全文获取类型
收费全文 | 27988篇 |
免费 | 996篇 |
国内免费 | 162篇 |
专业分类
化学 | 18652篇 |
晶体学 | 310篇 |
力学 | 486篇 |
综合类 | 2篇 |
数学 | 3750篇 |
物理学 | 3993篇 |
无线电 | 1953篇 |
出版年
2022年 | 238篇 |
2021年 | 330篇 |
2020年 | 492篇 |
2019年 | 476篇 |
2018年 | 302篇 |
2017年 | 303篇 |
2016年 | 649篇 |
2015年 | 578篇 |
2014年 | 699篇 |
2013年 | 1268篇 |
2012年 | 1431篇 |
2011年 | 1788篇 |
2010年 | 908篇 |
2009年 | 857篇 |
2008年 | 1467篇 |
2007年 | 1576篇 |
2006年 | 1533篇 |
2005年 | 1446篇 |
2004年 | 1238篇 |
2003年 | 1015篇 |
2002年 | 1013篇 |
2001年 | 398篇 |
2000年 | 392篇 |
1999年 | 329篇 |
1998年 | 343篇 |
1997年 | 368篇 |
1996年 | 415篇 |
1995年 | 344篇 |
1994年 | 290篇 |
1993年 | 329篇 |
1992年 | 284篇 |
1991年 | 252篇 |
1990年 | 246篇 |
1989年 | 199篇 |
1988年 | 201篇 |
1987年 | 222篇 |
1986年 | 184篇 |
1985年 | 275篇 |
1984年 | 308篇 |
1983年 | 226篇 |
1982年 | 268篇 |
1981年 | 306篇 |
1980年 | 251篇 |
1979年 | 223篇 |
1978年 | 265篇 |
1977年 | 211篇 |
1976年 | 207篇 |
1975年 | 181篇 |
1974年 | 195篇 |
1973年 | 193篇 |
排序方式: 共有10000条查询结果,搜索用时 66 毫秒
941.
Chrif F. Matta Christopher N. Cow Paul H. M. Harrison 《Journal of Molecular Structure》2003,660(1-3):81-97
X-ray crystallography and theoretical analysis were applied to explore the molecular basis for the efficient and selective Claisen-like condensations of diacylglycolurils. The crystal structures of 1-acetyl-6-benzoyl-3,4,7,8-tetramethylglycoluril (4b), and of 1-(3′-oxo-3′-phenylpropionyl)-3,4,7,8-tetramethylglycoluril (5b), the product of base-promoted intramolecular condensation of 4b, were obtained by X-ray diffraction. The acetyl (Ac) group in 4b is essentially coplanar with the attached tetrahydroimidazolone ring of the glycoluril core (τ=7°), while the benzoyl (Bz) group is twisted by τ=45° relative to a plane through the ring to which it is bonded. Product 5b contains a flat amide (τ=7°). Ab initio energy optimizations of the experimental structures for 4b and 5b give optimized geometries which are not dramatically altered, suggesting that crystal packing effects are small. An atoms-in-molecules study of the delocalization of the Fermi hole reveals that electrons in the Bz C=O group of 4b are delocalized into the phenyl ring as well as into the urea moiety of the glycoluril core. This effect stabilizes the Bz over the Ac carbonyl group, and accounts for selective twisting of the Bz group. The Laplacian of the electron density reveals a non-bonded valence shell charge concentration at O of the Ac group, corresponding to a lone-pair region, aligned with a charge depletion in the valence shell of the Bz C=O carbon [(C15–O16C18)=113°]. The angle of approach [(O16C18=O19)] is 100°, equal to the angle for ideal nucleophilic attack on a carbonyl group. Oxygen atom O16 is thus poised to attack C18; only the O16C18 distance (3.248 Å) seems to prevent reaction. These results suggest that the same distance restraint may prevent O-acylation in the enolate intermediate 6b derived from4b. By contrast, the transition state for C-acylation, leading from 6b towards product 5b requires a different geometry, which may explain the observed selectivity for C-acylation in this enolate. The results show that, as 4b is converted to 5b, amide torsional strain is relieved, which may account for the high reactivity of 4b and the efficiency and irreversibility of this condensation process. This study provides a starting point for quantitative correlation of substrate structure in diacylglycolurils with kinetic data for the rearrangement reaction. 相似文献
942.
Gucek M Makuc S Mlakar A Bericnik-Vrbovsek J Marsel J 《Rapid communications in mass spectrometry : RCM》2002,16(12):1186-1191
For the determination of glutathione (GSH) and its oxidized form (GSSG) in spruce needles their electrospray mass and MS/MS spectra were recorded with an ion trap mass spectrometer (ITMS, LCQ, Finnigan) and a triple stage quadrupole mass spectrometer (TSQ, Quattro II, Micromass). A study of the stability of GSH in aqueous solutions shows the presence of dimeric and trimeric forms of GSH, as well as GSSG, GSH-sulfonate and GSH-sulfinic acid. The same components were also found in extracts of spruce needles. We developed an assay which is suitable for monitoring low concentrations of GSH and similar compounds in plant tissues, employing the sensitivity and specificity of LC/MS/MS. Preliminary results on the mass spectrometric determination of GSH in spruce needles are given. 相似文献
943.
Bernd A Simon S Ramirez Bosca A Kippenberger S Diaz Alperi J Miquel J Villalba Garcia JF Pamies Mira D Kaufmann R 《Photochemistry and photobiology》1999,69(2):218-221
Extracts of Hypericum perforatum (St. John's wort) are used in the treatment of depression. They contain the plant pigment hypericin and hypericin derivates. These compounds have light-dependent activities. In order to estimate the potential risk of phototoxic skin damage during antidepressive therapy, we investigated the phototoxic activity of hypericin extract using cultures of human keratinocytes and compared it with the effect of the well-known phototoxic agent psoralen. The absorbance spectrum of our Hypericum extract revealed maxima in the whole UV range and in parts of the visible range. We cultivated human keratinocytes in the presence of different Hypericum concentrations and irradiated the cells with 150 mJ/cm2 UVB, 1 J/cm2 UVA or 3 h with a white light of photon flux density 2.6 mumol m-2 s-1. The determination of the bromodeoxyuridine incorporation rate showed a concentration- and light-dependent decrease in DNA synthesis with high hypericin concentrations (> or = 50 micrograms/mL) combined with UVA or visible light radiation. In the case of UVB irradiation a clear phototoxic cell reaction was not detected. We found phototoxic effects even with 10 ng/mL psoralen using UVA with the same study design as in the case of the Hypericum extract. These results confirm the phototoxic activity of Hypericum extract on human keratinocytes. However, the blood levels that are to be expected during antidepressive therapy are presumably too low to induce phototoxic skin reactions. 相似文献
944.
A review is presented on thiocyanate methods for the estimation of molybdenum in a wide variety of samples. They include conventional thiocyanate methods in which molybdenum forms an orange red complex with the thiocyanate ions and improved thiocyanate methods where the sensitivity is increased through the formation of ternary ion association complex. 相似文献
945.
The reaction of trimethylsilyl-substituted 2-aminopyridines with mixed chloro(dialkylamido)metal complexes (titanium and zirconium) leads via amine elimination to octahedral group 4 metal complexes that contain amine, amido, and aminopyridinato ligands. The X-ray crystal structure analyses of (4-Me-TMS-APy)(NMe(2))(HNMe(2))TiCl(2) (1) (crystallographic data: P2(1)/c (No. 14), monoclinic, a = 16.754(2) ?, b = 14.395(2) ?, c = 17.890(3) ?, beta = 110.28(1) degrees, Z = 8) and (6-Me-TMS-APy)(NEt(2))(HNEt(2))ZrCl(2) (2) (crystallographic data: P2(1)/n (No. 14) monoclinic, a = 10.125(1) ?, b = 16.331(1) ?, c = 15.276(2) ?, beta = 93.90(1), Z = 4) prove the compounds to be mononuclear with a cisoid arrangement of the two chloro ligands embedded in a reactive pocket determined by the steric demand of the three nitrogen containing ligands. Oligo- and polymerization studies with propene and 1-butene reveal the following results. First, 1 is a remarkably active precatalyst in contrast to the very low activity of 2. Second, MAO, a 1:1 mixture of i-Bu(3)Al/B(C(6)F(5))(3) (homogeneous polymerization) and ethylaluminum sesquichloride (if 1 is incorporated in a MgCl(2)-matrix) have shown to be the most active cocatalysts. Third, the polymers and oligomers are atactic. 相似文献
946.
Rik R. Tykwinski Franois Diederich Paul Seiler Volker Gramlich 《Helvetica chimica acta》1996,79(3):634-645
The synthesis of functionalized 1,1,2,2-tetraethynylethanes (= 3,4-diethynylhexa-1,5-diynes) as synthons for tetraethynylethenes (3,4-diethynylhex-3-ene-1,5-diynes) and as building blocks for three-dimensional acetylenic molecular scaffolding targeting the synthesis of the molecular carbon belts 3 and 4 is reported (Scheme 1). Reaction of diethyl oxalate and (trialkylsilyl)ethynyl Grignard reagents afforded the silyl-protected 3,4-diethynylhexa-1,5-diyne-3,4- diols 7 and 8 which were transformed in high yields into the cyclic carbonate 9 and the cyclic orthoesters 10–13 , respectively (Scheme 2). The solid-state structures of 9 and 10 were elucidated by X-ray crystallography. The alkyne protecting groups in 9, 10 , and 12 were smoothly removed to give the free tetraynes 14–16 as relatively stable oils in nearly quantitative yields (Scheme 3). Orthoesters 15 and 16 underwent Pd-catalyzed cross-coupling with iodobenzene to give the tetraphenyl derivatives 17 and 18 (Scheme 4). Thermal acid-catalyzed elimination of the orthoester moieties in 12 and 13 produced the silyl-protected tetraethynylethenes 19 and 20 and concluded a novel, simple three-step synthesis of these fully two-dimensionally conjugated π-chromophores (Scheme 5). 相似文献
947.
On the Reaction of Macrocycles with Lanthanoids. I. The Crystal Structure of [Li(thf)][(C22H22N4)2Ce] · THF In THF CeBr3 forms with [(TMTAA)Li2] the paramagnetic doubledecker complex [Li(thf)][(TMTAA)2Ce]. The complex crystallizes with 1 Mol THF per formula unit. The structure was characterized by X-ray single crystal structure analysis (space group C2 (No. 5), z = 6, a = 1741.8(2) pm, b = 1622.1(2) pm, c = 2540.4(3) pm, β = 104.72(1)°). The sandwich-like arrangement of the heterocyclic ligands leads to a quadratic-prismatic coordination of the Ce3+ ion. One macrocyclic ligand is additionally coordinated by a [Li(thf)]+ fragment. The coordination of the Li ion is square pyramidal. 相似文献
948.
Stacking techniques used independently and also with a high-sensitivity cell (HSC) were employed to optimise sensitivity and detection limits in the direct photometric detection of the following eight arsenic species by capillary zone electrophoresis (CZE): arsenite, arsenate, monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), 4-hydroxy-3-nitrophenylarsonic acid (Roxarsone), p-aminophenylarsonic acid (p-ASA), 4-nitrophenylarsonic acid (4-NPAA), and phenylarsonic acid (PAA) (target analytes). The stacking mechanisms, optimised stacking and separation conditions, and concentration sensitivity enhancement factors were discussed and compared for (i) normal stacking mode (NSM, sometimes also referred to as field-amplified stacking) in an uncoated fused-silica capillary in the counter-electroosmotic flow (EOF) mode, (ii) large-volume sample stacking (LVSS) with polarity switching, and (iii) the less often applied stacking method of co-EOF NSM stacking with EOF reversal using a poly(diallydimethylammonium chloride) (PDDAC)-coated capillary. The optimal injection volumes were 7.4, 60 and 17.2% of the total capillary volume, for the above three methods, respectively. LVSS with polarity switching gave the lowest limit of detection (LOD). The use of the HSC further reduced the LOD of each target analytes by a factor of 5-8 times. By combining LVSS and HSC, LODs of the target analytes could be reduced by a factor of 218-311, to 5.61, 9.15, 11.1, and 17.1 microg/L for As(III), DMA, MMA, and As(V), respectively. The method was demonstrated to be applicable to the determination of the target analytes in tap water and lake water, with recoveries in the range of 89.4-103.3%. 相似文献
949.
MacLean EJ Harris KD Kariuki BM Kitchin SJ Tykwinski RR Swainson IP Dunitz JD 《Journal of the American Chemical Society》2003,125(47):14449-14451
The transformation of ammonium cyanate into urea, first studied over 170 years ago by W?hler and Liebig, has an important place in the history of chemistry. To understand the nature of this solid state reaction, knowledge of the crystal structure of ammonium cyanate is a prerequisite. Employing neutron powder diffraction, we demonstrate conclusively that, in the structure of ammonium cyanate, the NH(4)(+) cation forms N-H...N hydrogen bonds to four cyanate N atoms at alternate corners of a distorted cube, rather than our previously proposed alternative arrangement with N-H...O hydrogen bonds to cyanate O atoms at the other four corners. 相似文献
950.
An interlaboratory study was performed on behalf of the UK Food Standards Agency to evaluate the effectiveness of an immunoaffinity column cleanup liquid chromatographic (LC) method for the determination of deoxynivalenol in a variety of cereals and cereal products at proposed European regulatory limits. The test portion was extracted with water. The sample extract was filtered a applied to an immunoaffinity column. After being washed with water, the deoxynivalenol was eluted with acetonitrile or methanol. Deoxynivalenol was quantitated by reversed-phase LC with UV determination. Samples of artificially contaminated wheat-flour, rice flour, oat flour, polenta, and wheat based breakfast cereal, naturally contaminated wheat flour, and blank (very low level) samples of each matrix were sent to 13 collaborators in 7 European countries. Participants were asked to spike test portions of all samples at a range of deoxynivalenol concentrations equivalent to 200-2000 ng/g deoxynivalenol. Average recoveries ranged from 78 to 87%. Based on results for 6 artificially contaminated samples (blind duplicates), the relative standard deviation for repeatability (RSDr) ranged from 3.1 to 14.1%, and the relative standard deviation for reproducibility (RSDR) ranged from 11.5 to 26.3%. The method showed acceptable within-laboratory and between-laboratory precision for all 5 matrixes, as evidenced by HorRat values < 1.3. 相似文献