全文获取类型
收费全文 | 2832篇 |
免费 | 59篇 |
国内免费 | 23篇 |
专业分类
化学 | 2182篇 |
晶体学 | 23篇 |
力学 | 44篇 |
数学 | 117篇 |
物理学 | 548篇 |
出版年
2022年 | 16篇 |
2021年 | 31篇 |
2020年 | 44篇 |
2019年 | 30篇 |
2018年 | 22篇 |
2017年 | 23篇 |
2016年 | 38篇 |
2015年 | 28篇 |
2014年 | 46篇 |
2013年 | 94篇 |
2012年 | 134篇 |
2011年 | 150篇 |
2010年 | 92篇 |
2009年 | 95篇 |
2008年 | 156篇 |
2007年 | 168篇 |
2006年 | 165篇 |
2005年 | 185篇 |
2004年 | 172篇 |
2003年 | 133篇 |
2002年 | 122篇 |
2001年 | 72篇 |
2000年 | 43篇 |
1999年 | 52篇 |
1998年 | 42篇 |
1997年 | 37篇 |
1996年 | 57篇 |
1995年 | 35篇 |
1994年 | 33篇 |
1993年 | 26篇 |
1992年 | 27篇 |
1991年 | 20篇 |
1990年 | 16篇 |
1989年 | 27篇 |
1988年 | 25篇 |
1987年 | 25篇 |
1986年 | 12篇 |
1985年 | 34篇 |
1984年 | 39篇 |
1983年 | 18篇 |
1982年 | 32篇 |
1981年 | 29篇 |
1980年 | 29篇 |
1979年 | 33篇 |
1978年 | 29篇 |
1977年 | 27篇 |
1976年 | 26篇 |
1975年 | 23篇 |
1974年 | 21篇 |
1973年 | 22篇 |
排序方式: 共有2914条查询结果,搜索用时 140 毫秒
51.
A simple and accurate titrimetric determination of calcium in the presence of larger amounts of magnesium is proposed. Calcium is extracted into a small volume of organic solvent as its glyoxal-bis(2-hydroxyanil) complex, and the calcium is titrated with EGTA. The end-point is sharp, and occurs when the red colour of the organic layer vanishes. This method has been successfully applied to the determination of calcium in sea-water with an error less than 0.1%. 相似文献
52.
Yoshimoto S Honda Y Murata Y Murata M Komatsu K Ito O Itaya K 《The journal of physical chemistry. B》2005,109(18):8547-8550
Adlayers of ZnOEP were prepared on reconstructed Au(100)-(hex) and unreconstructed Au(100)-(1 x 1) surfaces by immersing into a benzene solution containing ZnOEP molecules, and the adlayer structures were characterized by scanning tunneling microscopy (STM). A hexagonally arranged ZnOEP array was formed on an Au(100)-(hex) surface, whereas a rectangularly arranged ZnOEP array was found on an Au(100)-(1 x 1) surface. The adlayer structure of ZnOEP was dependent upon the underlying Au atomic arrangements. Furthermore, an investigation of the spuramolecular assembly for these modified surfaces was carried out by using an open-cage C(60) derivative (opened C(60)). A supramolecular assembled adlayer with a 1:1 composition of opened C(60)/ZnOEP was formed on Au(100)-(hex), whereas aggregates of opened C(60) were found on the ZnOEP-modified Au(100)-(1 x 1) surface. Electrochemical responses of opened C(60) were significantly influenced by underlying ZnOEP arrays. This finding suggests that precise control of underlying ZnOEP adlayers with the Au atomic structure is important to recognize the opened C(60) on them. 相似文献
53.
Yanagi T Kikuchi K Takeuchi H Ishikawa T Nishimura T Yamamoto I 《Chemical & pharmaceutical bulletin》2001,49(8):1018-1023
The synthetic route for a uterine relaxant, bis(2-[[(2S)-2-([(2R)-2-hydroxy-2-[4-hydroxy-3-(2-hydroxyethyl)-phenyl]ethyl]amino)-1,2,3,4-tetrahydronaphthalen-7-yl]oxy]-N,N-dimethylacetamide) sulfate (KUR-1246), was established by the coupling of optically active components, the bromohydrin 14 and the amine 24. We now describe the practical synthesis of these two optically active components. Bromohydrin 14 was obtained by the asymmetric borane reduction of the prochiral phenacyl bromide 13 using a catalyst prepared from aluminum triethoxide and a chiral amino alcohol. The other optically active component 24 was prepared from (S)-AMT. 相似文献
54.
We apply the singular value decomposition to compress the degrees of freedom of T3 amplitude for the CCSDT-1 method (compressed CCSDT-1). This method enables us to make the number of the T3 amplitudes less than that of the T2 amplitudes, making CCSDT-1 calculations much less expensive without losing accuracy. We perform test calculations on some atoms and molecules to investigate the applicability of this method. Computational results for the electronic energies as well as timings of these calculations are presented. 相似文献
55.
M. Saeki M. Nakada T. Kawasaki T. Nishimura T. Kitazawa M. Takeda 《Journal of Radioanalytical and Nuclear Chemistry》2006,270(2):379-384
Summary The correlations of isomer shifts in various neptunyl(V and VI) compounds with crystallographic structures were revaluated.
A linear correlation between the isomer shifts of neptunyl(VI) compounds and Np-O bond lengths of neptunyl group has been
demonstrated. On the other hand, it has been evidenced that the isomer shifts of neptunyl(V) compounds are correlated much
stronger with the mean Np-O distances in the crystals than the lengths in neptunyl(V) group. 相似文献
56.
Shigeru Shimada Osamu Yamazaki Yohichi Suzuki 《Journal of organometallic chemistry》2004,689(19):3012-3023
Hypervalent organobismuth compounds, 6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines, with 13 different substituents on the bismuth atom including halogens, alkyl, alkenyl, alkynyl, aryl, or phenylthio groups have been synthesized. A key compound, 12-chloro-6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocine, which is a precursor for other azabismocines, has been synthesized by two different procedures; one is based on Akiba’s method using 2-bromobenzylbromide as one of the starting materials and the other is a newly developed one using a cheaper starting material, 2-chlorobenzyl chloride. The structures of 12 new bismuth compounds were determined by X-ray diffraction. The eight-membered tetrahydroazabismocine ring has proved to be highly flexible and the hypervalent Bi-N bond distances vary ranging from 2.568(3) to 2.896(5) Å, depending on the electronic nature of the substituents on the bismuth atom. The Bi-N bond distances have good linear relationship against Hammett’s σm constants. 相似文献
57.
Osamu Matsumoto Eiji Hayami Mamoru Samejima Yasushi Kanzaki 《Plasma Chemistry and Plasma Processing》1984,4(1):33-42
The nitriding of titanium with argon-nitrogen (3%) and argon-nitrogen (3%)-hydrogen (2%) plasma jets at pressures of 190 torr was studied. The reaction kinetics obeyed mainly a parabolic law. The parabolic kinetic constants were 10–10–10–8 g2 cm–4 s–1, which were 2–3 orders of magnitude larger than those in R.F. discharges. From emission spectroscopy, nitrogen atoms in the excited states were observed. The nitrogen atoms can promote the nitriding reaction. The effect of the addition of hydrogen to nitrogen is also briefly discussed. 相似文献
58.
A NKT cell repertoire is characterized by the expression of the Valpha19-Jalpha26 invariant TCR alpha chain (Valpha19 NKT cell). This repertoire, as well as a well-established Valpha14-Jalpha281 invariant TCR alpha(+) NKT cell subset (Valpha14 NKT cell), has been suggested to have important roles in the regulation of the immune system and, thus, is a major therapeutic target. Here, we attempted to find specific antigens for Valpha19 NKT cells. Valpha19 as well as Valpha14 NKT cells exhibited reactivity to alpha-galactosyl ceramide (alpha-GalCer). Thus, a series of monoglycosyl ceramides with an axially oriented glycosidic linkage between the sugar and ceramide moiety were synthesized and their antigenicity to Valpha19 NKT cells was determined by measuring their immune responses in culture with glycolipids. Comprehensive examinations revealed substantial antigenic activity for Valpha19 NKT cells by alpha-mannosyl ceramide. 相似文献
59.
Nakamura T Ikemoto JY Fujitsuka M Araki Y Ito O Takimiya K Aso Y Otsubo T 《The journal of physical chemistry. B》2005,109(30):14365-14374
The dramatic changes of the lifetimes of the charge-separated (CS) states were confirmed in zinc porphyrin (ZnP)-oligothiophene (nT)-fullerene (C(60)) linked triads (ZnP-nT-C(60)) with the solvent polarity. After the selective excitation of the ZnP moiety of ZnP-nT-C(60), an energy transfer took place from the (1)ZnP moiety to the C(60) moiety, generating ZnP-nT-(1)C(60). In polar solvents, the CS process also took place directly via the (1)ZnP moiety, generating ZnP(*+)-nT-C(60)(*-), as well as the energy transfer to the C(60) moiety. After this energy transfer, an indirect CS process took place from the (1)C(60) moiety. In the less polar solvent anisole, the radical cation (hole) of ZnP(*+)-nT-C(60)(*-) shifted to the nT moiety; thus, the nT moiety behaves as a cation trapper, and the rates of the hole shift were evaluated to be in the order of 10(8) s(-1); then, the final CS states ZnP-nT(*+)-C(60)(*-) were lasting for 6-7 mus. In the medium polar solvent o-dichlorobenzene (o-DCB), ZnP-nT(*+)-C(60)(*-) and ZnP(*+)-nT-C(60)(*-) were present as an equilibrium, because both states have almost the same thermodynamic stability. This equilibrium resulted in quite long lifetimes of the CS states (450-910 mus) in o-DCB. In the more polar benzonitrile, the generation of ZnP-nT(*+)-C(60)(*-) was confirmed with apparent short lifetimes (0.6-0.8 mus), which can be explained by the fast hole shift to more stable ZnP(*+)-nT-C(60)(*-) followed by the faster charge recombination. It was revealed that the relation between the energy levels of two CS states, which strongly depend on the solvent polarity, causes dramatic changes of the lifetimes of the CS states in ZnP-nT-C(60); that is, the most appropriate solvents for the long-lived CS state are intermediately polar solvents such as o-DCB. Compared with our previous data for H(2)P-nT-C(60), in which H(2)P is free-base porphyrin, the lifetimes of the CS states of ZnP-nT-C(60) are approximately 30 times longer than those in o-DCB. 相似文献
60.
Adlhart C Sekiguchi O Uggerud E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):152-159
OH(+) is an extraordinarily strong oxidant. Complexed forms (L--OH(+)), such as H(2)OOH(+), H(3)NOH(+), or iron-porphyrin-OH(+) are the anticipated oxidants in many chemical reactions. While these molecules are typically not stable in solution, their isolation can be achieved in the gas phase. We report a systematic survey of the influence on L on the reactivity of L--OH(+) towards alkanes and halogenated alkanes, showing the tremendous influence of L on the reactivity of L--OH(+). With the help of with quantum chemical calculations, detailed mechanistic insights on these very general reactions are gained. The gas-phase pseudo-first-order reaction rates of H(2)OOH(+), H(3)NOH(+), and protonated 4-picoline-N-oxide towards isobutane and different halogenated alkanes C(n)H(2n+1)Cl (n=1-4), HCF(3), CF(4), and CF(2)Cl(2) have been determined by means of Fourier transform ion cyclotron resonance measurements. Reaction rates for H(2)OOH(+) are generally fast (7.2x10(-10)-3.0x10(-9) cm(3) mol(-1) s(-1)) and only in the cases HCF(3) and CF(4) no reactivity is observed. In contrast to this H(3)NOH(+) only reacts with tC(4)H(9)Cl (k(obs)=9.2x10(-10)), while 4-CH(3)-C(5)H(4)N-OH(+) is completely unreactive. While H(2)OOH(+) oxidizes alkanes by an initial hydride abstraction upon formation of a carbocation, it reacts with halogenated alkanes at the chlorine atom. Two mechanistic scenarios, namely oxidation at the halogen atom or proton transfer are found. Accurate proton affinities for HOOH, NH(2)OH, a series of alkanes C(n)H(2n+2) (n=1-4), and halogenated alkanes C(n)H(2n+1)Cl (n=1-4), HCF(3), CF(4), and CF(2)Cl(2), were calculated by using the G3 method and are in excellent agreement with experimental values, where available. The G3 enthalpies of reaction are also consistent with the observed products. The tendency for oxidation of alkanes by hydride abstraction is expressed in terms of G3 hydride affinities of the corresponding cationic products C(n)H(2n+1) (+) (n=1-4) and C(n)H(2n)Cl(+) (n=1-4). The hypersurface for the reaction of H(2)OOH(+) with CH(3)Cl and C(2)H(5)Cl was calculated at the B3 LYP, MP2, and G3(m*) level, underlining the three mechanistic scenarios in which the reaction is either induced by oxidation at the hydrogen or the halogen atom, or by proton transfer. 相似文献