全文获取类型
收费全文 | 1119篇 |
免费 | 47篇 |
国内免费 | 9篇 |
专业分类
化学 | 590篇 |
晶体学 | 10篇 |
力学 | 24篇 |
数学 | 67篇 |
物理学 | 347篇 |
无线电 | 137篇 |
出版年
2024年 | 5篇 |
2023年 | 30篇 |
2022年 | 35篇 |
2021年 | 38篇 |
2020年 | 46篇 |
2019年 | 43篇 |
2018年 | 41篇 |
2017年 | 40篇 |
2016年 | 62篇 |
2015年 | 27篇 |
2014年 | 51篇 |
2013年 | 98篇 |
2012年 | 60篇 |
2011年 | 75篇 |
2010年 | 40篇 |
2009年 | 39篇 |
2008年 | 52篇 |
2007年 | 53篇 |
2006年 | 35篇 |
2005年 | 36篇 |
2004年 | 20篇 |
2003年 | 12篇 |
2002年 | 25篇 |
2001年 | 11篇 |
2000年 | 9篇 |
1999年 | 8篇 |
1998年 | 11篇 |
1997年 | 4篇 |
1996年 | 17篇 |
1995年 | 17篇 |
1994年 | 6篇 |
1993年 | 5篇 |
1992年 | 15篇 |
1991年 | 6篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 9篇 |
1983年 | 14篇 |
1982年 | 6篇 |
1981年 | 3篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1978年 | 9篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1938年 | 2篇 |
排序方式: 共有1175条查询结果,搜索用时 15 毫秒
991.
Aravinda S Shamala N Bandyopadhyay A Balaram P 《Journal of the American Chemical Society》2003,125(49):15065-15075
The structural characterization in crystals of three designed decapeptides containing a double d-segment at the C-terminus is described. The crystal structures of the peptides Boc-Leu-Aib-Val-Xxx-Leu-Aib-Val-(D)Ala-(D)Leu-Aib-OMe, (Xxx = Gly 2, (D)Ala 3, Aib 4) have been determined and compared with those reported earlier for peptide 1 (Xxx = Ala) and the all l analogue Boc-Leu-Aib-Val-Ala-Leu-Aib-Val-Ala-Leu-Aib-OMe, which yielded a perfect right-handed alpha-helical structure. Peptides 1 and 2 reveal a right-handed helical segment spanning residues 1 to 7, ending in a Schellman motif with (D)Ala(8) functioning as the terminating residue. Polypeptide chain reversal occurs at residue 9, a novel feature that appears to be the consequence of a C-H.O hydrogen bond between residue 4 C(alpha)H and residue 9 CO groups. The structures of peptides 3 and 4, which lack the pro R hydrogen at the C(alpha) atom of residue 4, are dramatically different. Peptide 3 adopts a right-handed helical conformation over the 1 to 7 segment. Residues 8 and 9 adopt alpha(L) conformations forming a C-terminus type I' beta-turn, corresponding to an incipient left-handed twist of the polypeptide chain. In peptide 4, helix termination occurs at Aib(6), with residues 6 to 9 forming a left-handed helix, resulting in a structure that accommodates direct fusion of two helical segments of opposite twist. Peptides 3 and 4 provide examples of chiral residues occurring in the less favored sense of helical twist; (D)Ala(4) in peptide 3 adopts an alpha(R) conformation, while (L)Val(7) in 4 adopts an alpha(L) conformation. The structural comparison of the decapeptides reported here provides evidence for the role of specific C-H.O hydrogen bonds in stabilizing chain reversals at helix termini, which may be relevant in aligning contiguous helical and strand segments in polypeptide structures. 相似文献
992.
Two structurally close tetrasaccharides corresponding to the O-antigens of Escherichia coli O127 and Salmonella enterica O13 have been synthesized using a ‘unichemo’ approach and minimum number of reaction steps. The yields of all glycosylation steps were excellent with a high stereochemical outcome. A common synthetic strategy has been adopted for the simultaneous synthesis of two tetrasaccharides. 相似文献
993.
Vinay Kiran Abhishek Dixit Bhavesh Babulal Gabani Nuggehally R. Srinivas Ramesh Mullangi 《Biomedical chromatography : BMC》2020,34(11):e4938
Different options on performing incurred sample reanalysis (ISR) on dried blood spot (DBS) cards were investigated using drugs belonging to various therapeutic areas: (a) darolutamide (to treat prostate cancer) and (b) filgotinib (to treat rheumatoid arthritis). The proposed novel methodology included the generation of half-DBS and quarter-DBS discs after initial blood collection using the full-DBS discs. Accordingly, blood collection via DBS was performed in male BALB/c mice following intravenous and oral dosing of darolutamide; in male Sprague Dawley rats following intravenous and oral dosing of filgotinib. The ISR data generated from the full-DBS disc, half-DBS disc and quarter-DBS disc were compared for the assessment of the proposed methodology. Quantification of darolutamide and filgotinib was accomplished using liquid chromatography-electrospray ionization/tandem mass spectrometry methods. Darolutamide and filgotinib ISR samples, which were collected and prepared using full-, half- and quarter-DBS discs, met the acceptance criteria for ISR analysis. In conclusion, this is the first report showing a viable tool for the performance of ISR on DBS cards. The use of quarter- or half-DBS discs would aid in not only ISR but also in long-term storage experiments of analytes because it would avoid the need for additional blood sampling in patients. 相似文献
994.
Lugo-Mas P Dey A Xu L Davin SD Benedict J Kaminsky W Hodgson KO Hedman B Solomon EI Kovacs JA 《Journal of the American Chemical Society》2006,128(34):11211-11221
995.
De P Maji S Chowdhury AD Mobin SM Mondal TK Paretzki A Lahiri GK 《Dalton transactions (Cambridge, England : 2003)》2011,40(46):12527-12539
The present article describes ruthenium nitrosyl complexes with the {RuNO}(6) and {RuNO}(7) notations in the selective molecular frameworks of [Ru(II)([9]aneS(3))(bpy)(NO(+))](3+) (4(3+)), [Ru(II)([9]aneS(3))(pap) (NO(+))](3+) (8(3+)) and [Ru(II)([9]aneS(3))(bpy)(NO˙)](2+) (4(2+)), [Ru(II)([9]aneS(3))(pap)(NO˙)](2+) (8(2+)) ([9]aneS(3) = 1,4,7-trithiacyclononane, bpy = 2,2'-bipyridine, pap = 2-phenylazopyridine), respectively. The nitrosyl complexes have been synthesized by following a stepwise synthetic procedure: {Ru(II)-Cl} → {Ru(II)-CH(3)CN} → {Ru(II)-NO(2)} → {Ru(II)-NO(+)} → {Ru(II)-NO˙}. The single-crystal X-ray structure of 4(3+) and DFT optimised structures of 4(3+), 8(3+) and 4(2+), 8(2+) establish the localised linear and bent geometries for {Ru-NO(+)} and {Ru-NO˙} complexes, respectively. The crystal structures and (1)H/(13)C NMR suggest the [333] conformation of the coordinated macrocyclic ligand ([9]aneS(3)) in the complexes. The difference in π-accepting strength of the co-ligands, bpy in 4(3+) and pap in 8(3+) (bpy < pap) has been reflected in the ν(NO) frequencies of 1945 cm(-1) (DFT: 1943 cm(-1)) and 1964 cm(-1) (DFT: 1966 cm(-1)) and E°({Ru(II)-NO(+)}/{Ru(II)-NO˙}) of 0.49 and 0.67 V versus SCE, respectively. The ν(NO) frequency of the reduced {Ru-NO˙} state in 4(2+) or 8(2+) however decreases to 1632 cm(-1) (DFT: 1637 cm(-1)) or 1634 cm(-1) (DFT: 1632 cm(-1)), respectively, with the change of the linear {Ru(II)-NO(+)} geometry in 4(3+), 8(3+) to bent {Ru(II)-NO˙} geometry in 4(2+), 8(2+). The preferential stabilisation of the eclipsed conformation of the bent NO in 4(2+) and 8(2+) has been supported by the DFT calculations. The reduced {Ru(II)-NO˙} exhibits free-radical EPR with partial metal contribution revealing the resonance formulation of {Ru(II)-NO˙}(major)?{Ru(I)-NO(+)}(minor). The electronic transitions of the complexes have been assigned based on the TD-DFT calculations on their DFT optimised structures. The estimated second-order rate constant (k, M(-1) s(-1)) of the reaction of the nucleophile, OH(-) with the electrophilic {Ru(II)-NO(+)} for the bpy derivative (4(3+)) of 1.39 × 10(-1) is half of that determined for the pap derivative (8(3+)), 2.84 × 10(-1) in CH(3)CN at 298 K. The Ru-NO bond in 4(3+) or 8(3+) undergoes facile photolytic cleavage to form the corresponding solvent species {Ru(II)-CH(3)CN}, 2(2+) or 6(2+) with widely varying rate constant values, (k(NO), s(-1)) of 1.12 × 10(-1) (t(1/2) = 6.2 s) and 7.67 × 10(-3) (t(1/2) = 90.3 s), respectively. The photo-released NO can bind to the reduced myoglobin to yield the Mb-NO adduct. 相似文献
996.
Pabitra Kumar Paul Syed Arshad Hussain Debajyoti Bhattacharjee Mrinal Pal 《化学物理学报(中文版)》2011,24(3):348-352
Fabrication of complex molecular films of organic materials is one of the most important issues in modern nanoscience and nanotechnology. Soft materials with flexible properties have been given much attention and can be obtained through bottom up processing from functional molecules, where self-assembly based on supramolecular chemistry and designed assembly have become crucial processes and technologies. In this work, we report the successful incorporation of cationic laser dye rhodamine 6G abbreviated as R6G into the pre-assembled polyelectrolyte/surfactant complex film onto quartz substrate by electrostatic adsorption technique. Poly(allylamine hydrochloride) (PAH) was used as polycation and sodium dodecyl sulphate (SDS) was used as anionic surfactant. UV-Vis absorption spec-troscopic characterization reveals the formation of only H-type aggregates of R6G in their aqueous solution and both H- and J-type aggregates in PAH/SDS/R6G complex layer-by-layber films as well as the adsorption kinetics of R6G onto the complex films. The ratio of the absorbance intensity of two aggregated bands in PAH/SDS/R6G complex films is merely independent of the concentration range of the SDS solution used to fabricate PAH/SDS com-plex self-assembled films. Atomic force microscopy reveals the formation of R6G aggregates in PAH/SDS/R6G complex films. 相似文献
997.
Sen R Koner S Bhattacharjee A Kusz J Miyashita Y Okamoto K 《Dalton transactions (Cambridge, England : 2003)》2011,40(26):6952-6960
[Ru(bpy)(3)](2+) (bpy = 2,2'-bipyridine) ions were entrapped into the cavities of two-dimensional anionic sheet-like coordination polymeric networks of [M(dca)(3)](-) (dca = dicyanamide; M = Mn(II) and Fe(II)). The prepared compounds, {[Ru(bpy)(3)][Mn(dca)(3)](2)}(n) (1) and {[Ru(bpy)(3)][Fe(dca)(3)](2)}(n) (2), were structurally characterized by X-ray single crystal analysis. The spectroscopic properties of the [Ru(bpy)(3)](2+) ion dramatically changed on its entrapment in [M(dca)(3)](-). The [Ru(bpy)(3)](2+) moiety present in 1 and 2 exhibits novel dual photo-emission at room temperature. 相似文献
998.
Suresh Narva Surendar Chitti Suresh Amaroju Sridhar Goud Mallika Alvala Debanjan Bhattacharjee Nishant Jain Chandra Sekhar Kondapalli Venkata Gowri 《Journal of heterocyclic chemistry》2019,56(2):520-532
A series of 28 novel 2‐(4‐aminophenyl)benzothiazole analogues have been synthesized and characterized using various analytical techniques like 1H NMR, 13C NMR, electrospray ionization mass spectrometry, and IR and bioevaluated for their antiproliferative activity over a group of three human cancer cell lines, namely, lung cancer (A549), cervical cancer (HeLa), and breast cancer (MDA‐MB‐231), using sulforhodamine B assay method. Few synthesized molecules ( 5a , 5c , 5d , 5f , 7b , and 7j ) displayed effective growth inhibition (GI50) activity against the tested human cancer cell lines at lower micromolar concentration (GI50) values in the range 0.2–1.7 μM. Noticeably, compound 7b exhibited reasonable activity in all three cancer cell lines in the GI50 range 0.55–1.2 μM. Further, when 7b was screened for tubulin polymerization inhibition, it exhibited more than 55% inhibition at concentration of 5.0 μM. The molecular docking simulations supported the molecular interactions of the derivatives with the targeted receptor. These derivatives may serve as lead structures for development of potential anticancer drug candidates, and 7b might act as a potential microtubule polymerization inhibitor. 相似文献
999.
Savan K. Raj Abhishek Rajput Hariom Gupta 《Journal of Dispersion Science and Technology》2019,40(2):250-255
Graphene quantum dots (GQDs) have been prepared from graphene oxide (GO) and characterized by standard analytical techniques. The size of the prepared GQDs ranges from 2-10?nm. Aqueous dispersion of GQDs exhibited excitation-dependent emission behavior. Emission intensity of the aqueous dispersion found stable for the examined duration of about four months. GQDs exhibited selective recognition of Fe3+ and Cr3+ out of various common ions such as alkali, alkaline-earth and transition metal ions in aqueous medium through fluorescence quenching. The lower limit of detection of Fe3+ is 1?µM and that of Cr3+ is 4?µM. 相似文献
1000.
Abhishek Maurya Neha Kesharwani Payal Kachhap Vivek Kumar Mishra Nikita Chaudhary Chanchal Haldar 《应用有机金属化学》2019,33(9)
Liquid phase catalytic oxidation of a number of alkenes, for example, cyclohexene, cis‐cyclooctene, styrene, 1‐methyl cyclohexene and 1‐hexene, was performed using polymer‐anchored copper (II) complexes PS‐[Cu (sal‐sch)Cl] ( 5 ), PS‐[Cu (sal‐tch)Cl] ( 6 ), PS‐[CH2{Cu (sal‐sch)Cl}2] ( 7 ) and PS‐[CH2{Cu (sal‐tch)Cl}2] ( 8 ). Neat complexes [Cu (sal‐sch)Cl] ( 1 ), [Cu (sal‐tch)Cl] ( 2 ), [CH2{Cu (sal‐sch)Cl}2] ( 3 ) and [CH2{Cu (sal‐tch)Cl}2] ( 4 ) were isolated by reacting CuCl2·2H2O with [Hsal‐sch] ( I ), [Hsal‐tch] ( II ), [H2bissal‐sch] ( III ) and [H2bissal‐tch] ( IV ), respectively, in refluxing methanol. Complexes 1–4 have been covalently anchored in Merrifield resin through the amine nitrogen of the semicarbazide or thiosemicarbazide moiety. A number of analytical, spectroscopic and thermal techniques, such as CHNS analysis, Fourier transform‐infrared, UV–Vis, PMR, 13C‐NMR, electron paramagnetic resonance, scanning electron microscopy, energy‐dispersive X‐ray analysis, thermogravimetric analysis, atomic force microscopy, atomic absorption spectroscopy, and electrospray ionization‐mass spectrometry, were used to analyze and establish the molecular structure of the ligands ( I )–( IV ) and complexes ( 1 )–( 8 ) in solid state as well as in solution state. Grafted complexes 5 – 8 were employed as active catalysts for the oxidation of a series of alkenes in the presence of hydrogen peroxide. Copper hydroperoxo species ([CuIII (sal‐sch)‐O‐O‐H]), which is believed to be the active intermediate, generated during the catalytic oxidation of alkenes, are identified. It was found that supported catalysts are very economical, green and efficient in contrast to their neat complexes as well as most of the recently reported heterogeneous catalysts. 相似文献