全文获取类型
收费全文 | 2673篇 |
免费 | 79篇 |
国内免费 | 5篇 |
专业分类
化学 | 2137篇 |
晶体学 | 16篇 |
力学 | 35篇 |
数学 | 220篇 |
物理学 | 349篇 |
出版年
2023年 | 15篇 |
2022年 | 74篇 |
2021年 | 79篇 |
2020年 | 37篇 |
2019年 | 57篇 |
2018年 | 36篇 |
2017年 | 37篇 |
2016年 | 80篇 |
2015年 | 76篇 |
2014年 | 86篇 |
2013年 | 125篇 |
2012年 | 165篇 |
2011年 | 161篇 |
2010年 | 120篇 |
2009年 | 97篇 |
2008年 | 173篇 |
2007年 | 163篇 |
2006年 | 136篇 |
2005年 | 180篇 |
2004年 | 128篇 |
2003年 | 115篇 |
2002年 | 97篇 |
2001年 | 46篇 |
2000年 | 37篇 |
1999年 | 38篇 |
1998年 | 21篇 |
1997年 | 37篇 |
1996年 | 29篇 |
1995年 | 22篇 |
1994年 | 21篇 |
1993年 | 22篇 |
1992年 | 14篇 |
1991年 | 17篇 |
1990年 | 17篇 |
1989年 | 15篇 |
1988年 | 14篇 |
1987年 | 19篇 |
1986年 | 7篇 |
1985年 | 20篇 |
1984年 | 16篇 |
1983年 | 12篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 11篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1976年 | 7篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1972年 | 4篇 |
排序方式: 共有2757条查询结果,搜索用时 0 毫秒
101.
Karla G. Gutiérrez-Cuevas Rosa Julia Rodríguez-González Bertrand Donnio Damaso Navarro-Rodríguez 《Liquid crystals》2013,40(4):534-545
In this article, we report on the synthesis and thermotropic behaviour of methacrylic polymers containing 4′-(4-alkyloxyphenyl)azobenzene mesogens attached to the backbone through n-alkyloxy spacers of 6 or 10 methylene groups. Polymerisations were carried out via free radicals using azobisisobutyronitrile (AIBN) as initiator. Chemical structures of polymers and their precursors were characterised by 1H NMR spectroscopy. Thermogravimetric analysis showed that azopolymers are thermally stable up to temperatures around 300°C. The thermotropic liquid-crystalline (LC) behaviour was studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and X-ray diffraction (XRD). Results indicate that all synthesised mesogens, monomers and polymers developed two or more orthogonal LC phases in wide temperature ranges. Mesogens and monomers developed nematic and smectic phases, whereas polymers exhibited only smectic phase. In polymers, the arrangement of mesogens depends on the relative length of the spacer and the terminal flexible chain; two distinct structural models were proposed based on chemical interactions and steric constrains. The trans–cis photoisomerisation of monomers and polymers in solution was also studied. High cis-isomer contents (>80%) were reached in relative short irradiation times despite the steric constrains imposed by the polymer backbone. 相似文献
102.
Domenico Grasso Carmelo La Rosa Antonio Raudino Felice Zuccarello 《Liquid crystals》2013,40(12):1699-1705
Abstract Scanning dilatometric and calorimetric measurements were performed in order to obtain information on correlations between various phenomena involving a lipid vesicle. Scanning dilatometry has been shown to be a fast and reliable tool which gives complementary information to that obtained using differential scanning calorimetry and also, provides a means with which to follow dynamic processes without the introduction of perturbing probes into the lipid matrix. The systems examined were vesicles built up from mixtures of neutral and charged lipids in the presence of mono- and divalent inorganic cations. The studied processes were the gel-liquid crystal transition, lateral phase separation in mixed lipid vesicles and fusion between vesicles. 相似文献
103.
Tagless extraction-retentate chromatography: a new global protein digestion strategy for monitoring differential protein expression 总被引:5,自引:0,他引:5
A new global protein digestion and selective peptide extraction strategy for the purpose of monitoring differential protein expression, coined as tagless extraction-retentate chromatography, is introduced. Target protein populations are firstly digested under reduced and alkylated conditions, and resultant peptides selectively extracted via covalent attachment to methionine residues by bromoacetyl reactive groups tethered to the surface of glass beads packed in small reaction vessels. After conjugation, reactive beads are stringently washed to remove nonspecifically bound peptides and then later treated with beta-mercaptoethanol to release captured methionine peptides in their nascent state, without complicating affinity tags. Recovered methionine containing peptides are profiled using the surface-enhanced laser desorption/ionization (SELDI) retentate chromatography mass spectrometry (RCMS) method. Selected peptides are further studied employing ProteinChip tandem mass spectrometry (MS/MS) analysis to identify their parent proteins. This approach has been applied to an Escherichia coli lysate model system and has demonstrated facility in reducing global digest complexity, sensitivity to low protein expression levels, and significant quantitative capability. It is envisioned that tagless extraction-RCMS will evolve to be a valuable approach for both basic research and clinical proteomics endeavors. 相似文献
104.
Ciminiello P Dell'Aversano C Fattorusso E Forino M Magno S Di Rosa M Ianaro A Poletti R 《Journal of the American Chemical Society》2002,124(44):13114-13120
A detailed analysis of the causative toxins contained in the hepatopancreas of toxic mussels from the northern Adriatic sea has been carried out. Along with some DSP (diarrhetic shellfish poisoning) type toxins, such as okadaic acid, yessotoxin, and their derivatives, which are involved in a number of human intoxications throughout the world, we have now isolated a new cytotoxin, a polychlorinated sulfolipid 1, whose gross structure has been elucidated by spectral analysis, including various 2D NMR techniques. The relative stereochemistry of 1 was elucidated by successful application of the J-based configuration analysis developed for acyclic compounds using carbon-proton spin-coupling constants ((2,3)J(C,H)) and proton-proton spin-coupling constants ((3)J(H,H)); its absolute stereochemistry was established by the Mosher method. Compound 1 possesses in vitro cytotoxicity against WEHI 164 and RAW 264.7 cells. 相似文献
105.
Four new two-ligand complexes of copper(II) with 2,2′-bipyridine and one of three different α-hydroxycarboxylic acids (lactic, H2LACO; 2-methyllactic, H2MLACO; and mandelic, H2MANO) were prepared. Complexes 1–3 of general formula [Cu(HL)2(bipy)]·nH2O (HL=monodeprotonated acid), were characterized by elemental analysis, IR, electronic and EPR spectroscopy, magnetic measurements and thermogravimetric analysis. Complexes 1 (HL=HLACO, n=2), 2 (HL=HMLACO, n=1) and 3a (the result of attempted recrystallization of 3, of formula [Cu(HMANO)(bipy)2](HMANO)·H2MANO·CH3CN were studied by X-ray diffractometry. The copper atom is in an elongated, tetragonally distorted octahedral environment in 1 and 2 and in 3a has a coordination polyhedron intermediate between a square pyramid and a trigonal bipyramid, as evaluated in terms of the parameter τ. In 1 and 2 the α-hydroxycarboxylato ligand is bidentate and monoanionic but in 3a there are three forms: a monodentate monoanion, a monoanionic counterion, and a neutral molecule. 相似文献
106.
The linking of pyrimidines to polystyrene supports via either a 2- or 4-thioether provides access to pteridines through solid-phase synthesis. Oxidative cleavage (dimethyldioxirane) followed by nucleophilic substitution by amines, azide, or water completes a traceless synthesis of pteridines. 相似文献
107.
Francesco A Bottino Anna Rosa Cinquegrani Giovanna Di Pasquale Leonardi Lucrezia Antonino Pollicino 《European Polymer Journal》2003,39(11):2203-2208
A series of new poly(arylene ether sulfone)s has been obtained by solution condensation polymerisation starting from 1,5- and 2,6-bis-(4-fluorosulfonyl)naphthalene with various aromatic dihydroxy compounds. The polymers, obtained in quantitative yields, possessed inherent viscosities in the range 0.28-0.68 dl g−1, had good thermal stability (10% weight loss temperatures were above 405 and 420 °C respectively in nitrogen and air) and high glass transition temperatures (in the range 217-258 °C). They have been characterised by elemental and infrared analyses, GPC and wide-angle X-ray diffraction. The properties of these poly(arylene ether sulfone)s have been compared with those of the corresponding poly(arylene ether ketone)s. 相似文献
108.
Inductively coupled plasma optical emission spectrometry (ICP-OES) was applied to the analysis of major and minor elements of Ni-Nb alloys obtained by aluminothermic reduction process. Digestion of samples was made using a mixture of HF+HNO3. Minor and trace elements were determined without matrix separation. The precision for all constituents was <3%. Recoveries for the analyte-spiked samples were 95%. 相似文献
109.
Carballo R Casas JS García-Martínez E Pereiras-Gabián G Sánchez A Sordo J Vázquez-López EM 《Inorganic chemistry》2003,42(20):6395-6403
The reactions of methylacetoacetate and ethyl 2-methylacetoacetate thiosemicarbazones (H(2)L(A) and H(2)L(B), respectively) with [ReX(CO)(5)] and [ReX(CO)(3)(CH(3)CN)(2)] (X = Cl, Br) were explored under various experimental conditions. Besides the adducts fac-[ReX(CO)(3)(H(2)L)], in which the rhenium is coordinated to three carbonyl groups, the X anion, and the N,S-bidentate thiosemicarbazone ligand, the following complexes were also isolated: fac-[ReBr(CO)(3)(Hpyz(B))], the tetrameric complexes fac-[Re(pyz(A))(CO)(3)](4) and fac-[Re(pyz(B))(CO)(3)](4), and fac-[Re(pyz(B))(CO)(3)(H(2)O)] (where Hpyz(A) and Hpyz(B) are pyrazolones derived by cyclization of H(2)L(A) and H(2)L(B), respectively). The cyclization reactions were monitored by (1)H NMR spectroscopy and the complexes isolated were identified by elemental analysis, mass spectrometry, IR and (1)H NMR spectroscopy, and in some cases by X-ray diffractometry. The isolation and the full structural identification of the rather unusual fac-[ReBr(CO)(3)(Hpyz(B))], which contains the enol form of the pyrazolone ligand, affords new insight into the cyclization of thiosemicarbazones derived from beta-keto esters. 相似文献
110.
Rosa Caballol Josep M. Ribó Francesc R. Trull Asunción Vallés 《Monatshefte für Chemie / Chemical Monthly》1987,118(8-9):993-1010
The applicability of the MINDO/3 method is evaluated for calculations on dipyrrolic partial structures of bile pigments. It is shown that this method cannot be used for an accurate conformational analysis. However, when applying the frontier orbital model for reactivity parameters, a good picture of the HOMO and the LUMO distribution can be obtained in this type of molecules.
Reaktivität von Pyrrolpigmenten, 9. Mitt. MINDO/3-Rechnungen von dipyrrolischen Partialmodellen von Gallenpigmenten
Zusammenfassung Es werden die Einsatzmöglichkeiten von MINDO/3 für den Fall dipyrrolischer Partialstrukturen der Gallenpigmente aufgezeigt. Die Methode ist für eine genaue Konformationsanalyse nicht geeignet. Unter Verwendung der Reaktionsparameter des Frontier-Orbital-Modells läßt sich jedoch ein gutes Bild der HOMO- und LUMO-Verteilung für diesen Verbindungstyp gewinnen.相似文献