全文获取类型
收费全文 | 429篇 |
免费 | 8篇 |
国内免费 | 2篇 |
专业分类
化学 | 249篇 |
晶体学 | 5篇 |
力学 | 16篇 |
数学 | 67篇 |
物理学 | 102篇 |
出版年
2022年 | 4篇 |
2021年 | 9篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 12篇 |
2017年 | 4篇 |
2016年 | 11篇 |
2015年 | 10篇 |
2014年 | 7篇 |
2013年 | 20篇 |
2012年 | 19篇 |
2011年 | 29篇 |
2010年 | 14篇 |
2009年 | 22篇 |
2008年 | 28篇 |
2007年 | 24篇 |
2006年 | 25篇 |
2005年 | 22篇 |
2004年 | 22篇 |
2003年 | 20篇 |
2002年 | 11篇 |
2001年 | 8篇 |
2000年 | 3篇 |
1999年 | 4篇 |
1998年 | 9篇 |
1997年 | 5篇 |
1996年 | 12篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 10篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1966年 | 1篇 |
1963年 | 2篇 |
排序方式: 共有439条查询结果,搜索用时 218 毫秒
121.
Federica Rizzi Rachele Castaldo Tiziana Latronico Pierluigi Lasala Gennaro Gentile Marino Lavorgna Marinella Striccoli Angela Agostiano Roberto Comparelli Nicoletta Depalo Maria Lucia Curri Elisabetta Fanizza 《Molecules (Basel, Switzerland)》2021,26(14)
Mesoporous silica nanostructures (MSNs) attract high interest due to their unique and tunable physical chemical features, including high specific surface area and large pore volume, that hold a great potential in a variety of fields, i.e., adsorption, catalysis, and biomedicine. An essential feature for biomedical application of MSNs is limiting MSN size in the sub-micrometer regime to control uptake and cell viability. However, careful size tuning in such a regime remains still challenging. We aim to tackling this issue by developing two synthetic procedures for MSN size modulation, performed in homogenous aqueous/ethanol solution or two-phase aqueous/ethyl acetate system. Both approaches make use of tetraethyl orthosilicate as precursor, in the presence of cetyltrimethylammonium bromide, as structure-directing agent, and NaOH, as base-catalyst. NaOH catalyzed syntheses usually require high temperature (>80 °C) and large reaction medium volume to trigger MSN formation and limit aggregation. Here, a successful modulation of MSNs size from 40 up to 150 nm is demonstrated to be achieved by purposely balancing synthesis conditions, being able, in addition, to keep reaction temperature not higher than 50 °C (30 °C and 50 °C, respectively) and reaction mixture volume low. Through a comprehensive and in-depth systematic morphological and structural investigation, the mechanism and kinetics that sustain the control of MSNs size in such low dimensional regime are defined, highlighting that modulation of size and pores of the structures are mainly mediated by base concentration, reaction time and temperature and ageing, for the homogenous phase approach, and by temperature for the two-phase synthesis. Finally, an in vitro study is performed on bEnd.3 cells to investigate on the cytotoxicity of the MNSs. 相似文献
122.
Federico Cozzi Italo Pellegrini Gianpiero Adami Edoardo Reisenhofer Massimo Bovenzi Pierluigi Barbieri 《Central European Journal of Chemistry》2009,7(3):395-401
Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to identify sulphur compounds in PM10 samples
collected simultaneously at two sites with different environmental situations in the province of Trieste (NE of Italy), during
summer and winter seasons respectively. The first site is an industrial site located near a steel mill plant and the second
is a coastal site. The sulphur speciation at the industrial site has shown the presence of the following sulphur compounds
in both seasons: organic compounds (thiophenes or Polycyclic Aromatic Sulphur Heterocycles — PAHs) and sulphates while in
the winter season sulphites were also present. In the coastal site organic compounds (thiophenes or PASHs) and sulphate were
found during winter season, moreover bisulphates were found during summer season. Relative percentages of the different sulphur
compounds have shown that sulphate is the most abundant form of sulphur in the industrial site samples during both seasons
and in the coastal site sample collected during the winter season (> 98%); in the coastal site sample collected during the
summer season the relative percentages of bisulphate and sulphate were around 40% and 60% respectively.
相似文献
123.
Adami G Capriglia L Barbieri P Cozzi F Lo Coco F Acquavita A Reisenhofer E 《Annali di chimica》2006,96(9-10):601-612
The following metals: Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were determined by inductively coupled plasma - atomic emission spectroscopy (ICP-AES) in fluvial sediments of Rosandra Creek, using two different, strong and mild sediment decomposition methods. The purpose was to obtain information about the contamination by metals and distribution paths of pollutants in the area crossed by Rosandra Creek: this little river is the unique epigeous watercourse in the Italian Karst and very few data can be found in literature. In this area, we can find a natural park, but also agricultural activities and an industrial district that was recently defined as "polluted site of national interest". By comparing the results of the strong and mild extraction we have obtained the percentage of extraction and enrichment factors for each metal in the different sediments of the sites R2 and R3 exposed to pollution, while the site R1 was considered as a pristine one because situated in the natural park. The computed enrichment factors are generally not very high, but copper, lead and zinc have factors that require attention. The principal component analysis (PCA) shows that the typically anthropogenic metals (as Cr, Pb, Cu and Zn) constitute the first factor, while the lithogenic metals, as Fe and Ni, constitute the second one; moreover the score plots permit to classify and distinguish the 3 sites: site R3, possibly the more exposed to contamination, has high scores both for anthropogenic and lithogenic metals. 相似文献
124.
Focante F Camurati I Resconi L Guidotti S Beringhelli T D'Alfonso G Donghi D Maggioni D Mercandelli P Sironi A 《Inorganic chemistry》2006,45(4):1683-1692
Reaction between 7-azaindole and B(C6F5)3 quantitatively yields 7-(C6F5)3B-7-azaindole (4), in which B(C6F5)3 coordinates to the pyridine nitrogen of 7-azaindole, leaving the pyrrole ring unreacted even in the presence of a second equivalent of B(C6F5)3. Reaction of 7-azaindole with H2O-B(C6F5)3 initially produces [7-azaindolium]+[HOB(C6F5)3]- (5) which slowly converts to 4 releasing a H2O molecule. Pyridine removes the borane from the known complexes (C6F5)3B-pyrrole (1) and (C6F5)3B-indole (2), with formation of free pyrrole or indole, giving the more stable adduct (C6F5)3B-pyridine (3). The competition between pyridine and 7-azaindole for the coordination with B(C6F5)3 again yields 3. The molecular structures of compounds 4 and 5 have been determined both in the solid state and in solution and compared to the structures of other (C6F5)3B-N-heterocycle complexes. Two dynamic processes have been found in compound 4. Their activation parameters (DeltaH = 66 (3) kJ/mol, DeltaS = -18 (10) J/mol K and DeltaH = 76 (5) kJ/mol, DeltaS = -5 (18) J/mol K) are comparable with those of other (C6F5)3B-based adducts. The nature of the intramolecular interactions that result in such energetic barriers is discussed. 相似文献
125.
In this paper, we discuss some relations between zeros of Lucas–Lehmer polynomials and the Gray code. We study nested square roots of 2 applying a “binary code” that associates bits 0 and 1 to “plus” and “minus” signs in the nested form. This gives the possibility to obtain an ordering for the zeros of Lucas–Lehmer polynomials, which take the form of nested square roots of 2. 相似文献
126.
Guidotti S Camurati I Focante F Angellini L Moscardi G Resconi L Leardini R Nanni D Mercandelli P Sironi A Beringhelli T Maggioni D 《The Journal of organic chemistry》2003,68(14):5445-5465
The reaction of pyrroles and indoles with B(C(6)F(5))(3) and BCl(3) produces 1:1 B-N complexes containing highly acidic sp(3) carbons, for example, N-[tris(pentafluorophenyl)borane]-5H-pyrrole (1) and N-[tris(pentafluorophenyl)borane]-3H-indole (2), that are formed by a new formal N-to-C hydrogen shift, the mechanism of which is discussed. With some derivatives, restricted rotation around the B-N bond and/or the B-C bonds was observed by NMR techniques, and some rotational barriers were calculated from experimental data. The acidity of the sp(3) carbons in these complexes is shown by their ability to protonate NEt(3), with formation of pyrrolyl- and indolyl-borate ammonium salts. The driving force for this reaction is given by the restoration of the aromaticity of the heterocycle. 相似文献
127.
Greci L Castagna R Carloni P Stipa P Rizzoli C Righi L Sgarabotto P 《Organic & biomolecular chemistry》2003,1(21):3768-3771
N,N-Dimethyl-p-nitrosoaniline reacts with benzoyl chloride affording a complex salt containing a cation, a hybrid between a nitrenium ion and an iminium ion. The salt reacts with nucleophiles (indoles, indolizines) yielding compounds characterized by a new carbon-nitrogen bond, derived from the nitrenium ion form. According to the type of nucleophile, the reaction, to differing extents, is in competition with an electron transfer process which leads to the formation of the dimer of the nucleophile and of the azoxy corresponding to the N,N-dimethyl-p-nitrosoaniline. In one of the reactions studied, a chlorinated azoxy derivative was also isolated, and its structure was elucidated by X-ray analysis. 相似文献
128.
129.
Quadrelli P Scrocchi R Piccanello A Caramella P 《Journal of combinatorial chemistry》2005,7(6):887-892
The synthesis of 1,2,4-oxadiazole-4-oxides on polystyrenic solid phase docked at the position 3 of the heterocyclic ring has been performed through the cycloaddition of stable supported nitrile oxides to amidoximes. The photochemical cycloreversion of these heterocycles afforded the free nitrosocarbonyl intermediates that were trapped by suitable dienes or enes. The method is proposed as a clean and environmental friendly approach to the fleeting nitrosocarbonyl intermediates, which afford valuable adducts for various synthetic applications. The isomeric heterocycles docked at the position 5 of the ring have also been obtained by cycloaddition of nitrile oxides to supported amidoximes. Their photolysis afforded resin-bound nitrosocarbonyls that were trapped with dienes affording valuable supported adducts suitable for further elaboration on solid-phase chemistry. 相似文献
130.
Giorgio Tosi Pierluigi Stipa Gabriele Bocelli 《Monatshefte für Chemie / Chemical Monthly》1988,119(4):487-494
The Dinitrone 2,2-diphenyl-3,3-bi-3H-indole-1,1-dioxide acts as a demethylating and dehydrogenating agent. The mechanism of interaction of the dinitrone with donors and acceptors does not involve intermediate charge-transfer complexes probably due to a self association between dinitrone molecules (as supported by X-ray determinations). The crystal structure of the dinitrone was obtained by direct methods;a=9.967 (2),b=19.817 (3),c=10.875 (2) Å, =111.2 (2)°, space group P21/n. The finalR andR
w
were 0.089 and 0.063 for all measured reflexes.
2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid: Molekulare Wechselwirkungen und Kristallstruktur
Zusammenfassung Das Dinitron 2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid wirkt als Demethylierungs- und Oxydationsmittel. Die Wechselwirkung des Dinitrons mit Elektronen-Acceptoren und Elektronen-Donatoren geht wegen der Selbstassoziation zwischen den Dinitron-Molekülen ohne die dazwischenliegende Bildung eines Charge-Transfer-Komplexes vor sich; das wird auch von Röntgenstrukturuntersuchungen gestützt. Die Kristallstruktur wurde mit direkten Methoden ermittelt:a=9.967 (2),b=19.817 (3),c=10.875 (2) Å; =111.2 (2)°. P21/n. Die endgültigen WerteR undR w waren 0.089 und 0.063 für alle gemessenen Reflexe.相似文献