全文获取类型
收费全文 | 706篇 |
免费 | 24篇 |
国内免费 | 1篇 |
专业分类
化学 | 594篇 |
晶体学 | 14篇 |
力学 | 5篇 |
数学 | 55篇 |
物理学 | 63篇 |
出版年
2024年 | 2篇 |
2023年 | 6篇 |
2022年 | 24篇 |
2021年 | 19篇 |
2020年 | 12篇 |
2019年 | 8篇 |
2018年 | 12篇 |
2017年 | 12篇 |
2016年 | 14篇 |
2015年 | 25篇 |
2014年 | 17篇 |
2013年 | 28篇 |
2012年 | 54篇 |
2011年 | 81篇 |
2010年 | 26篇 |
2009年 | 26篇 |
2008年 | 44篇 |
2007年 | 51篇 |
2006年 | 47篇 |
2005年 | 43篇 |
2004年 | 41篇 |
2003年 | 26篇 |
2002年 | 27篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1998年 | 1篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 11篇 |
1994年 | 9篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1991年 | 3篇 |
1988年 | 4篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 1篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1934年 | 1篇 |
1905年 | 1篇 |
排序方式: 共有731条查询结果,搜索用时 15 毫秒
51.
Pettinari C Marchetti F Lupidi G Quassinti L Bramucci M Petrelli D Vitali LA da Silva MF Martins LM Smoleński P Pombeiro AJ 《Inorganic chemistry》2011,50(21):11173-11183
Five new silver(I) complexes of formulas [Ag(Tpms)] (1), [Ag(Tpms)(PPh(3))] (2), [Ag(Tpms)(PCy(3))] (3), [Ag(PTA)][BF(4)] (4), and [Ag(Tpms)(PTA)] (5) {Tpms = tris(pyrazol-1-yl)methanesulfonate, PPh(3) = triphenylphosphane, PCy(3) = tricyclohexylphosphane, PTA = 1,3,5-triaza-7-phosphaadamantane} have been synthesized and fully characterized by elemental analyses, (1)H, (13)C, and (31)P NMR, electrospray ionization mass spectrometry (ESI-MS), and IR spectroscopic techniques. The single crystal X-ray diffraction study of 3 shows the Tpms ligand acting in the N(3)-facially coordinating mode, while in 2 and 5 a N(2)O-coordination is found, with the SO(3) group bonded to silver and a pendant free pyrazolyl ring. Features of the tilting in the coordinated pyrazolyl rings in these cases suggest that this inequivalence is related with the cone angles of the phosphanes. A detailed study of antimycobacterial and antiproliferative properties of all compounds has been carried out. They were screened for their in vitro antimicrobial activities against the standard strains Enterococcus faecalis (ATCC 29922), Staphylococcus aureus (ATCC 25923), Streptococcus pneumoniae (ATCC 49619), Streptococcus pyogenes (SF37), Streptococcus sanguinis (SK36), Streptococcus mutans (UA159), Escherichia coli (ATCC 25922), and the fungus Candida albicans (ATCC 24443). Complexes 1-5 have been found to display effective antimicrobial activity against the series of bacteria and fungi, and some of them are potential candidates for antiseptic or disinfectant drugs. Interaction of Ag complexes with deoxyribonucleic acid (DNA) has been studied by fluorescence spectroscopic techniques, using ethidium bromide (EB) as a fluorescence probe of DNA. The decrease in the fluorescence of DNA-EB system on addition of Ag complexes shows that the fluorescence quenching of DNA-EB complex occurs and compound 3 is particularly active. Complexes 1-5 exhibit pronounced antiproliferative activity against human malignant melanoma (A375) with an activity often higher than that of AgNO(3), which has been used as a control, following the same order of activity inhibition on DNA, i.e., 3 > 2 > 1 > 5 > AgNO(3)? 4. 相似文献
52.
The first dinitrogen complexes with the hydrosoluble PTA ligand, or its protonated form PTA-H, trans-[ReCl(N2)(PTA-H)n(PTA)(4-n)]n+ (n = 0-4), are prepared, shown to be soluble and stable in water, interconvertible by stepwise protonation/deprotonation and to form, upon N2 loss, the corresponding penta-coordinate compounds. Dinitrogen displacement by CO affords trans-[ReCl(CO)(PTA)4]. 相似文献
53.
Water-soluble Co (III) and Co (II) complexes with P- or N-coordinated PTA or PTA oxide ligands, respectively, have been prepared and fully characterized, constituting the first examples of cobalt compounds bearing PTA or any ligand with a cage-like PTA core, the latter complex providing also the first PTA oxide coordination to a metal center. 相似文献
54.
Giovanni Di Fabio Valeria RomanucciMauro De Nisco Silvana PedatellaCinzia Di Marino Armando Zarrelli 《Tetrahedron letters》2013
A new and preparative oxidation of silibinin has been developed to give access to two different silibinin derivatives known for their enhanced antioxidant properties. Conventional heating methods were compared with results obtained from microwave (MW) heating. The base-catalysed oxidation of silibinin under MW heating is a very efficient method for the preparation of 2,3-dehydrosilybin and a related silybin rearrangement product. This latter compound shows enhanced radical scavenging properties. Optimised conditions were used to prepare 2,3-dehydrosilybins A and B from optically pure silybins A and B. An efficient, preparative purification method was also developed to enable isolation of different products in high purity. 相似文献
55.
Field LM Lahti PM Palacio F Paduan-Filho A 《Journal of the American Chemical Society》2003,125(33):10110-10118
Mn(hfac)(2) and Cu(hfac)(2) form coordination complexes with 5-(4-[N-tert-butyl-N-aminoxyl]phenyl)pyrimidine, PyrimPh-NIT. (Mn[PyrimPh-NIT](hfac)(2))(2) and (Cu[PyrimPh-NIT](hfac)(2))(2), 1 and 2, respectively, are cyclic M(2)L(2) dimers that exhibit strong exchange coupling between the coordinated paramagnetic dication (M) and nitroxide (NIT) unit. The M-NIT exchange is strongly antiferromagnetic (AFM) in 1 and strongly ferromagnetic (FM) in 2. Magnetic susceptibility measurements for 1 were fitted to an AFM spin pairing model with J/k = -0.25 K between Mn-NIT spin sites units. Complex 2 also exhibits AFM spin pairing between S = 1 Cu-NIT spin units that is somewhat field dependent at low temperature. The fit of corrected paramagnetic susceptibility chi(T) to an AFM spin pairing model at 200 Oe yields J/k = (-)3.8 K, quite similar to earlier measurements at 1000 Oe yielding J/k = (-)5.0 K. At 1.40 K, the magnetization of 2 does not approach saturation until somewhat above 170 kOe, giving an S-shaped curve; at 0.55 K, the magnetization curve shows steps characteristic of field-induced crossover between the S = 0 ground state and excited spin states. From the steps in the 0.55 K data, we estimate J/k = (-)3.8-4.0 K for 2, in good agreement with the analysis of chi(T). 相似文献
56.
Simple modular di- and tripeptides with a primary amine at the N-terminus catalyze the aqueous asymmetric aldol reaction between unmodified ketones and aldehydes to furnish the corresponding beta-hydroxy ketones with up to 86% ee in water and 99% ee in aqueous media. 相似文献
57.
Makarycheva-Mikhailova AV Bokach NA Kukushkin VY Kelly PF Gilby LM Kuznetsov ML Holmes KE Haukka M Parr J Stonehouse JM Elsegood MR Pombeiro AJ 《Inorganic chemistry》2003,42(2):301-311
Pt(IV)-mediated addition of the sulfimide Ph2S = NH and the mixed sulfide/sulfimides o- and p-[PhS(=NH)](PhS)-C6H4 by the S=NH group to the metal-bound nitriles in the platinum(IV) complexes [PtCl4(RCN)2] proceeds smoothly at room temperature in CH2Cl2 and results in the formation of the heterodiazadiene compounds [PtCl4[NH=C(R)N=SR'Ph]2] (R' = Ph, R = Me, Et, CH2Ph, Ph; R' = o- and p-(PhS)C6H4; R = Et). While trans-[PtCl4(RCN)2] (R = Et, CH2Ph, Ph) reacting with Ph2S=NH leads exclusively to trans-[PtCl4[NH=C(R)N=SPh2]2], cis/trans-[PtCl4(MeCN)2] leads to cis/trans mixtures of [PtCl4[NH=C(Me)N=SPh2]2] and the latter have been separated by column chromatography. Theoretical calculations at both HF/HF and MP2//HF levels for the cis and trans isomers of [PtCl4[NH=C(Me)N=SMe2]2] indicate a higher stability for the latter. Compounds trans-[PtCl4[E-NH=C(R)N=SPh2]2] (R = Me, Et) and cis-[PtCl4[E-NH=C(Me)N=SPh2][Z-NH=C(Me)N=SPh2]] have been characterized by X-ray crystallography. The complexes [PtCl4[NH=C(R)N=SPh2]2] undergo hydrolysis when treated with HCl in nondried CH2Cl2 to achieve the amidines [PtCl4[NH=C(NH2)R]2] the compound with R = Et has been structurally characterized) and Ph2SO. The heterodiazadiene ligands, formed upon Pt(IV)-mediated RCN/sulfimide coupling, can be liberated from their platinum(IV) complexes [PtCl4[NH=C(R)N=SR'Ph]2] by reaction with Ph2PCH2CH2PPh2 (dppe) giving free NH=C(R)=SR'Ph and the dppe oxides, which constitutes a novel route for such rare types of heterodiazadienes whose number has also been extended. The hybrid sulfide/sulfimide species o- and p-[PhS(=NH)](PhS)C6H4 also react with the Pt(II) nitrile complex [PtCl2(MeCN)2] but the coupling--in contrast to the Pt(IV) species--gives the chelates [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh]]. The X-ray crystal structure of [PtCl2[M-I=C(Me)N=S(Ph)C6H4SPh-o]] reveals the bond parameters within the metallacycle and shows an unusual close interaction of the sulfide sulfur atom with the platinum. 相似文献
58.
Branscombe ND Atkins AJ Marin-Becerra A McInnes EJ Mabbs FE McMaster J Schröder M 《Chemical communications (Cambridge, England)》2003,(9):1098-1099
Multi-frequency EPR spectroscopy on 61Ni-labelled samples of [Ni2(L)]3+ confirms extensive charge-delocalisation between the Ni(III) centre and thiolate donors in the Ni(II)Ni(III) complex. 相似文献
59.
Organocatalytic cross-aldol reactions catalyzed by cyclic secondary amines in aqueous media provide a direct route to a variety of aldols including carbohydrate derivatives and may warrant consideration as a prebiotic route to sugars. 相似文献
60.
Tom Schoonjans Antonio Brunetti Bruno Golosio Manuel Sanchez del Rio Vicente Armando Solé Claudio Ferrero Laszlo Vincze 《Spectrochimica Acta Part B: Atomic Spectroscopy》2011,66(11-12):776-784
This work presents the recent developments of xraylib, an ANSI C library that provides convenient access to a large number of X-ray related databases, with a focus on quantitative X-ray fluorescence applications. The enhancements include improved X-ray fluorescence production cross sections that take into account cascade effects and M-lines, as well as revised line energies, atomic level widths, Compton broadening profiles etc. A full overview of the complete application programming interface is presented. 相似文献