全文获取类型
收费全文 | 966篇 |
免费 | 7篇 |
国内免费 | 3篇 |
专业分类
化学 | 648篇 |
晶体学 | 24篇 |
力学 | 25篇 |
数学 | 88篇 |
物理学 | 191篇 |
出版年
2023年 | 3篇 |
2022年 | 13篇 |
2021年 | 25篇 |
2020年 | 12篇 |
2019年 | 15篇 |
2018年 | 10篇 |
2017年 | 7篇 |
2016年 | 24篇 |
2015年 | 12篇 |
2014年 | 10篇 |
2013年 | 64篇 |
2012年 | 41篇 |
2011年 | 44篇 |
2010年 | 39篇 |
2009年 | 32篇 |
2008年 | 59篇 |
2007年 | 56篇 |
2006年 | 45篇 |
2005年 | 55篇 |
2004年 | 42篇 |
2003年 | 32篇 |
2002年 | 54篇 |
2001年 | 14篇 |
2000年 | 11篇 |
1999年 | 13篇 |
1998年 | 9篇 |
1997年 | 14篇 |
1996年 | 17篇 |
1995年 | 12篇 |
1994年 | 11篇 |
1993年 | 16篇 |
1992年 | 4篇 |
1991年 | 10篇 |
1990年 | 7篇 |
1989年 | 11篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 8篇 |
1985年 | 9篇 |
1984年 | 11篇 |
1983年 | 10篇 |
1982年 | 11篇 |
1981年 | 10篇 |
1980年 | 11篇 |
1979年 | 11篇 |
1978年 | 12篇 |
1977年 | 6篇 |
1976年 | 8篇 |
1975年 | 4篇 |
1973年 | 6篇 |
排序方式: 共有976条查询结果,搜索用时 15 毫秒
101.
102.
(R)-Phenylglycinol is shown to be an efficient building block for the synthesis of chiral amino diols in pure diastereomeric form by epoxide ring-opening reactions. The reaction with rac-trans-stilbene oxide gives [HOCH(2)-(R)-PhCH]NH[(S)-PhCH-(R)-PhCHOH] [2(R)-3(R)-4(S)-HNO(2)H(2)] in 32% yield, which can be methylated at nitrogen to give enantiomerically pure [HOCH(2)-(R)-PhCH]NCH(3)[(S)-PhCH-(R)-PhCHOH] [2(R)-3(R)-4(S)-MeNO(2)H(2)]. These amino diol ligands have been used to prepare chiral dioxomolybdenyl complexes of the formula N(R)-2(R)-3(R)-4(S)-(HNO(2))MoO(2) (1) and N(R)-2(R)-3(R)-4(S)-(MeNO(2))MoO(2) (2). The absolute configuration at each stereocenter in the Mo(VI) complexes has been established by (1)H NOESY spectroscopy. The configuration determined for 1 has been confirmed by an X-ray analysis. Crystal data: orthorhombic P2(1)2(1)2(1), a =7.620(3), b = 13.589(2), c = 20.339(3) ?, Z = 4, R = 0.0336. The structure consists of a polymeric chain of N(R)-2(R)-3(R)-4(S)-(HNO(2))MoO(2) molecules connected through unsymmetrical Mo=O --> Mo bridges. Each metal center is coordinated in a distorted octahedral geometry by a cis dioxo unit and by two trans alkoxo atoms. The coordination polyhedron is completed by a nitrogen atom and by a bridging oxo oxygen atom from an adjacent molecule. Compound 2 catalyzes the oxidation of PPh(3) to OPPh(3) by DMSO through a mechanism that involves the intermediacy of a Mo(IV) species. 相似文献
103.
Martina Schfer Ehmke Pohl Karen Schmidt-Bse George M. Sheldrick Rolf Hermann Adriano Malabarba Marino Nebuloni Giancarlo Pelizzi 《Helvetica chimica acta》1996,79(7):1916-1924
The crystal structure of a glycopeptide antibiotic A–40926 aglycone was investigated by X-ray analysis at ?120°. A-40926 crystallises in the orthorhombic space group P212121 with two monomers in the asymmetric unit, a = 21.774(4), b = 28.603(7), c = 29.757(4) Å. ‘Conventional’ direct methods approach failed to solve the structure, but a novel iterative real/reciprocal space procedure was successful. Refinement against 11248 F2 data led to R1 = 13.3% for 6770 F > 4σ (F). The two monomers of A-40926 have similar conformations and are bound by antiparallel H-bonds to form a ‘chain’ structure of connecting dimers. The antibiotic molecule possesses a ‘binding pocket’ for the C-terminal carboxy group of the cell-wall protein, which is consisten with suggestions based on NMR data and the recently reported crystal structure of ureido-balhimycin. In A-40926 the monomers are polymerically linked by H-bonds, quite unlike the tight dimer formation observed in ureido-balhimycin. 相似文献
104.
G. Battistoni C. Bloise P. Campana V. Chiarella A. Ciocio E. Iarocci G. Murtas G. Nicoletti L. Satta E. Bellotti E. Fiorini C. Liguori P. Negri A. Pullia S. Ragazzi M. Rollier P. Serri L. Zanotti G. Bologna C. Castagnoli A. Castellina B. D'Ettorre Piazzoli P. Galeotti G. Mannocchi P. Picchi O. Saavedra S. Vernetto D. Cundy M. Price 《Il Nuovo Cimento C》1986,9(2):196-209
Summary Muon underground data collected in the NUSEX experiment at Mont Blanc have been analysed concerning the following topics:
I) vertical muon intensity, II) prompt muon flux, III) muons from the direction of Cygnus X-3. Preliminary results from the
analysis of more than 20 000 muons are presented and discussed.
Riassunto Gli eventi di muoni rivelati sottoterra nell'esperimento NUSEX al Monte Bianco sono stati analizzati per studiare I) l'intensità verticale dei muoni, II) il flusso di muoni pronti, III) l'eccesso di muoni dalla direzione di Cygnus X-3. In questo lavoro sono presentati c discussi i risultati preliminari ottenuti dal'lanalisi di piú di 20.000 eventi.
Резюме Был проведен анализ данных, собранных в экспеимемнте NUSEX на Мон Блане. Анализировались следующие вопросы: 1) интенсивность вертикальных мюонов, 2) поток мгновенных (быстрых) мюонов, 3) мюоны, движущиеся в направлении от Лебедь X-3. Приводятся и обсуждаются предварительные результаты анализа для более, чем 20 000 муонов.相似文献
105.
Minardi Giovannina Mura Emanuela Pistuddi Angelo M. Solinas Costantino Bacchi Alessia Pelizzi Corrado Pelizzi Giancarlo Chelucci Giorgio 《Transition Metal Chemistry》1999,24(4):481-485
Chelating properties of C2-symmetric chiral bipyridine ligands are discussed. In particular we report the syntheses of the cobalt(II), nickel(II), zinc(II) and copper(II) complexes of (4S,5S)-2,2-dimethyl-4,5-bis(2-pyridyl)-1,3-dioxolane. All compounds have been characterized by IR spectroscopy, and an X-ray diffraction analysis has been carried out on one of them: Co(L)(NO3)2. The ligand coordinates the cobalt atom by the two nitrogen donors N(1) and N(2). A seven-membered chelation ring is formed, presenting a remarkable non-crystallographic twofold pseudosymmetry around the axis connecting Co and the midpoint of the C(6)–C(7) bond. The metal also binds two monodentate nitrates, thus completing a distorted coordination tetrahedron. 相似文献
106.
Let (ℋ
t
)
t≥0 be the Ornstein-Uhlenbeck semigroup on ℝ
d
with covariance matrix I and drift matrix −λ(I+R), where λ>0 and R is a skew-adjoint matrix and denote by γ
∞ the invariant measure for (ℋ
t
)
t≥0. Semigroups of this form are the basic building blocks of Ornstein-Uhlenbeck semigroups which are normal on L
2(γ
∞). We investigate the weak type 1 estimate of the Riesz transforms for (ℋ
t
)
t≥0. We prove that if the matrix R generates a one-parameter group of periodic rotations then the first order Riesz transforms are of weak type 1 with respect
to the invariant measure γ
∞. We also prove that the Riesz transforms of any order associated to a general Ornstein-Uhlenbeck semigroup are bounded on
L
p
(γ
∞) if 1<p<∞.
The authors have received support by the Italian MIUR-PRIN 2005 project “Harmonic Analysis” and by the EU IHP 2002-2006 project
“HARP”. 相似文献
107.
Fernando Cruz Moraes Sonia Tomie Tanimoto Giancarlo Richard Salazar‐Banda Sergio Antonio Spinola Machado Lucia Helena Mascaro 《Electroanalysis》2009,21(9):1091-1098
The electrochemical detection of the hazardous pollutant 4‐nitrophenol (4‐NP) at low potentials, in order to avoid matrix interferences, is an important research challenge. This study describes the development, electrochemical characterization and utilization of a multiwall carbon nanotube (MWCNT) film electrode for the quantitative determination of 4‐NP in natural water. Electrochemical impedance spectroscopy measurements showed that the modified surface exhibits a decrease of ca. 13 times in the charge transfer resistance when compared with a bare glassy carbon (GC) surface. Voltammetric experiments showed the possibility to oxidize a hydroxylamine layer (produced by the electrochemical reduction of 4‐NP on the GC/MWNCT surface) in a potential region which is approximately 700 mV less positive than that needed to oxidize 4‐NP, thus minimizing the interference of matrix components. The limit of detection for 4‐NP obtained using square‐wave voltammetry (0.12 μmol L?1) was lower than the value advised by EPA. A natural water sample from a dam located in São Carlos (Brazil) was spiked with 4‐NP and analyzed by the standard addition method using the GC/MWCNT electrode, without any further purification step. The recovery procedure yielded a value of 96.5% for such sample, thus confirming the suitability of the developed method to determine 4‐NP in natural water samples. The electrochemical determination was compared with that obtained by HPLC with UV‐vis detection. 相似文献
108.
109.
N-Propargylic beta-enaminones have been used as common intermediates for the synthesis of polysubstituted pyrroles and pyridines. Best results have been obtained using DMSO as solvent. In the presence of Cs(2)CO(3) N-propargylic beta-enaminones are cyclized to pyrroles in good to high yields, whereas omitting bases and using CuBr leads to the selective formation of pyridines. 相似文献
110.
Giancarlo Masci Marco Diociaiuti Vittorio Crescenzi 《Journal of polymer science. Part A, Polymer chemistry》2008,46(14):4830-4842
Thermosensitive anionic block copolymers of sodium 2‐acrylamido‐2‐methylpropanesulfonate (AMPS) and N‐isopropylacrylamide (NIPAAM) with different block lengths were prepared by atom transfer radical polymerization (ATRP). Controlled polymerization was achieved by using ethyl 2‐chloropropionate (ECP) as initiator and CuCl/CuCl2/tris(2‐dimethylaminoethyl)amine (Me6TREN) catalytic system in DMF:water 50:50 (v/v) mixtures at 20 °C. Blocks lengths ranging from 36 to 98 repeating units were obtained. The association properties in aqueous solutions at different NaCl ionic strengths were studied as a function of temperature and polymer concentration by dynamic light scattering, fluorescence spectroscopy, and energy‐filtered transmission electron microscopy. The block copolymers with a higher pNIPAAM/pAMPS ratio formed spherical core‐shell type micelles independently of the ionic strength. The block copolymers with lower pNIPAAM/pAMPS ratio formed core‐shell type micelles at high ionic strength. Larger particles were observed at low ionic strength, which could be due to the formation of vesicles or compound micelles/micellar clusters. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4830–4842, 2008 相似文献