contrast to low optical induction which only in the hydrogenation of -methylcinnamic alcohol with 1.5 to 2% leads to values different from zero.
3. Mitt.:H. Brunner undW. Pieronczyk, J. Chem. Res., im Druck. 相似文献
85.
Isbli L. Nantes Giuseppe Cilento Etelvino J. H. Bechara Aníbal E. Vercesi† 《Photochemistry and photobiology》1995,62(3):522-527
Plant and animal mitochondria promote the aerobic oxidation of diphenylacetaldehyde (DPAA). This process is accompanied by chemiluminescence and rotenone-insensitive oxygen uptake. Tn rat liver and potato tubers, mitochondrial swelling is concurrently detected. Light emission and oxygen consumption decreased (about 50%) in cytochrome c-depleted mitochondria. A model system–cytochrome c or b5/dihexadecylphosphate liposomes–was also able to oxidize DPAA with parallel reduction of the cytochrome. Reduction of respiratory complex I or I plus II by addition of rotenone or antimycin A, respectively, did not prevent DPAA oxidation. However, when all cytochrome was reduced by addition of cyanide, aldehyde oxidation was completely suppressed. Altogether these data indicate that respiratory cytochromes are responsible for DPAA oxidation with production of excited species and consequent mitochondrial permeabilization. 相似文献
86.
LONG-RANGE TRIPLET-SINGLET ENERGY TRANSFER FROM ENZYME GENERATED TRIPLET ACETONE TO XANTHENE DYES 总被引:1,自引:0,他引:1
Enzyme-generated and protected acetone transfers its energy to xanthene dyes by a nontrivial process. The relative populations of the S1 state are indicative of the operation of a heavy atom effect, being 1:15:100 for fluorescein, eosine and Rose Bengal. On the other hand Stern-Volmer constants and k ET 0 values are similar for the three dyes and are remarkably higher than for collisional processes.
It is tentatively suggested that at least for eosine and Rose Bengal, a triplet-triplet cxciton transfer may occur to populate an upper triplet state of the dye followed by heavy-atom enhanced intersystem crossing to the S1 state. 相似文献
It is tentatively suggested that at least for eosine and Rose Bengal, a triplet-triplet cxciton transfer may occur to populate an upper triplet state of the dye followed by heavy-atom enhanced intersystem crossing to the S
87.
Graziano Guella Ines Mancini Giuseppe Chiasera Francesco Pietra 《Helvetica chimica acta》1992,75(1):303-309
It is shown that in the red seaweed Jaurencia microcladia, collected in the Mediterranean off the torrent Il Rogiolo, the new branched C15 acetogenin rogiolenyne D ( = (+)-(2S,3S,7R))-3-(bromomethyl)-7-[(Z)-1-chlorohexen-3-en-5-nyyl)]-2-ethyl-2,3,6,7-tetrahydrooxepin; (+)- ?3 co-occurs with the already reported rogiolenyne A ((?)- 1 ) and B ((?)- 2a , suggesting the lineage (+)- 3 →(?)- 1 (?)- 2a ,Which is realized here chemically. The relative configurations are established via NMR analysis and chemical transformations as regards the seven-membered ring, while recourse is made to conformational analysis for the side chain. The absolute configuration is established via the Mosher's NMR method applied to the MPTA esters of (?)- 2a . 相似文献
88.
This paper describes the synthesis of a bicyclic beta-amino acid scaffold in both pure enantiomeric forms and its application as chiral auxiliary in an intramolecular version of the Ugi multicomponent reaction (U-5C-4CR) to prepare alpha-amino acid derivatives of both D- and L-series in a straightforward and very stereoselective manner. The mild conditions required for the Ugi condensation and for the removal of the chiral auxiliary make this method very attractive to prepare a wide range of differently structured N-alkylated and unalkylated amino acid derivatives. 相似文献
89.
Maria Grazia Bonicelli Gianfranco Ceccaroni Franco Gauzzi Giuseppe Mariano 《Thermochimica Acta》2005,430(1-2):95-99
Differential scanning calorimetry (DSC) and particle size measurements were carried out on disproportionation products of pure SnO to investigate the fusion and solidification behaviour of Sn droplets and their catalytic nucleation on Sn oxides. If disproportionation reaction takes place at T ≥ 798 K, the products are metallic Sn and SnO2; but for 523 < T < 798 K, SnO2 is replaced by an intermediate oxide (IO) SnxO(1+x). On melting, samples with IO show a drop of melting point of metallic tin due to Gibbs–Thomson effect; no lowering of melting point was observed in samples with SnO2. On the other hand, if solidification occurs in the presence of IO, Tin droplets always displayed three distinct exothermic solidification peaks, but if it takes place in the presence of SnO2, only one exothermic peak is observed. Undercooling values and contact angles were determined for each of the heterogeneous nucleation processes. The different behaviour of metallic Tin droplets was related to the different lattice symmetry of SnO2 and IO, which act as nucleation catalysts. 相似文献
90.
Bonomo RP Cucinotta V Giuffrida A Impellizzeri G Magri A Pappalardo G Rizzarelli E Santoro AM Tabbi G Vagliasindi LI 《Dalton transactions (Cambridge, England : 2003)》2005,(1):150-158
An aqueous solution spectroscopic (Vis and EPR) study of the copper(II) complexes with the Ac-HGGG-NH2 and Ac-PHGGGWGQ-NH2 polypeptides (generically designated as L) suggests square base pyramids ascribable to [Cu(L)H(-2)] complex species, which contain three nitrogen donor atoms, arising from imidazole and peptide groups, in the equatorial plane and for a pseudo-octahedral geometry in the case of [CuLH-3]- and [Cu(L)H-4]2- which have four nitrogen donor atoms in their equatorial plane. The coordination sphere of the copper complex in the [Cu(L)H(-2)] species, which is present at neutral pH values, is completed by two oxygen donor atoms. ESI-MS spectra ascertained that water molecules are not present in the coordination equatorial plane of this latter species, in comparison with other copper(II) complexes with ligands bearing nitrogen and oxygen donor atoms and surely having equatorial water molecules. This indicates the coordination of a carbonyl oxygen atom in the equatorial plane has to be invoked. However, no direct proof about the involvement of a carbonyl group oxygen donor atom apically linked to copper was obtained, due to the flexibility of these structures at room temperature. Additionally, the low A(ll) value leads one to consider another oxygen atom of a carbonyl group being involved in the apical bond to copper in a fast exchange fashion. This apical interaction, which may also involve a water molecule, is more pronounced in the Cu-Ac-HGGG-NH2 than in the analogous Cu-Ac-PHGGGWGQ-NH2 system, probably because of the presence of tryptophan and proline in the polypeptide sequence. 相似文献