全文获取类型
收费全文 | 1212篇 |
免费 | 41篇 |
国内免费 | 8篇 |
专业分类
化学 | 674篇 |
晶体学 | 8篇 |
力学 | 73篇 |
数学 | 115篇 |
物理学 | 391篇 |
出版年
2023年 | 9篇 |
2022年 | 12篇 |
2021年 | 6篇 |
2019年 | 19篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 23篇 |
2015年 | 25篇 |
2014年 | 35篇 |
2013年 | 41篇 |
2012年 | 82篇 |
2011年 | 91篇 |
2010年 | 53篇 |
2009年 | 56篇 |
2008年 | 68篇 |
2007年 | 73篇 |
2006年 | 67篇 |
2005年 | 58篇 |
2004年 | 39篇 |
2003年 | 38篇 |
2002年 | 31篇 |
2001年 | 26篇 |
2000年 | 29篇 |
1999年 | 12篇 |
1998年 | 10篇 |
1997年 | 16篇 |
1996年 | 18篇 |
1995年 | 9篇 |
1994年 | 14篇 |
1993年 | 28篇 |
1992年 | 19篇 |
1991年 | 23篇 |
1990年 | 20篇 |
1989年 | 10篇 |
1988年 | 11篇 |
1987年 | 12篇 |
1985年 | 9篇 |
1984年 | 9篇 |
1983年 | 7篇 |
1982年 | 13篇 |
1981年 | 11篇 |
1980年 | 12篇 |
1979年 | 15篇 |
1978年 | 12篇 |
1977年 | 10篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1970年 | 7篇 |
1969年 | 8篇 |
1967年 | 5篇 |
排序方式: 共有1261条查询结果,搜索用时 15 毫秒
991.
A rapid access to the piperizinohydroisoquinoline motif, which has feature of the saframycins and related pentacyclic antitumor alkaloids is described. The key features of the synthetic strategy include (1) a controlled mono-Pictet-Spengler cyclization of the symmetrical 3,6-bis-[(2,5-dimethoxy-phenyl)methyl]piperizine-2,5-dione (1), with aldehydes to give 2, under a critically controlled ratio of acetic acid and trifluoroacetic acid as solvent and (2) reduction of the activated amide to the hemiaminal, which then undergoes an unexpected dehydrogenation reaction to remove the steric hindrance for the second Pictet-Spengler cyclization to form the pentacyclic piperizinohydroisoquinoline 6. The in vitro antitumor activity of these compounds was tested against five human cancer cell lines (A549 lung, HeLa cervical, SAS oral, SKHep1 hepatoma and PC-3 prostate carcinoma). The pentacyclic saframycin analogues 6, 7 and 9 showed only weak activities. Interestingly, compound 6, having a closer relation to cribrostatin IV, is selective towards oral cancer. 相似文献
992.
Three new briarane-type diterpenoids, designated as robustolides A-C (1-3), were obtained from the female gorgonian coral Ellisella robusta. The structures of briaranes 1-3 were elucidated by the interpretation of spectral data analysis and the structure of 1 was further confirmed by a single-crystal X-ray diffraction analysis. Briaranes 1 and 2 were found to show weak activity against the bacteria Pseudomonas aeruginosa and Staphylococcus aureus. 相似文献
993.
Kuo‐Chen Chiang Fung Fuh Wong Chih‐Shiang Chang Mann‐Jen Hour Yu‐Ling Wang Shaw‐Bing Wen Mou‐Yung Yeh 《Journal of heterocyclic chemistry》2007,44(3):591-596
Recently, New functionalized oxadiazole‐triazolopyridinone hybrid compounds were investigated as photoluminescent materials. In this work, we introduce triazolopyridinone to synthesize a series of oxadiazole‐triazolopyridinone hybrid derivatives as potential photoluminescent materials and explore the effect of modification of the triazolopyridinone moiety. The λmax values of the photoluminescence (PL) spectra of 1,3,4‐oxadiazole‐triazolopyridinone hybrids are promoted to longer wavelengths (470‐486 nm) than the traditional 1,2,3‐triazole derivatives (410‐425 nm) in solutions. PL spectra 5a, 5d , and 5g of the vacuum evaporated films on quartz substrates, with a maximum at 487 nm, shows a red‐shift (~15‐20 nm), with respect to the solution spectrum. The solution fluorescence quantum yields (Φf) were measured, all of which fell into the range 0.65‐0.76, and were determined relative to that of 2‐phenyl‐5‐(4‐biphenyl)‐1,3,4‐oxadiazole in benzene (Φf = 0.80). 1,3,4‐Oxadiazole‐triazolopyridinone hybrid derivatives show clearly non‐reversible reduction processes in cyclic voltammogram measurements. Following spectroscopic studies and observation of the electrochemical behaviors, 1,3,4‐oxadiazole‐triazolopyridinone derivatives were determined to be potential efficient bluegreenish photoluminescent materials. 相似文献
994.
Several new stereoisomers of 3,4,6-trihydroxyazepanes and 7-hydroxymethyl-3,4,5-trihydroxyazepanes as well as known 3,4,5-trihydroxyazepanes were synthesized as potent glycosidase inhibitors from D-(-)-quinic acid in an efficient manner. The key step employs dihydroxylation of protected chiral 1,4,5-cyclohex-2-enetriols under RuCl3/NaIO4/phosphate buffer (pH 7) condition, followed by reductive amino cyclization. We found the choice of an appropriate protecting group to C1-OH of chiral 1,4,5-cyclohex-2-enetriols would increase the yields of cyclization. The preliminary biological data indicate some of these azepanes possess potent inhibition against alpha-mannosidase and alpha-fucosidase. 相似文献
995.
Chiang CT Freindorf M Furlani T DeLeon RL Richard JP Garvey JF 《The journal of physical chemistry. A》2007,111(27):6068-6076
The interaction between ammonia and the benzene radical cation has been investigated by gas-phase studies of mass selected ion clusters {C(6)H(6)-(NH(3))(n=0-8)}(+) via tandem quadrupole mass spectrometry and through calculations. Experiments show a special stability for the cluster ion that contains four ammonias: {C(6)H(6)(NH(3))(4)}(+). Calculations provide evidence that the first ammonia forms a weak dative bond to the cyclohexadienyl radical cation, {C(6)H(6)-NH(3)}(+), where there is a transfer of electrons from ammonia to benzene. Additional solvating ammonia molecules form stabilizing hydrogen bonds to the ring-bound ammonia {C(6)H(6)-NH(3)}(+).(NH(3))(n), which cause cooperative changes in the structure of the cluster complex. Free ammonia is a weak hydrogen bond donor, but electron transfer from NH(3) to the benzene ring that strengthens the dative bond will increase the hydrogen acidity and the strength of the cluster hydrogen bonds to the added ammonia. A progressive "tightening" of this dative bond is observed upon addition of the first, second, and third ammonia to give a cluster stabilized by three N-(+)H x N hydrogen bonds. This shows that the energetic cost of tightening the dative bond is recovered with dividends in the formation of stable cluster hydrogen bonds. 相似文献
996.
Sakthivel A Pedro FM Chiang AS Kühn FE 《Dalton transactions (Cambridge, England : 2003)》2007,(3):320-326
Cyclopentadienyl ruthenium phosphane and carbene complexes are grafted on the surface of mesoporous SBA-15 molecular sieves through an aminosilane linker. The nature of the support after the grafting is examined by powder XRD, TEM and N(2) adsorption/desorption analysis. Elemental analysis, FT-IR, DRIFTS, TG-MS and MAS-NMR studies confirm the successful grafting of the complexes on the surface. The grafted materials are applied for catalytic aldehyde olefination and cyclopropanation. 相似文献
997.
Goodwin JM Chiang PC Brynda M Penkina K Olmstead MM Patten TE 《Dalton transactions (Cambridge, England : 2003)》2007,(28):3086-3092
Addition of two equivalents of CuCl to deprotonated bis-(2-(2-pyridyl)ethyl)-2-(N-toluenesulfonylamino)ethylamine (PETAEA) and its derivatives yielded new types of dinuclear Cu(I) complexes, Cu(mu-PETAEA)CuCl, Cu(mu-PEMAEA)CuCl, and Cu(mu-PENAEA)CuCl (PEMAEA is the 4-methoxyphenyl derivative of PETAEA and PENAEA is the 4-nitrophenyl derivative), exhibiting a four coordinate N(4)Cu center, a two coordinate NCuCl center, and a metal-metal distance within the range of 2.6572(8) to 2.6903(3) A. Analysis of the covalent radii for four coordinate and two coordinate copper(I), the acute copper-nitrogen-copper angles, and density functional theory (DFT) calculations suggest a weak attraction between the two copper atoms. The complexes apparently formed in a two-step process with the formation of the tetracoordinate mononuclear complex preceding the coordination of a second equivalent of CuCl to the lone pair of the sulfonamidate ligand. 相似文献
998.
Zhang LM Zhang ZP Adachi I Aihara H Aulchenko V Aushev T Bakich AM Balagura V Barberio E Bay A Belous K Bitenc U Bondar A Bozek A Bracko M Brodzicka J Browder TE Chang P Chao Y Chen A Chen KF Chen WT Cheon BG Chiang CC Cho IS Choi Y Choi YK Dalseno J Danilov M Dash M Drutskoy A Eidelman S Epifanov D Fratina S Gabyshev N Gokhroo G Golob B Ha H Haba J Hara T Hastings NC Hayasaka K Hayashii H Hazumi M Heffernan D Hokuue T Hoshi Y Hou WS Hsiung YB Hyun HJ Iijima T Ikado K Inami K Ishikawa A 《Physical review letters》2007,99(13):131803
We report a measurement of D0-D(0) mixing parameters in D(0) --> K(s)(0) pi(+) pi(-) decays using a time-dependent Dalitz-plot analysis. We first assume CP conservation and subsequently allow for CP violation. The results are based on 540 fb(-1) of data accumulated with the Belle detector at the KEKB e(+)e(-) collider. Assuming negligible CP violation, we measure the mixing parameters x = (0.80 +/- 0.29(-0.07-0.14)(+0.09+0.10))% and y = (0.33+/-0.24(-0.12-0.08)(+0.08+0.06))%, where the errors are statistical, experimental systematic, and systematic due to the Dalitz decay model, respectively. Allowing for CP violation, we obtain the CP-violating parameters |q / p| = 0.86(-0.29-0.03)(+0.30+0.06) +/- 0.08 and arg(q/p) = (-14(-18-3-4)(+16+5+2)) degrees . 相似文献
999.
The Na(+) ion encapsulated within the Preyssler heteropolyoxoanion, [NaP5W30O110](14-), was exchanged with Pu(III) under hydrothermal conditions to obtain [Pu(III)P5W30O110](12-) (abbreviated [PuPA](12-)) with hybrid electrochemical properties resulting from the combination of the key redox behaviors of the Pu cation and the P-W-O anion. The electroanalytical chemistry of this two-center, multielectron redox system in a 1 M HCl electrolyte shows that Pu(III) is oxidized to Pu(IV) at the half-wave potential, E(1/2), of +0.960 V versus Ag/AgCl, which is 0.197 V more positive than the corresponding electrode potential for the Pu(III) aqua ion also in 1 M HCl, indicating the stabilization of the trivalent Pu cation by its encapsulation in the Preyssler polyoxometalate (POM). This effect is uncommon in actinide-POM chemistry, wherein electrode potential shifts of the opposite nature (to more negative values), leading to the stabilization of the tetravalent ions by complexation, are renowned. Moreover, in cyclic voltammetry measurements of the Pu(III) aqua ion and [PuPA](12-), the peak currents, i(p), for the one-electron Pu(III)/Pu(IV) processes show different dependencies with the scan rate, nu. The former shows proportionality with nu(1/2), indicating freely diffusing species, whereas the latter shows proportionality with nu, indicating a surface-confined one. The first of the five successive two-electron, W-centered reduction processes in [PuPA](12-) occurs at E(1/2) = -0.117 V versus Ag/AgCl, which is 1.077 V less than the E(1/2) for the Pu(III)/Pu(IV) oxidation, thereby providing an experimental, electrochemical measure of the highest occupied molecular orbital/lowest unoccupied molecular orbital energy gap, which compares well with values previously obtained by density-functional theory, complete active space-self consistent field, and post-Hartree-Fock calculations for a series of M(n+)-exchanged systems, [MPA](n-15) for 1 < or = n < or = 4 (Fernandez, J. A.; Lopez, X.; Bo, C.; de Graff, C.; Baerends, E. J.; Poblet, J. M. J. Am Chem. Soc. 2007, 129, 12244-12253). It was not possible to prepare the Np-exchanged Preyssler anion in the manner of [PuPA](12-), because of the instability of tri- and tetravalent Np to oxidation and the formation of the neptunyl(V) ion, which also could not be exchanged for Na(+). 相似文献
1000.
This study develops a crossform CE microfluidic device in which a single-circular barrier or a double-circular barrier is introduced at the cross-channel intersection. Utilizing a conventional crossform injection scheme, it is shown that these barriers reduce sample leakage and deliver a compact sample band into the separation channel, thereby ensuring an enhanced detection performance. A series of numerical and experimental investigations are performed to investigate the effects of the barrier type and the barrier ratio on the flow streamlines within the microchannel and to clarify their respective effects on the sample leakage ratio and sample plug variance during the injection process. The results indicate that a single-circular barrier injector with a barrier ratio greater than 20% and a double-circular barrier injector with a barrier ratio greater than 40% minimize the sample leakage ratio and produce a compact sample plug. As a result, both injectors have an excellent potential for use in high-quality, high-throughput chemical analysis procedures and in many other applications throughout the micro-total analysis systems field. 相似文献