全文获取类型
收费全文 | 647篇 |
免费 | 20篇 |
国内免费 | 2篇 |
专业分类
化学 | 565篇 |
晶体学 | 3篇 |
力学 | 6篇 |
数学 | 43篇 |
物理学 | 52篇 |
出版年
2023年 | 9篇 |
2022年 | 24篇 |
2021年 | 18篇 |
2020年 | 15篇 |
2019年 | 16篇 |
2018年 | 13篇 |
2017年 | 14篇 |
2016年 | 21篇 |
2015年 | 17篇 |
2014年 | 18篇 |
2013年 | 36篇 |
2012年 | 41篇 |
2011年 | 65篇 |
2010年 | 22篇 |
2009年 | 32篇 |
2008年 | 55篇 |
2007年 | 52篇 |
2006年 | 28篇 |
2005年 | 32篇 |
2004年 | 17篇 |
2003年 | 15篇 |
2002年 | 13篇 |
2001年 | 5篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1997年 | 2篇 |
1993年 | 6篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1987年 | 2篇 |
1984年 | 4篇 |
1981年 | 3篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 5篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 4篇 |
1968年 | 2篇 |
1954年 | 2篇 |
1937年 | 2篇 |
1936年 | 2篇 |
1934年 | 2篇 |
1932年 | 3篇 |
1928年 | 1篇 |
1922年 | 1篇 |
1919年 | 3篇 |
1898年 | 1篇 |
1879年 | 1篇 |
排序方式: 共有669条查询结果,搜索用时 15 毫秒
571.
Kang C Troyer JL Robertson EM Rothgeb DW Hossain E Wyrwas RB Parmenter CS Jarrold CC 《The Journal of chemical physics》2008,128(10):104309
Anion photoelectron spectra of the O(2)(-) . arene and O(4)(-) . arene complexes with p-xylene and p-difluorobenzene are presented and analyzed with the aid of calculations on the anions and corresponding neutrals. Relative to the adiabatic electron affinity of O(2), the O(2)(-) . arene spectra are blueshifted by 0.75-1 eV. Solvation energy alone does not account for this shift, and it is proposed that a repulsive portion of the neutral potential energy surface is accessed in the detachment, resulting in dissociative photodetachment. O(2)(-) is found to interact more strongly with the p-difluorobenzene than the p-xylene. The binding motif involves the O(2)(-) in plane with the arene, interacting via electron donation along nearby C-H bonds. A peak found at 4.36(2) eV in the photoelectron spectrum of O(2)(-) . p-difluorobenzene (p-DFB) is tentatively attributed to the charge transfer state, O(2)(-) . p-DFB(+). Spectra of O(4)(-) . arene complexes show less blueshift in electron binding energy relative to the spectrum of bare O(4)(-), which itself undergoes dissociative photodetachment. The striking similarity between the profiles of the O(4)(-) . arene complexes with the O(4)(-) spectrum suggests that the O(4)(-) molecule remains intact upon complex formation, and delocalization of the charge across the O(4)(-) molecule results in similar structures for the anion and neutral complexes. 相似文献
572.
Two polymeric pseudostationary phases, one an acrylamide polymer and the second a siloxane polymer, have been investigated for the separation of naphthalene-2,3-dicarboxaldehyde (NDA)-derivatized amino acids and small peptides. The dervatized amino acids were detected by UV absorbance and laser-induced fluorescence (LIF) detection. The polymers provided very high efficiency and good selectivity for the separation of the amino acids. The separation selectivity using the polymers was significantly different from that of SDS micelles, and there were subtle differences in selectivities between the polymers. Although very good detection limits were obtained with LIF detection, a significant background signal was observed when the polymers were not washed to remove fluorescent impurities. The polymers did not separate the peptides very well. It is postulated that the fixed covalent structure of the polymers prevents them from interacting strongly or efficiently with the peptides, which are large in relation to the analytes typically separated by electrokinetic chromatography using polymers. 相似文献
573.
Carmen A. Roba Cristina Jimenez Călin Baciu Simion Beldean-Galea Erika Levei Emil Cordoš 《Central European Journal of Chemistry》2011,9(4):598-604
In the present study, a simple procedure for the isolation by solid-phase extraction (SPE) and quantification by UV-Vis spectrometry
(400 nm) of the humic acids (HAs) in the natural waters was developed. Seven different sorbents: Porapak P (polystyrene-divinylbenzene
copolymer), Florisil (chemical composition: 84.0% SiO2, 15.5% MgO and 0.5% Na2SO4), Silica gel C18 (octadecyl silane), Strata X (surface modified polystyrene-divinylbenzene), Strata NH2 (silica-based trifunctional amino ligand), Strata SAX (silica-based trifunctional quaternary amine) and Strata C18-E (silica-based
trifunctional C18 with hydrophobic end-capping of silanols) were tested. The HAs, adsorbed on SPE cartridges, were eluted
using: NaOH (0.1 M), sodium dodecyl sulphate (SDS) (20 g L−1), and a 1:1 v/v mixture of SDS (20 g L−1) and NaOH (0.1 M). The extraction efficiency was evaluated by comparing the HAs recovery levels. The repeatability of results
was estimated by the relative standard deviation (RSD). The data confirmed that Porapak P, Silica gel C18, Florisil, Strata
NH2 and Strata X could be good alternatives for the traditional isolation of the aquatic HAs with XAD resin. The proposed method
was applied for the determination of HAs in some waters sampled from the Western Romanian Plain. The content of HAs was correlated
with the arsenic concentration and total organic carbon (TOC) level.
相似文献
574.
Gregory B. Kharas Selena M. Russell Robert Cisler Tess L. Capen Erika A. Chlupsa Lisa A. Debellis 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(4):261-264
Electrophilic trisubstituted ethylene monomers, halogen ring‐disubstituted 2‐phenyl‐1,1‐dicyanoethylenes, RC6H3CH?C(CN)2 (where R is 2,3‐diCl, 2,4‐diCl, 2,6‐diCl, 3,4‐diCl, 3,5‐diCl, 2,4‐diF, 2,5‐diF, 2,6‐diF, 3,4‐diF, 3,5‐diF, 2‐Cl, 6‐F) were synthesized by piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and malononitrile, and characterized by CHN elemental analysis, IR, 1H‐and 13C‐NMR. Novel copolymers of the ethylenes and vinyl acetate were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1H and 13C‐NMR, GPC, DSC, and TGA. High Tg of the copolymers, in comparison with that of polyvinyl acetate, indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 220–800°C range. 相似文献
575.
The DOOO radical has been produced by three-body association between OD and O2 in a supersonic free-jet expansion and investigated using action spectroscopy, an IR-UV double-resonance technique. Partially rotationally structured bands observed at 2635.06 and 5182.42 cm(-1) are assigned to the OD stretch fundamental (nu(OD)) and overtone (2nu(OD)), respectively, of the trans-DOOO radical. Unstructured bands observed in both spectral regions are assigned to cis-DOOO. Nascent OD X(2)Pi product state distributions following vibrational predissociation appear to be nearly statistical with respect to the degree of rotational excitation, but display a marked propensity for Pi(A') Lambda-doublets, which is interpreted as a signature of a planar dissociation. The energetically highest open OD X(2)Pi product channel implies an upper limit dissociation energy D0 < or = 1856 cm(-1) or 5.31 kcal mol(-1). This value allows refinement of the upper limit D0 of the atmospherically important HOOO isotopomer, suggesting that it is marginally less stable than previously thought. 相似文献
576.
Mara Tsesarskaia Erika Galindo Gyula Szókán George Fisher 《Biomedical chromatography : BMC》2009,23(6):581-587
d ‐Aspartate (d ‐Asp) and N‐methyl‐d ‐aspartate (NMDA) occur in the neuroendocrine systems of vertebrates and invertebrates, where they play a role in hormone release and synthesis, neurotransmission, and memory and learning. N‐methyl‐d ‐glutamate (NMDG) has also been detected in marine bivalves. Several methods have been used to detect these amino acids, but they require pretreatment of tissue samples with o‐phthaldialdehyde (OPA) to remove primary amino acids that interfere with the detection of NMDA and NMDG. We report here a one‐step derivatization procedure with the chiral reagent N‐α‐(5‐fluoro‐2,4‐dinitrophenyl)‐(d or l )‐valine amide, FDNP‐Val‐NH2, a close analog of Marfey's reagent but with better resolution and higher molar absorptivity. The diastereomers formed were separated by HPLC on an ODS‐Hypersil column eluted with TFA/water–TFA/MeCN. UV absorption at 340 nm permitted detection levels as low as 5–10 pmol. d ‐Asp, NMDA and NMDG peaks were not obscured by other primary or secondary amino acids; hence pretreatment of tissues with OPA was not required. This method is highly reliable and fast (less than 40 min HPLC run). Using this method, we detected d ‐Asp, NMDA and NMDG in several biological tissues (octopus brain, optical lobe and bucchal mass; foot and mantle of the mollusk Scapharca broughtonii), confirming the results of other researchers. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
577.
Michaela Harmošová Mária Vilková Martin Kello Lukáš Smolko Erika Samol'ová Dominika Šebová Ivan Potočňák 《Acta Crystallographica. Section C, Structural Chemistry》2023,79(8):316-323
A new zirconium(IV) complex, diaquabis(8-hydroxyquinoline-2-carboxylato-κ3N,O2,O8)zirconium(IV) dimethylformamide disolvate, [Zr(C10H5NO3)2(H2O)2]·2C3H7NO or [Zr(QCa)2(H2O)2]·2DMF ( 1 ) (HQCaH is 8-hydroxyquinoline-2-carboxylic acid and DMF is dimethylformamide), was prepared and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray structure analysis. Complex 1 is a mononuclear complex in which the ZrIV atoms sit on the twofold axis and they are octacoordinated by two N and six O atoms of two tridentate anionic QCa2− ligands, and two aqua ligands. Outside the coordination sphere are two DMF molecules bound to the complex unit by hydrogen bonds. The structure and stability of complex 1 in dimethyl sulfoxide were verified by NMR spectroscopy. The cytotoxic properties of 1 and HQCaH were studied in vitro against eight cancer cell lines, and their selectivity was tested on the BJ-5ta noncancerous cell line. Both the complex and HQCaH exhibited low activity, with IC50 > 200 µM. DNA and human serum albumin (HSA) binding studies showed that 1 binds to calf thymus (CT) DNA via intercalation and is able to bind to the tryptophan binding site of HSA (Trp-214). 相似文献
578.
Bartholomew ER Bertz SH Cope S Dorton DC Murphy M Ogle CA 《Chemical communications (Cambridge, England)》2008,(10):1176-1177
Neutral organocopper(III) complexes have been prepared from organocuprate(I) reagents and alkyl halides in the presence of certain strongly electron donating ligands. 相似文献
579.
Asher WB Hoskins SN Slasor LA Morris DH Cook EM Bautista DL 《Journal of chemical information and modeling》2007,47(5):1906-1912
In this study, we have developed a two model system to mimic the active and inactive states of a G-protein coupled receptor specifically the alpha1A adrenergic receptor. We have docked two agonists, epinephrine (phenylamine type) and oxymetazoline (imidazoline type), as well as two antagonists, prazosin and 5-methylurapidil, into two alpha1A receptor models, active and inactive. The best docking complexes for both agonists had hydrophilic interactions with D106, while neither antagonist did. Prazosin and oxymetazoline had hydrophobic interactions with F308 and F312. We predict from our study that the active state is stabilized by the interaction of F193 with I114, L197, V278, F281, and V282. The active state is further stabilized by the interaction of F312 with L75, V79, and L80. We also predict that the inactive state of the receptor is stabilized by the interaction of F312 with W102, F288, and M292. 相似文献
580.
Jabbari-Farouji S Mizuno D Atakhorrami M MacKintosh FC Schmidt CF Eiser E Wegdam GH Bonn D 《Physical review letters》2007,98(10):108302
We provide a direct experimental test of the fluctuation-dissipation theorem (FDT) in an aging colloidal glass. The use of combined active and passive microrheology allows us to independently measure both the correlation and response functions in this nonequilibrium situation. Contrary to previous reports, we find no deviations from the FDT over several decades in frequency (1 Hz-10 kHz) and for all aging times. In addition, we find two distinct viscoelastic contributions in the aging glass, including a nearly elastic response at low frequencies that grows during aging. 相似文献