全文获取类型
收费全文 | 2611篇 |
免费 | 80篇 |
国内免费 | 9篇 |
专业分类
化学 | 1734篇 |
晶体学 | 26篇 |
力学 | 58篇 |
数学 | 312篇 |
物理学 | 570篇 |
出版年
2023年 | 18篇 |
2022年 | 80篇 |
2021年 | 81篇 |
2020年 | 55篇 |
2019年 | 57篇 |
2018年 | 55篇 |
2017年 | 42篇 |
2016年 | 81篇 |
2015年 | 88篇 |
2014年 | 82篇 |
2013年 | 154篇 |
2012年 | 168篇 |
2011年 | 179篇 |
2010年 | 118篇 |
2009年 | 110篇 |
2008年 | 157篇 |
2007年 | 123篇 |
2006年 | 110篇 |
2005年 | 108篇 |
2004年 | 88篇 |
2003年 | 58篇 |
2002年 | 73篇 |
2001年 | 45篇 |
2000年 | 44篇 |
1999年 | 41篇 |
1998年 | 35篇 |
1997年 | 35篇 |
1996年 | 28篇 |
1995年 | 31篇 |
1994年 | 32篇 |
1993年 | 28篇 |
1992年 | 33篇 |
1991年 | 25篇 |
1990年 | 17篇 |
1989年 | 10篇 |
1988年 | 22篇 |
1987年 | 9篇 |
1986年 | 12篇 |
1985年 | 17篇 |
1984年 | 17篇 |
1983年 | 12篇 |
1982年 | 29篇 |
1981年 | 12篇 |
1980年 | 15篇 |
1978年 | 7篇 |
1977年 | 10篇 |
1976年 | 9篇 |
1975年 | 5篇 |
1974年 | 9篇 |
1973年 | 6篇 |
排序方式: 共有2700条查询结果,搜索用时 35 毫秒
71.
Modifications in the thermal degradation mechanism of polypropylene caused by interactions between the degrading polymer, a chloroparaffin and bismuth carbonate (typical fire retardant additives) are studied.Preliminary TVA and pyrolysis-GLC results show that volatilisation of the polymer occurs at lower temperatures with production of a larger proportion of higher boiling chain fragments in the mixture than in the pure polymer.The products of a strongly exothermal reaction occurring when the two additives are heated together, as shown by DTA and TG, could play an important role in modifying the thermal degradation behaviour of polypropylene in the mixture. 相似文献
72.
Lopes SC Goormaghtigh E Cabral BJ Castanho MA 《Journal of the American Chemical Society》2004,126(17):5396-5402
The organization of the polyene antibiotic filipin in membranes containing cholesterol is a controversial matter of debate. Two contradictory models exist, one suggesting a parallel and the other perpendicular organization of filipin with respect to the plane of the membrane. UV-vis linear dichroism, ATR-FTIR, and fluorescence anisotropy decay techniques were combined to study the orientation of filipin in model systems of membranes composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) or 1,2-palmitoyl-sn-glycero-3-phosphocholine (DPPC) with and without cholesterol. Filipin's orientation is determined by the presence/absence of cholesterol when it is inserted in gel crystalline phase model membranes. When cholesterol (33%) is present in DPPC bilayers, filipin stands perpendicular to the membrane surface as expected in "pore-forming" models. At variance, absence of cholesterol leaves filipin in an essentially random organization in the lipidic matrix. In liquid crystalline phase bilayers (POPC) filipin's orientation is perpendicular to the membrane surface even in absence of cholesterol. Thus filipin's activity/organization depends not only on cholesterol presence but also in the lipid phase domain it is inserted in. These findings were combined with spectroscopy and microscopy data in the literature, solving controversial matters of debate. 相似文献
73.
Summary A fast, sensitive, high performance liquid chromatographic method for the simultaneous determination of cholesterol hydroperoxides
and other major oxysterols, using two different detection systems (ultraviolet at 210 nm and light scattering), is here described.
The hydroperoxy derivatives were obtained by cholesterol photoxidation, isolated by thin layer chromatography and joined with
a standard mixture of 10 oxysterols (epoxy, hydroxy and keto derivatives). Aliquots were directly injected onto a 5-μm particle
size, 25×0.46 cm i.d. Spherisorb S5 CN normal phase column, usingn-hexane/anhydrous ethanol (97:3, v/v) as mobile phase and a flow rate of 0.8 mL min−1. This method allowed, in a single isocratic analysis, the separation and quantification of the primary and secondary cholesterol
oxidation products in 30 minutes. The light scattering detector was particularly useful for the determination of nonderivatized
5,6-epoxides and cholestane-3β,5α,6β-triol. The sensitivity of both detectors was very similar for most of the oxysterols,
except for the 5,6-epoxides and the 7-ketocholesterol. The method suitability for the determination of cholesterol oxidation
products in food matrices was successfully tested on a saponified lipid extract from egg yolk powder. 相似文献
74.
Ferreira AR de A Vilela GV Amorim MB Perry KP da Silva AJ Dias AG Costa PR 《The Journal of organic chemistry》2004,69(12):4013-4018
The conjugate addition of benzylic phenylsulfonyl carbanions (2a'-d') to enoates derived from d-(+)-mannitol (E- or Z-1a-c) was studied using THF and THF/HMPA as solvent. Under kinetic conditions (-78 degrees C), enoate E-1a,b led to a mixture of syn-(R,S) and anti-(S,S) adducts (55/45), and syn-(R,S) adducts were the main product obtained ( approximately 90/10) from enoate Z-1a. Under thermodynamic conditions (-78 degrees C to room temperature) syn-(R,S) adducts were also preferentially formed ( approximately 90/10), despite the geometry at the double bond in the acceptor. Enoate 1c (E/Z = 57/43), bearing an additional benzyl group at the alpha-position, also reacted with carbanions 2'a,b, under thermodynamic conditions, leading to syn-adducts in excellent de (control at the three newly generated stereogenic centers). The adducts were quantitatively transformed into the corresponding beta-gamma-disubstituted gamma-butyrolactones and alpha,beta,gamma-trisubstituted gamma-butyrolactones. (1)H NMR studies (NOE and J-coupling) of these lactones allowed us to determine their configuration at the newly generated chiral centers. The reduction of the C-S bond in adducts syn-(R,S) with Na/Hg, followed by treatment of the resulting products in aqueous acid media, led to enantioenriched beta-benzyl-gamma-hydroxymethyl-gamma-butyrolactones. The conformational equilibrium of enoates E- and Z-1b was evaluated by theoretical calculations (ab initio, MP2/6-31G), and a mechanistic rationale was proposed to explain the observed stereoselectivities. 相似文献
75.
G. A. Costa E. A. Franceschi A. Tawansi 《Journal of Thermal Analysis and Calorimetry》1984,29(4):665-671
Electrical resistivity, magnetic susceptibility, X-ray diffraction and differential thermal analysis have been performed over a wide temperature range on binary compounds RCu. Melting points or decomposition temperatures for RCu (R=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb and Dy) phases and a number of FeB-CsCl structural transitions are reported, and heats and entropies of transformation are evaluated. Large hysteresis effects are observed for the structural transformations at different temperatures.In LaCu and CeCu no structural transformation was detected, while TbCu and DyCu failed to reveal any high-temperature thermal effect of transformation. In EuCu a nonreproducible thermal effect was evidenced after thermal cycling.
The authors are grateful to Prof. A. Iandelli for his interest and for helpful discussion.
This work was supported by the Italian Consiglio Nazionale delle Ricerche. 相似文献
Zusammenfassung Messungen der elektrischen Leitfähigkeit und der magnetischen Susceptibilität sowie röntgendiffraktometrische und differentialthermoanalytische Untersuchungen von binären Verbindungen des Typs RCu wurden in einem weiten Temperaturbereich ausgeführt. Schmelzpunkte bzw. Zersetzungstemperaturen von RCu-Phasen (R=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb und Dy) und eine anzahl von Phasenübergängen im System FeB-CsCl sind zusammen mit den bestimmten Entropiewerten der Phasenübergänge angegeben. Die Temperaturabhängigkeit der Phasenübergänge weist eine ausgeprägte Hysterese auf. In den Systemen LaCu und CeCu konnten keine Phasenübergänge festgestellt werden, während sich bei TbCu und DyCu kein auf einen Phsenübergang hinweisender thermischer Effekt im Hochtemperaturbereich zeigt. Bei EuCu wurde ein nicht-reproduzierbarer thermischer Effekt nach einem thermischen Kreisprozeß nachgewiesen.
, , RCu. RCu (=La, , Pr, Nd,Sm, Eu, Gd, Tb Dy) , FeB-CsCl, . . LaCu , TbCu DyCu - . EuCu .
The authors are grateful to Prof. A. Iandelli for his interest and for helpful discussion.
This work was supported by the Italian Consiglio Nazionale delle Ricerche. 相似文献
76.
This work describes the preparation of a new modified electrode containing a ruthenium complex (cis-aquadimethylbipyridyltriphenylphosphineruthenium II), bonded to a stable polyphenol film. This modified electrode promotes the fast electrocatalytic oxidation of safrol (5-allyl-benzo[1,3]dioxole) and isosafrol (5-propenyl-benzo[1,3]dioxole), giving two interesting products benzo[1,3]dioxole-5-carbaldehyde (piperonal) and 3-benzo[1,3]dioxol-5-yl-propenal respectively, with good yields. The electrode preparation can be carried out at a potential range which does not interfere on the anchored electroactive ruthenium complex, but it allows for the phenol oxidation to occur and therefore polymerize forming the polyphenol film. The catalytic character of this modified electrode is showed by its high turnover numbers. The procedure to isolate the products is very simple. 相似文献
77.
Gian Paolo Chiusoli Mirco Costa Luciano Pallini Giuliana Terenghi 《Transition Metal Chemistry》1982,7(6):304-306
Summary In presence of nickel or palladium catalysts, nucleophiles can attack vinylcyclopropanes with concomitant ring cleavage. With palladium catalysts in presence of appropriate substituents the terminal carbon atom of the resulting open chain is able to add to two molecules of a conjugated diene giving rise to long-chain unsaturated compounds. 相似文献
78.
We studied the Y–Ba–Cu–O/Ag equilibrium diagram in oxygen atmosphere around the composition YBa2Cu3Ox/Ag35 mass%. We found a high thermal effect: the peritectic decomposition temperature of Y-123 phase is lowered from 1040
to 940°C. We demonstrate here that the nature of the phenomenon is not chemical. We explained it as the result of a mechanical
segregation of Y-123 decomposition products from Y-123 phase, performed by silver.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
79.
Marta Catellani Gian Paolo Chiusoli Mirco Costa 《Journal of organometallic chemistry》1995,500(1-2):69-80
Chelating or metallacycle-forming substrates are very useful for directing organometallic reactions. This review covers the more recent research that has been carried out in the authors' laboratory. Rhodium(I)- and (III)-catalysed reactions of C---C coupling of butadiene with N-allylamides or N-alkylbutenamides are described. These reactions are controlled by the size and strength of the chelate ring formed by double-bond insertion into the crotyl-rhodium bond (formed from butadiene) and their regioselectivity can change with the oxidation state of the metal. Rhodium(I)-catalysed reactions of butadiene with enamides are also chelation controlled and lead to different products, depending on the substituents at nitrogen. Cobalt(II) metallacycles have been utilized for promoting some organic reactions. It has been shown that alkenes can be catalytically incorporated into cobaltacyclopentadiene rings, that spirocycles can be obtained from diynes, carbon monoxide and acrylic esters and that a Pauson-Khand-type reaction can be combined with a Michael-type reaction to prepare catalytically new cyclopentenones. The use of palladacycles, derived from norbornene insertion into aryl-palladium bonds, followed by cyclization, has allowed the selective functionalization of either end of the metallacycle and the formation of condensed rings. Conversion of a palladium(II) into a palladium(IV) metallacycle, and catalytic processes involving these intermediates, have been achieved. The formation of alkylaromatic palladacycles has also been exploited for the selective meta functionalization of the aromatic moiety by means of alkyl groups, accompanied by expulsion of the norbornene molecule. 相似文献
80.
Bonhommeau S Bréfuel N Pálfi VK Molnár G Zwick A Salmon L Tuchagues JP Sanchez Costa J Létard JF Paulsen H Bousseksou A 《Physical chemistry chemical physics : PCCP》2005,7(15):2909-2914
A quasi-quantitative photo-induced low-spin (LS)-->high-spin (HS) conversion of FeII ions has been observed in the [Fe(TRIM)2]Cl2 complex by irradiating the sample with blue light (488 nm) at 10 K. The time dependence of the HS-->LS relaxation has been studied between 10 K and 44 K by means of magnetic susceptibility measurements. These relaxation curves could be satisfactorily fitted by mono-exponential decays including tunnelling effect except for temperatures below 30 K. The introduction of a distribution of vibrational frequencies into this model improved significantly the fits in the low-temperature range and gave a good agreement with the experimental data in the whole temperature range suggesting a multi-rate relaxation process in this complex. 相似文献