全文获取类型
收费全文 | 40003篇 |
免费 | 718篇 |
国内免费 | 328篇 |
专业分类
化学 | 18737篇 |
晶体学 | 294篇 |
力学 | 1643篇 |
综合类 | 12篇 |
数学 | 10709篇 |
物理学 | 9654篇 |
出版年
2023年 | 95篇 |
2022年 | 148篇 |
2021年 | 221篇 |
2020年 | 306篇 |
2019年 | 314篇 |
2018年 | 1322篇 |
2017年 | 1598篇 |
2016年 | 1124篇 |
2015年 | 1005篇 |
2014年 | 937篇 |
2013年 | 1262篇 |
2012年 | 3963篇 |
2011年 | 3176篇 |
2010年 | 2328篇 |
2009年 | 1994篇 |
2008年 | 1249篇 |
2007年 | 1269篇 |
2006年 | 1204篇 |
2005年 | 4997篇 |
2004年 | 4336篇 |
2003年 | 2667篇 |
2002年 | 854篇 |
2001年 | 459篇 |
2000年 | 234篇 |
1999年 | 309篇 |
1998年 | 257篇 |
1997年 | 211篇 |
1996年 | 161篇 |
1995年 | 132篇 |
1994年 | 127篇 |
1993年 | 118篇 |
1992年 | 239篇 |
1991年 | 221篇 |
1990年 | 191篇 |
1989年 | 178篇 |
1988年 | 153篇 |
1987年 | 94篇 |
1986年 | 84篇 |
1985年 | 95篇 |
1984年 | 77篇 |
1983年 | 76篇 |
1982年 | 69篇 |
1981年 | 77篇 |
1979年 | 76篇 |
1978年 | 69篇 |
1977年 | 62篇 |
1976年 | 129篇 |
1975年 | 79篇 |
1974年 | 63篇 |
1973年 | 82篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
911.
P. Berastegui S. HullF.J. Garc? Garc? J. Grins 《Journal of solid state chemistry》2002,168(1):294-305
The structures of the oxyorthogermanate La2(GeO4)O and the apatite-structured La9.33(GeO4)6O2 have been refined from powder neutron diffraction data. La2(GeO4)O crystallizes in a monoclinic unit cell (P21/c) and is cation stoichiometric in contrast to previous reports. La9.33(GeO4)6O2 crystallizes in a hexagonal unit cell (P63/m) and the powder diffraction data show anisotropic peak broadening that is observed in electron diffraction patterns as incommensurate diffuse spots at hkq reciprocal planes (with q=1.6-1.7) and can be attributed to a correlated disorder in the “apatite channels”. This compound was doped up to a nominal composition close to M2La8(GeO4)6O2 with M=Ca, Sr, Ba. The dopant ions preferentially occupy the 4f sites as the number of La vacancies decreases. The measured ionic conductivity of La9.33(GeO4)6O2 is about 3 orders of magnitude larger than for La2(GeO4)O at high temperatures and decreases with increasing dopant content from the highest value of about 0.16 S cm−1 at 1160 K. 相似文献
912.
A modified thiocyanate method without extraction by using rhodamine 6G as a secondary ligand was developed. Molybdenum in 1.0×10−2 M HCl, after the addition of ascorbic acid, was heated for 10 min in a 90 °C water bath for reduction. Suitable amounts of glycerine, Triton X-100, rhodamine 6G solutions and 2+1 (v/v) 9 M H2SO4+3 M KHSO4 were added in this order. This solution was allowed to cool to room temperature and the absorbance at 570 nm was measured against a reagent blank 45 min after the addition of thiocyanate solution and the second aliquot of Triton X-100 solution. The complex was stable for at least 4 h, the order of reagent addition was important, and thiocyanate should be in large excess. Beer’s law was obeyed over the range 0.9×10−6 to 1.1×10−5 M Mo with the molar absorptivity being 1.1×105 l mol−1 cm−1. The R.S.D. for the determination of 0.7 mg Mo l−1 was 1.83% (n=8). Possible interferences of various cations and anions on molybdenum determination were studied. The proposed method was applied to the determination of molybdenum in a dental alloy, Wiron 99. 相似文献
913.
5-Hydroxytryptamino-induced calcium sparks in cultured rat stomach fundus smooth muscle cells 总被引:1,自引:0,他引:1
With the imaging fluorescence probe of Ca2+ (fluo-3) and a laser scanning confocal micro-scope, the spontaneous localized calcium release event was first discovered in resting rat cardiac myocytes by Cheng[1] in 1993. A mathematical simulation is developed with computer in order to reveal the effect, which is immediately suggested that these events are likely to reflect the local-ized release of Ca2+ from a small cluster of ryanodine-sensitive Ca2+ release channels in sar-coplasmic reticulum … 相似文献
914.
Dmitri S. Kilin Kiril Tsemekhman Oleg V. Prezhdo Eduard I. Zenkevich Christian von Borczyskowski 《Journal of photochemistry and photobiology. A, Chemistry》2007,190(2-3):342-351
The observed resonance energy transfer in nanoassemblies of CdSe/ZnS quantum dots and pyridyl-substituted free-base porphyrin molecules [Zenkevich et al., J. Phys. Chem. B 109 (2005) 8679] is studied computationally by ab initio electronic structure and quantum dynamics approaches. The system harvests light in a broad energy range and can transfer the excitation from the dot through the porphyrin to oxygen, generating singlet oxygen for medical applications. The geometric structure, electronic energies, and transition dipole moments are derived by density functional theory and are utilized for calculating the Förster coupling between the excitons residing on the quantum dot and the porphyrin. The direction and rate of the irreversible exciton transfer is determined by the initial photoexcitation of the dot, the dot–porphyrin coupling and the interaction to the electronic subsystem with the vibrational environment. The simulated electronic structure and dynamics are in good agreement with the experimental data and provide real-time atomistic details of the energy transfer mechanism. 相似文献
915.
Christian NP Reilly JP Mokler VR Wincott FE Ellington AD 《Journal of the American Society for Mass Spectrometry》2001,12(6):744-753
To probe the mechanism of gas-phase oligonucleotide ion fragmentation, modified oligonucleotides were studied using matrix-assisted laser desorption/ionization. The oligonucleotides were of the form 5'-TTTTXTTTTT, where X was a modified nucleotide. Modifications included substitution of hydroxy, methoxy, amino, and allyl groups at the 2'-position of the deoxyribose. The modified ribose contained adenine, guanine, cytosine, or uracil bases. For comparison, we studied oligomers where X was an unmodified adenosine, guanosine, cytidine, thymidine, or uridine deoxyribonucleotide. We found a very strong dependence of the matrix-to-analyte ratio on fragmentation for these oligomers. Analysis of these modifications suggests that the initial fragmentation step in MALDI-MS involves a two-step (E1) elimination of the base. 相似文献
916.
Christian Vogt 《manuscripta mathematica》1983,41(1-3):217-232
This paper deals with two quite unrelated properties of toroidal groups. After some preliminary remarks in section 0, we calculate in section 1 the Dolbeault cohomology groups of a toroidal group under an additional assumption which assures that those are at least finite-dimensional. In particular, we obtain a Hodge decomposition for these special toroidal groups. In section 2, we first give a new proof of a theorem of Cousin concerning the sections of topologically trivial line bundles on toroidal groups. As an application, we then show that, in a sense to be made precise, most abelian complex Lie groups of dimension ≥2 do not have any hypersurfaces. 相似文献
917.
Albert Defoin Hans Fritz Christian Schmidlin Jacques Streith 《Helvetica chimica acta》1987,70(3):554-569
N-Acylnitroso derivatives 6 which were prepared by in-situ oxidation of the corresponding hydroxamic acids 5 reacted instantaneously and in high yields with dihydropyridine 4 . The Diels-Alder adducts 8 were formed regiospecifically with the acylnitroso dienophiles 6a–c , whereas the dienophiles 6d–f gave mixtures of both regioisomers 7 and 8 . These and some other results [2] were best explained by the FMO theory. The Diels-Alder adducts 7 and 8 gave the corresponding ‘anti’-cis-glycols when reacted with OsO4/N-methylmorpholine N-oxide. Hydrogenolysis of the N–O bond followed by peracetylation led to the expected aminolyxose derivatives 14 and 16 . A similar sequence, using 4 and the hydroxamic-acid derivative 18 of (+)-D-mandelic acid led, with a poor asymmetric induction, to a mixture of the expected optically active aminolyxose compounds 19A / 19B . 相似文献
918.
Liya?Wang Zhiliang?Liu Chenxi?Zhang Zhanquan?Liu Daizheng?Liao Zonghui?JiangEmail author Shiping?Yan 《中国科学B辑(英文版)》2003,46(6):533-541
A novel one-dimensional manganese(II) complex containing nitronyl nitroxide radical [Mn2(IM2-py)2(Ac)2(μ1,1-N3)(μ1,3-N3) · EtOH]
n
was synthesized and characterized structurally and magnetically. It crystallizes in the monoclinic space group p21/n. Each Mn(II) ion is six-coordinated in a distorted octahedral environment. The two N atoms of the nitronyl nitroxide radical
and the two O atoms of acetate ligands are in the equatorial plane, whereas the two different azido bridging ligands are in
trans axial position. Mn(II) ions are linked by nitrogen atom of μ1,1-azido and oxygen atoms of two carboxy groups to form a Mn-Mn unit. Mn-Mn units are linked by azido ligands through μ1,3 bridging style to form a one-dimensional chain. The compound is connected by the coordination bonds, π-π interactions and
hydrogen bonds as a three-dimensional structure. Magnetic susceptibility data support that there are stronger antiferromagnetic
interactions between the radical and Mn(II) ion, weak antiferromagnetic interactions between the Mn-R units, and very weak
antiferromagnetic interactions between the R-Mn-Mn-R units. 相似文献
919.
The fabrication and electrochemical characteristics of a penicillamine (PCA) self-assembled monolayer modified gold electrode were investigated. The self-assembled electrode shows obvious electrocatalytic activity for the oxidation of epinephrine (EP). In phosphate buffer (pH 7.73), a sensitive oxidation peak was observed at 0.190V with the PCA modified Au electrode. The peak current is proportional to the concentration of EP in the range of 2.0×10–56.0×10–4molL–1 and 5.0×10–6 2.0×10–4molL–1 for cyclic voltammetry (CV) and differential pulse voltammetry (DPV) with the detection limits of 1.8×10–7 and 1.3×10–7molL–1, respectively. The possible reaction mechanism is also discussed. The PCA self-assembled monolayer modified gold electrode is highly stable and can be applied to the determination of EP in practical injection samples. Application is simple, rapid and produces accurate results. 相似文献
920.
Jenny?ZevallosEmail author Alejandro?Toro-Labbé Otilia?Mó Manuel?Yá?ez 《Structural chemistry》2005,16(3):295-303
High level ab initio and density functional theory calculations have been carried out to investigate the relative stability of the different conformers of hyponitrous acid and its mono- and dithio-derivatives. Geometries and vibrational frequencies were obtained at the B3LYP/6-311+G(d,p) level and final energies through B3LYP/6-311++G(3df,2pd) single point calculations. The reliability of this theoretical scheme has been assessed by comparing these DFT results with those obtained at the G3 level of theory, for some suitable cases. The cis conformers of hyponitrous acid and its mono- and dithio-derivatives are systematically more stable than the
trans ones because in the cis conformation a dative interaction between the nitrogen-lone pairs and the σNX^* antibonding orbital is significantly favored. Quite interestingly, in general, the conformers presenting an intramolecular hydrogen bond (IHB) are not the global minima of the corresponding potential energy surfaces and only for hyponitrous acid the conformer with a OH ⋅s O IHB is slightly more stable than the cis conformer without IHB. The low stability of the tautomers with IHB is closely related with another weak intramolecular interaction which involves the lone-pairs of the chalcogen atoms and the πNN* antibondig orbital, and which is significantly perturbed when the IHB is formed. 相似文献