全文获取类型
收费全文 | 665篇 |
免费 | 44篇 |
国内免费 | 4篇 |
专业分类
化学 | 415篇 |
晶体学 | 17篇 |
力学 | 23篇 |
数学 | 139篇 |
物理学 | 119篇 |
出版年
2023年 | 12篇 |
2022年 | 27篇 |
2021年 | 23篇 |
2020年 | 28篇 |
2019年 | 26篇 |
2018年 | 22篇 |
2017年 | 21篇 |
2016年 | 42篇 |
2015年 | 16篇 |
2014年 | 27篇 |
2013年 | 42篇 |
2012年 | 48篇 |
2011年 | 46篇 |
2010年 | 17篇 |
2009年 | 17篇 |
2008年 | 27篇 |
2007年 | 37篇 |
2006年 | 26篇 |
2005年 | 18篇 |
2004年 | 12篇 |
2003年 | 16篇 |
2002年 | 20篇 |
2001年 | 17篇 |
2000年 | 7篇 |
1999年 | 6篇 |
1997年 | 2篇 |
1996年 | 9篇 |
1995年 | 2篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 9篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 7篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1973年 | 7篇 |
1969年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有713条查询结果,搜索用时 15 毫秒
11.
Proton affinities of a series of triphenyl Group Va compounds have been determined by bracketing using reactant ion monitoring: (C6H5)3N = 904 ± 8 kJ mol?1, (C6H5)3P = 968 ± 5 kJ mol?1, (C6H5)3As = 904 ± 8 kJ mol?1 and (C6H5)3Sb = 846 ± 8 kJ mol?1. The large difference in substituent effect of phenyl for hydrogen between As or P and N may result from overlap of the 2p orbitals of N with the sp2 orbitals on the ring carbons and lack of overlap for P or As. Proton affinities of phenylalkylphosphine oxides are essentially the same, 904 ± 8 kJ mol?1, independent of alkyl group. 相似文献
12.
Reactions between the Os(VI)-nitrido complexes cis- and trans-[Os(VI)(tpy)(Cl)2(N)]+ (tpy is 2,2':6',2"-terpyridine) and triphenylphosphine sulfide, SPPh3, give the corresponding Os(IV)-phosphoraniminato, [Os(IV)(tpy)(Cl)2(NPPh3)]+, and Os(II)-thionitrosyl, [Os(II)(tpy)(Cl)2(NS)]+, complexes as products. The Os-N bond length and Os-N-P angle in cis-[Os(IV)(tpy)(Cl)2(NPPh3)](PF6) are 2.077(6) A and 138.4(4) degrees. The rate law for formation of cis- and trans-[Os(IV)(tpy)(Cl)2(NPPh3)]+ is first order in both [Os(VI)(tpy)(Cl)2(N)]+ and SPPh3 with ktrans(25 degrees C, CH3CN) = 24.6 +/- 0.6 M(-1) s(-1) and kcis(25 degrees C, CH3CN) = 0.84 +/- 0.09 M(-1) s(-1). As found earlier for [Os(II)(tpm)(Cl)2(NS)]+, both cis- and trans-[Os(II)(tpy)(Cl)2(NS)]+ react with PPh3 to give [Os(IV)(tpy)(Cl)2(NPPh3)]+ and SPPh3. For both complexes, the reaction is first order in each reagent with ktrans(25 degrees C, CH3CN) = (6.79 +/- 0.08) x 10(2) M(-1) s(-1) and kcis(25 degrees C, CH3CN) = (2.30 +/- 0.07) x 10(2) M(-1) s(-1). The fact that both reactions occur rules out mechanisms involving S atom transfer. These results can be explained by invoking a common intermediate, [Os(IV)(tpy)(Cl)2(NSPPh3)]+, which undergoes further reaction with PPh3 to give [Os(IV)(tpy)(Cl)2(NPPh3)]+ and SPPh3 or with [Os(VI)(tpy)(Cl)2(N)]+ to give [Os(IV)(tpy)(Cl)2(NPPh3)]+ and [Os(II)(tpy)(Cl)2(NS)]+. 相似文献
13.
A series of donor-stabilized N-silylphosphoranimine salts [DMAP.PCl2=NSiMe3]+X- (DMAP = 4-(dimethylamino)pyridine) were prepared by the reaction of Cl3P=NSiMe3 with DMAP in the presence of silver salts AgX (X = OSO2CF3, BF4, and SbF6). Repeating the reaction in the absence of AgX gave the chloride salt [DMAP.PCl2=NSiMe3]Cl which has been shown to be in equilibrium with free DMAP and Cl3P=NSiMe3. Attempts to stabilize a N-silylphosphoranimine cation with phosphine donors led to unexpected imine transfer chemistry. For example, Cl3P=NSiMe3 reacts with phosphines, R3P (R = nBu and Ph), to produce the metathesis products PCl3 and R3P=NSiMe3 which subsequently react together to afford the N-phosphinophosphoranimines R3P=N-PCl2 and ClSiMe3 as a byproduct. 相似文献
14.
15.
16.
Mohanad A. Hussein Dr. Uyen P. N. Tran Dr. Vien T. Huynh Dr. Junming Ho Dr. Mohan Bhadbhade Prof. Dr. Herbert Mayr Dr. Thanh V. Nguyen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(4):1471-1475
Tropylium bromide undergoes noncatalyzed, regioselective additions to a large variety of Michael acceptors. In this way, acrylic esters are converted into β-bromo-α-cycloheptatrienylpropionic esters. The reactions are interpreted as nucleophilic attack of bromide ions at the electron-deficient olefins and the approach of the tropylium ion to the incipient carbanion. Quantum chemical calculations were performed to elucidate the analogy to the amine- or phosphine-catalyzed Rauhut–Currier reactions. Subsequent synthetic transformations of the bromo-cycloheptatrienylated adducts are reported. 相似文献
17.
Gregory B. Kharas Xue Tian Trang H. Huynh Thomas W. Lyons Lani A. Macartney Dylan Smith 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(5):469-473
Electrophilic trisubstituted ethylene monomers, halogen ring‐disubstituted 2‐cyano‐N,N‐dimethyl‐3‐phenyl‐2‐propenamides, RC6H3CH?C(CN)CON(CH3)2 (where R is 2,3‐dichloro, 2,4‐dichloro, 2,6‐dichloro, 3,4‐dichloro, 3,5‐dichloro, 2,3‐difluoro, 2,4‐difluoro, 2,6‐difluoro, 3,4‐difluoro, 3,5‐difluoro), were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and N,N‐dimethyl cyanoacetamide, and characterized by CHN elemental analysis, IR, 1H‐ and 13C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1H and 13C NMR, GPC, DSC, and TGA. High Tg of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 300–450°C range. 相似文献
18.
Hyojin Lee Chi P. Huynh Stephen C. Hawkins Mustafa Musameh Dae Hyung Kim 《Liquid crystals》2013,40(3):322-327
We investigated the orientational and electro-optical properties of a nematic liquid crystal (LC) aligned with a directly spinnable carbon nanotube (CNT) web functioning both as an electrode and as an alignment layer. The LC molecules were uniformly oriented along the drawing direction of the CNT web and the spatially averaged birefringence was comparable to a rubbed polyimide sample. The CNT web sample also showed smaller residual DC and hysteresis compared to the polyimide sample. 相似文献
19.
Thien Y Vu Prof. Anna Chrostowska Prof. Thi Kieu Xuan Huynh Prof. Saïd Khayar Prof. Alain Dargelos Katarzyna Justyna Dr. Beata Pasternak Prof. Stanisław Leśniak Prof. Curt Wentrup 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(44):14983-14988
Thermal reactions of N‐benzylidene‐ and N‐(2‐pyridylmethylidene)‐tert‐butylamines ( 5 and 13 ) under FVT conditions have been investigated. Unexpectedly, at 800 °C, compound 5 yields 1,2‐dimethylindole and 3‐methylisoquinoline. In the reaction of 13 at 800 °C, 3‐methylimidazo[1,5‐a]pyridine was obtained as the major product. Mechanisms of these reactions have been proposed on the basis of DFT calculations. Furthermore, UV‐photoelectron spectroscopy combined with FVT has been applied for direct monitoring and characterization of the thermolysis products in situ. 相似文献
20.
Specific ion effects on the electrophoretic mobility of small,highly charged peptides: A modeling study 下载免费PDF全文
Stuart A. Allison Hengfu Wu Tuyen M. Bui Lac Dang Giang H. Huynh Tam Nguyen Linda Soegiarto Bi C. Truong 《Journal of separation science》2014,37(17):2403-2410
In this work, we use coarse‐grained modeling to study the free solution electrophoretic mobility of small highly charged peptides (lysine, arginine, and short oligos thereof (up to nonapeptides)) in NaCl and Na2SO4 aqueous solutions at neutral pH and room temperature. The experimental data are taken from the literature. A bead modeling methodology that treats the electrostatics at the level of the nonlinear Poisson Boltzmann equation developed previously in our laboratory is able to account for the mobility of all peptides in NaCl, but not Na2SO4. The peptide mobilities in Na2SO4 can be accounted for by including sulfate binding in the model and this is proposed as one possible explanation for the discrepancy. Oligo arginine peptides bind more sulfate than oligo lysines and sulfate binding increases with the oligo length. 相似文献