全文获取类型
收费全文 | 3330篇 |
免费 | 79篇 |
国内免费 | 22篇 |
专业分类
化学 | 2068篇 |
晶体学 | 19篇 |
力学 | 145篇 |
数学 | 495篇 |
物理学 | 704篇 |
出版年
2024年 | 4篇 |
2023年 | 35篇 |
2022年 | 78篇 |
2021年 | 114篇 |
2020年 | 100篇 |
2019年 | 80篇 |
2018年 | 58篇 |
2017年 | 46篇 |
2016年 | 130篇 |
2015年 | 91篇 |
2014年 | 134篇 |
2013年 | 172篇 |
2012年 | 223篇 |
2011年 | 257篇 |
2010年 | 145篇 |
2009年 | 128篇 |
2008年 | 200篇 |
2007年 | 193篇 |
2006年 | 209篇 |
2005年 | 193篇 |
2004年 | 149篇 |
2003年 | 128篇 |
2002年 | 126篇 |
2001年 | 49篇 |
2000年 | 25篇 |
1999年 | 29篇 |
1998年 | 32篇 |
1997年 | 38篇 |
1996年 | 36篇 |
1995年 | 22篇 |
1994年 | 22篇 |
1993年 | 18篇 |
1992年 | 7篇 |
1991年 | 16篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 11篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1983年 | 9篇 |
1982年 | 12篇 |
1981年 | 14篇 |
1980年 | 7篇 |
1979年 | 10篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 9篇 |
排序方式: 共有3431条查询结果,搜索用时 0 毫秒
71.
Stefano Caramori Dr. Jérôme Husson Dr. Marc Beley Prof. Carlo A. Bignozzi Prof. Roberto Argazzi Dr. Philippe C. Gros Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(8):2611-2618
Mixtures of polypyridine FeII and CoII complexes are used as electron mediators in Ru–thienyltpy‐sensitised solar cells (tpy=terpyridine). The use of the metalorganic redox couples allows for improved charge‐collection efficiency with respect to the classical iodide/iodine couple which, when associated to Ru–tpy2 dyes, usually produces poor performance. The improved charge collection is explained by a combination of effective dye regeneration and decreased recombination with the oxidised electrolyte on the basis of data obtained by transient spectroscopy and photoelectrochemical measurements. The efficiency of the regeneration cascade is also critically dependent upon the ability of the CoII complex to intercept FeIII centres, as clearly indicated by chronocoulometry experiments. 相似文献
72.
Lorenzo Di Terlizzi Prof. Stefano Protti Prof. Davide Ravelli Prof. Maurizio Fagnoni 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(26):e202200313
With the aim of generating new, thermally inaccessible diradicals, potentially able to induce a double-strand DNA cleavage, the photochemistry of a set of chloroaryl-substituted carboxylic acids in polar media was investigated. The photoheterolytic cleavage of the Ar−Cl bond occurred in each case to form the corresponding triplet phenyl cations. Under basic conditions, the photorelease of the chloride anion was accompanied by an intramolecular electron-transfer from the carboxylate group to the aromatic radical cationic site to give a diradical species. This latter intermediate could then undergo CO2 loss in a structure-dependent fashion, according to the stability of the resulting diradical, or abstract a hydrogen atom from the medium. In aqueous environment at physiological pH (pH=7.3), both a phenyl cation and a diradical chemistry was observed. The mechanistic scenario and the role of the various intermediates (aryl cations and diradicals) involved in the process was supported by computational analysis. 相似文献
73.
Giovanni Fronza Claudio Fuganti Piero Grasselli Stefano Servi 《Tetrahedron letters》1985,26(40):4961-4964
Baker's yeast mediated reduction of the α-acetoxy ketones (1)–(3) proceeds with high enantio- and stereoselectivity to give the carbinols (4)–(6), easily converted into the masked chiral deoxy sugars (12)–(14), from which {=D}- and {=L}-deoxysugars have been obtained. 相似文献
74.
Ricardo Bossio Stefano Marcaccini Valerio Parrini Roberto Pepino 《Journal of heterocyclic chemistry》1985,22(4):1147-1148
2-(Benzimidazol-2-ylamino)pyridine (4a) , 2-(benzimidazol-2-ylamino)pyrazine (4b) , and 2-(benzimidazol-2-ylamino)thiazole (4c) underwent a ring-closure reaction on treatment with phosgene affording 6H-pyrimido-[1′,2′:5,4][1,3,5]triazino[1,2-a]benzimidazol-6-one (1a) , 6H-pyrazino[1′,2′:5,4][1,3,5]triazino[1,2-a]benzimidazol-6-one (1b) , and 5H-thiazolo[2′,3′:4,5][1,3,5]triazino[1,2-a]benzimidazol-5-one (1c) respectively. The structure of these hitherto unknown heterocyclic systems was confirmed by their ir and mass spectra. 相似文献
75.
Dr. Anil Reddy Marri Edoardo Marchini Dr. Valentin Diez Cabanes Dr. Roberto Argazzi Dr. Mariachiara Pastore Prof. Stefano Caramori Prof. Carlo Alberto Bignozzi Dr. Philippe C. Gros 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(65):16260-16269
A series of six new Fe(II)NHC-carboxylic sensitizers with their ancillary ligand decorated with functions of varied electronic properties have been designed with the aim to increase the metal-to- surface charge separation and light harvesting in iron-based dye-sensitized solar cells (DSSCs). ARM130 scored the highest efficiency ever reported for an iron-sensitized solar cell (1.83 %) using Mg2+ and NBu4I-based electrolyte and a thick 20 μm TiO2 anode. Computational modelling, transient absorption spectroscopy and electrochemical impedance spectroscopy (EIS) revealed that the electronic properties induced by the dimethoxyphenyl-substituted NHC ligand of ARM130 led to the best combination of electron injection yield and spectral sensitivity breadth. 相似文献
76.
Melania Melis Mariano Mastinu Stefano Pintus Tiziana Cabras Roberto Crnjar Iole Tomassini Barbarossa 《Molecules (Basel, Switzerland)》2021,26(8)
Taste plays an important role in processes such as food choices, nutrition status and health. Salivary proteins contribute to taste sensitivity. Taste reduction has been associated with obesity. Gender influences the obesity predisposition and the genetic ability to perceive the bitterness of 6-n-propylthiouracil (PROP), oral marker for food preferences and consumption. We investigated variations in the profile of salivary proteome, analyzed by HPLC-ESI-MS, between sixty-one normal weight subjects (NW) and fifty-seven subjects with obesity (OB), based on gender and PROP sensitivity. Results showed variations of taste-related salivary proteins between NW and OB, which were differently associated with gender and PROP sensitivity. High levels of Ps-1, II-2 and IB-1 proteins belonging to basic proline rich proteins (bPRPs) and PRP-1 protein belonging to acid proline rich proteins (aPRPs) were found in OB males, who showed a lower body mass index (BMI) than OB females. High levels of Ps-1 protein and Cystatin SN (Cyst SN) were found in OB non-tasters, who had lower BMI than OB super-tasters. These new insights on the role of salivary proteins as a factor driving the specific weight gain of OB females and super-tasters, suggest the use of specific proteins as a strategic tool modifying taste responses related to eating behavior. 相似文献
77.
A routine method for the determination of chloride, nitrate and sulfate anions in rainwater by capillary electrophoresis was developed. The system uses an end-column non-suppressed conductivity detector. Linear calibration plots were generated from 0.050 to 20 mg/l, which is the range generally found in wet depositions. Accuracy and precision were evaluated by analyzing certified standards of simulated rainwater and environmental samples, or by comparing CE results with those obtained by IC, the reference technique for anion analysis in wet deposition. The reproducibility of the method was satisfactory except at the lower and upper limits of the analytical range. Sensitivity lay in the range of few μg/l. 相似文献
78.
Copper(II) complexes with the herbicide N-(phosphonomethyl)glycine (glyphosate) have been investigated in aqueous solution by means of pH-metric measurements at different temperatures, 5 = T = 45 degrees C, calorimetry and visible spectrophotometry. Potentiometric data, at all the considered temperatures in the range 2.5 = pH = 10.5, can be explained assuming the formation of the species CuLH(0), CuL(-), CuLH(2 -)(- 1), CuL(4 -)(2) and Cu(2)L(+). By using thermodynamic data and calculated electronic spectra for each complex a structural definition is proposed for the different species. Copper(II)-glyphosate complexes are quite stable and must be taken into account in the speciation of natural fluids. 相似文献
79.
Sergio Brückner Paul J. Phillips Khaled Mezghani Stefano V. Meille 《Macromolecular rapid communications》1997,18(1):1-7
The non-parallel chain structure determined for γ-phase isotactic polypropylene (γ-iPP) is confirmed by Rietveld analysis for highly isotactic high molecular mass iPP crystallized at 200 MPa. The new refinement shows that: (i) stereoregularity or crystallization pressure do not significantly influence the lattice dimensions; (ii) defect inclusion in γ-iPP crystals is unlikely. The α and γ forms have nearly identical bulk internal energy and density, but α-iPP should be normally kinetically favored over γ-iPP which may in turn predominate due to its greater ability to host defects at the crystalline-amorphous interface. 相似文献
80.
Giovanni Ricci Giuseppe Leone Giorgia Zanchin Benedetta Palucci Alessandra Forni Anna Sommazzi Francesco Masi Stefano Zacchini Massimo Guelfi Guido Pampaloni 《Molecules (Basel, Switzerland)》2021,26(13)
Some novel cobalt diphenylphosphine complexes were synthesized by reacting cobalt(II) chloride with (2-methoxyethyl)diphenylphosphine, (2-methoxyphenyl)diphenylphosphine, and 2-(1,1-dimethylpropyl)-6-(diphenylphosphino)pyridine. Single crystals suitable for X-ray diffraction studies were obtained for the first two complexes, and their crystal structure was determined. The novel compounds were then used in association with methylaluminoxane (MAO) for the polymerization of 1,3-butadiene, and their behavior was compared with that exhibited in the polymerization of the same monomer by the systems CoCl2(PnPrPh2)2/MAO and CoCl2(PPh3)2/MAO. Some significant differences were observed depending on the MAO/Co ratio used, and a plausible interpretation for such a different behavior is proposed. 相似文献