全文获取类型
收费全文 | 913篇 |
免费 | 22篇 |
国内免费 | 2篇 |
专业分类
化学 | 783篇 |
晶体学 | 1篇 |
力学 | 8篇 |
数学 | 65篇 |
物理学 | 80篇 |
出版年
2024年 | 2篇 |
2023年 | 9篇 |
2022年 | 56篇 |
2021年 | 45篇 |
2020年 | 14篇 |
2019年 | 25篇 |
2018年 | 10篇 |
2017年 | 13篇 |
2016年 | 31篇 |
2015年 | 31篇 |
2014年 | 28篇 |
2013年 | 77篇 |
2012年 | 66篇 |
2011年 | 58篇 |
2010年 | 47篇 |
2009年 | 37篇 |
2008年 | 48篇 |
2007年 | 57篇 |
2006年 | 61篇 |
2005年 | 55篇 |
2004年 | 50篇 |
2003年 | 28篇 |
2002年 | 29篇 |
2001年 | 9篇 |
2000年 | 9篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1983年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1973年 | 2篇 |
1969年 | 1篇 |
排序方式: 共有937条查询结果,搜索用时 10 毫秒
101.
Philippe Zinck Andreia Valente Fanny Bonnet Ana Violante André Mortreux Marc Visseaux Simona Ilinca Rob Duchateau Pascal Roussel 《Journal of polymer science. Part A, Polymer chemistry》2010,48(4):802-814
The ability of various rare earth borohydride and chloride complexes/n‐butylethylmagnesium systems to operate styrene chain transfer polymerization in mild conditions has been assessed. Thirteen precatalysts have been considered: the rare earth trisborohydrides Ln(BH4)3(THF)x (x = 3, Ln = Nd (1), La (2), Sm (3), x = 2, Ln = Y (4), Sc (5)), the rare earth chlorides LnCl3(THF)x (x = 3, Ln = Nd (6), La (7), Sm (8), Y (9), x = 2, Ln = Sc (10)), the mixed La(BH4)2Cl(THF)2.6 (11) and the half‐lanthanidocenes Cp*Ln(BH4)2(THF)2 (Ln = Nd (12), La (13)). Six systems were found to be active precatalysts for the polymerization of styrene. 1 , 2 , and 11 led to an efficient transmetalation of the growing polystyrene chain with the simultaneous occurrence of βH elimination, whereas 7 , 12 , and 13 led to catalyzed chain growth behavior. It is noteworthy that the catalyzed chain growth obtained with 12 and 13 occurs with significant stereoselectivity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 802–814, 2010 相似文献
102.
A new, one-step preparation of 1,4-di(2,2':6',2' '-terpyridin-4'-yl)benzene was employed in the synthesis of a linear trinuclear Ru(II) complex, which was compared to mononuclear and dinuclear analogues using UV-vis spectrometry, cyclic voltammetry, and ability to sensitize the photogeneration of methyl viologen radical cation. The chain length-dependent increase in sensitization ability was consistent with an increasing molar absorbance and with an end-on approach of the photoreactants mitigating the increasing charge. 相似文献
103.
Cianetti S Négrerie M Vos MH Martin JL Kruglik SG 《Journal of the American Chemical Society》2004,126(43):13932-13933
Cytochrome c (cyt c) is an electron-transfer heme protein that also binds nitric oxide (NO). In resting cyt c, two endogenous ligands of the heme iron are histidine-18 (His) and methionine-80 (Met) side chains, and NO binding requires the cleavage of one of the axial bonds. Previous femtosecond transient absorption studies suggested the photolysis of either Fe-His or Fe-Met bonds. We aimed at unequivocally identifying the internal side chain that is photodissociated in ferrous cyt c and at monitoring heme structural dynamics, by means of time-resolved resonance Raman (TR3) spectroscopy with approximately 0.6 ps time resolution. The Fe-His stretching mode at 216 cm-1 has been observed in photoproduct TR3 spectra for the first time for a c-type heme. The same transient mode was observed for a model ferrous cyt c N-fragment (residues 1-56) ligated with two His in the resting state. Our TR3 data reveal that upon ferrous cyt c photoexcitation, (i) distal Met side chain is instantly released, producing a five-coordinated domed heme structure, (ii) proximal His side chain, coupled to the heme, exhibits distortion due to strain exerted by the protein, and (iii) alteration in heme-cysteine coupling takes place along with the relaxation of the protein-induced deformations of the heme macrocycle. 相似文献
104.
Domenico Acierno Eugenio Amendola Simona Concilio Pio Iannelli Antonio Massa Paola Scarfato 《Macromolecular Symposia》2002,180(1):61-72
The use of the same thermoplastic polymer for both the matrix and the filler in the preparation of composites is very attractive, because such composites are in principle fully recyclable. Recently it has been reported the preparation of a mono-material composite (MMC) made of polypropylene to be used in automobile parts. In this work we report on the preparation and characterization of matrices for quasi MMC made of poly(ethylene terephthalate) (PET). Particularly we found PET copolymers containing isophthalate (IPA) units adequate to be used as matrix. 相似文献
105.
The formation and stability of some polycation/azo dye multilayers by the alternate adsorption of one polycation of integral type having 95 mol% of N,N-dimethyl-2-hydroxypropyleneammonium chloride repeat units (PCA5) and four multicharged azo dyes: Crocein Scralet MOO (CSMOO), Ponceau SS (PSS), Direct Blue 1 (DB 1) and Direct Red 80 (DR 80) are discussed in this paper. The dyes were different either by the number of sulfonic groups (PSS, DB 1 and DR 80) or by their position (CSMOO and PSS). The multilayer growth, when PCA5 was adsorbed from 0.2 M Na2SO4 aqueous solution, was followed by UV-Vis spectroscopy and by electrokinetic measurements. Solid state polycation/azo dye complexes were also prepared to get qualitative information on the charge compensation in the multilayers. 相似文献
106.
V Colombo C Montoro A Maspero G Palmisano N Masciocchi S Galli E Barea JA Navarro 《Journal of the American Chemical Society》2012,134(30):12830-12843
Two isoreticular series of pyrazolate-based 3D open metal-organic frameworks, MBDP_X, adopting the NiBDP and ZnBDP structure types [H(2)BDP = 1,4-bis(1H-pyrazol-4-yl)benzene], were synthesized with the new tagged organic linkers H(2)BDP_X (X = -NO(2), -NH(2), -OH). All of the MBDP_X materials have been characterized through a combination of techniques. IR spectroscopy proved the effective presence of tags, while X-ray powder diffraction (XRPD) witnessed their isoreticular nature. Simultaneous TG/DSC analyses (STA) demonstrated their remarkable thermal stability, while variable-temperature XRPD experiments highlighted their high degree of flexibility related to guest-induced fit processes of the solvent molecules included in the channels. A structural isomer of the parent NiBDP was obtained with a sulfonate tagged ligand, H(2)BDP_SO(3)H. Structure solution from powder diffraction data collected at three different temperatures (room temperature, 90, and 250 °C) allowed the determination of its structure and the comprehension of its solvent-related flexible behavior. Finally, the potential application of the tagged MOFs in selective adsorption processes for gas separation and purification purposes was investigated by conventional single component adsorption isotherms, as well as by advanced experiments of pulse gas chromatography and breakthrough curve measurements. Noteworthy, the results show that functionalization does not improve the adsorption selectivity (partition coefficients) for the resolution of gas mixtures characterized by similar high quadrupole moments (e.g., CO(2)/C(2)H(2)); however, the resolution of gas mixtures containing molecules with highly differentiated polarities (i.e., N(2)/CO(2) or CH(4)/CO(2)) is highly improved. 相似文献
107.
Caterina Viglianisi Stefano Menichetti Giulio Assanelli Maria Carmela Sacchi Incoronata Tritto Simona Losio 《Journal of polymer science. Part A, Polymer chemistry》2012,50(22):4647-4655
A new family of ethylene‐based copolymers with controlled amounts of a norbornene comonomer (NArOH) bearing a stabilizing antioxidant functionality (2,6‐di‐tert‐butyl phenol) was prepared. Due to unavoidable exo/endo equilibrium operative in NArOH comonomer, a complete and detailed NMR assignment of the structure of the prepared ethylene/NArOH copolymers was carried out for the determination of the exo/endo ratio inside the polymer. These novel functionalized comonomers can be considered suitable starting material for preparing ethylene‐based copolymers, with tunable comonomer content, as non‐releasing macromolecular antioxidant additives for specific application in safe food and/or drug packaging © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
108.
Synthesis,solid-state photophysical properties and electropolymerization of novel diazulenyl ethenes
Eugenia Andreea Dragu Simona Nica Matei Raicopol Adriana Baran Dan-Florin Anghel Bogdan Cojocaru Laszlo Tarko Alexandru C. Razus 《Tetrahedron letters》2012,53(21):2611-2614
The novel 1,2-di(azulen-1-yl)cyclopent-1-ene 3 was conveniently synthesized via a two-step procedure involving Vilsmeier–Haack acylation of azulene with N,N,N′,N′-tetraethylglutaramide (TEGA) and POCl3, followed by an intramolecular McMurry coupling of the resulting diketone. In contrast with the previously reported (E)-1,2-di(azulen-1-yl)ethene that shows negligible fluorescence in the solid state, alkene 3 displays fluorescence emission from the S2 excited state of the azulene moieties. This compound easily polymerizes upon electrochemical oxidation, leading to the formation of a conducting polymer film at the electrode surface. 相似文献
109.
A new family of five-membered cyclic nitrones bearing functional groups at positions 2 and 5 were tested in 1,3-cycloadditions with various dipolarophiles. These reactions gave the corresponding cycloadducts as single diastereomers in high yields. The reaction scope was examined, 23 compounds were isolated and fully characterized. The comparison of the reactivity was carried out by a study of reaction conversions while different nitrones or dipolarophiles were used. In addition, the exceptional reactivity of nitrone bearing benzylamino group in position 2 was studied. The formation of the nitrone complex and evaluation of its reactivity in 1,3-DC is presented. 相似文献
110.
Pichini S Pellegrini M Pacifici R Marchei E Murillo J Puig C Vall O García-Algar O 《Rapid communications in mass spectrometry : RCM》2003,17(17):1958-1964
A high-performance liquid chromatography (HPLC) method with mass spectrometric detection is described for determination of arecoline in newborn meconium, urine and cord serum, using pilocarpine as internal standard. The analytes were extracted from neonatal biological matrices with chloroform/isopropanol (95:5, v/v) at alkaline pH. Extracts were analyzed by HPLC coupled to an electrospray (ESI) interface and a quadrupole mass spectrometer. Chromatography was performed on a C(8) reversed-phase column using 10 mM ammonium acetate (pH 4.3)/acetonitrile (90:10, v/v) as mobile phase. The mass spectrometer was operated in selected ion monitoring mode. The method was validated over the concentration range 0.005-1.00 micro g/g meconium, 0.004-1.00 micro g/mL cord serum and 0.001-1.00 micro /mL urine. Mean recoveries ranged between 86.5 and 90.7% for arecoline in the different biological matrices, with precision always better than 10%. The quantification limits of arecoline were 0.005 micro g/g meconium, 0.004 micro g/mL cord serum, and 0.001 micro g/mL urine. The method was applied to the analysis of neonatal biological matrices to assess eventual fetal exposition to arecoline. Two newborns from Asian mothers who declared areca nut consumption presented arecoline in meconium with concentrations in the range 0.006-0.008 micro g/g; also the urine from one neonate tested positive for the drug. 相似文献