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81.
Mamta Chahar 《Tetrahedron》2008,64(27):6488-6493
New deoxycholic acid-based cyclic receptors bearing imidazolium and benzimidazolium moieties bridged with o-xylelene and 1,8-dimethylenenaphthalene groups have been synthesized. Anion binding studies using 1H NMR revealed that receptors having naphthalenic group as spacer exhibit very high selectivity for fluoride ion over other anions while receptors with o-xylelene group show a preference for the chloride ion. 相似文献
82.
83.
Rapid rotation of guanine base derivatives about Pt-N7 bonds results in fluxional behavior of models of the key DNA intrastrand G-G cross-link leading to anticancer activity of Pt(II) drugs (G = deoxyguanosine). This behavior impedes the characterization of LPtG2 models (L = one bidentate or two cis-unidentate carrier ligands; G = guanine derivative not linked by a phosphodiester group). We have examined the formation of LPtG2 adducts with G = 5'- and 3'-GMP and L = sp(2) N-donor bidentate carrier ligands [5,5'-dimethyl-2,2'-bipyridine (5,5'-Me2bipy), 3-(4'-methylpyridin-2'-yl)-5,6-dimethyl-1,2,4-triazine) (MepyMe2t), and bis-3,3'-(5,6-dialkyl-1,2,4-triazine) (R4dt)]. NMR spectroscopy provided conclusive evidence that these LPt(5'-GMP)2 complexes exist as interconverting mixtures of head-to-tail (HT) and head-to-head (HH) conformers. For a given G, the rates of G base rotation about the Pt-N7 bonds of LPtG2 models decrease in the order Me4dt > Et4dt > MepyMe2t > 5,5'-Me2bipy. This order reveals that the pyridyl ring C6 atom + H atom grouping is large enough to impede the rotation, but the equivalently placed triazine ring N atom + N lone pair grouping is sterically less impeding. For the first time, the two possible HH conformers (HHa and HHb) in the case of an unsymmetrical L have been identified in our study of (MepyMe2t)Pt(5'-GMP)2. Although O6-O6 clashes involving the two cis G bases favor the HT over the HH arrangement for most LPtG2-type complexes, the HH conformer of (R4dt)Pt(5'-GMP)2 adducts has a high abundance (approximately 50%). We attribute this high abundance to a reduction in O6-O6 steric clashes permitted by the overall low steric effects of R4dt ligands. Under the reaction conditions used, 3'-GMP forms a higher abundance of the LPt(GMP)2 adduct than does 5'-GMP, a result attributable to more favorable second-sphere communication in the LPt(3'-GMP)2 adduct than in the LPt(5'-GMP)2 adduct. 相似文献
84.
Karuna Maheshwari Manish Kumar Srivastava Sanjiv Saxena 《Phosphorus, sulfur, and silicon and the related elements》2017,192(5):506-512
Two new sets of diethylgermanium(IV) complexes of the types Et2GeA2 and Et2GeB2 have been generated by the reactions of diethylgermanium(IV) dichloride with sodium salts of N-protected amino acids (AH) [where AH = , R = -CH(CH3)C2H5: A1H, R = -CH2CH(CH3)2: A2H, R = -CH(CH3)2: A3H] and with sodium salts of sterically demanding heterocyclic β-diketones (BH) [where BH = , R’ = -C6H5: B1H, R’ = -p-(Cl)C6H4: B2H, R’ = -CH3: B3H, R = -C2H5: B4H], respectively in 1:2 molar ratios in refluxing dry benzene. Plausible structures of these complexes were suggested on the basis of physico-chemical and spectroscopic studies. It is suggested that the complexes of the types Et2GeA2 and Et2GeB2 contain four coordinated and six coordinated germanium centers, respectively. The ligands and organogermanium(IV) complexes were evaluated for their free radical scavenging activity by DPPH method. These compounds/complexes demonstrate potential antioxidant activity. 相似文献
85.
Platinum anticancer drug DNA intrastrand cross-link models, LPt(d(G*pG*)) (G* = N7-platinated G residue, L = R(4)dt = bis-3,3'-(5,6-dialkyl)-1,2,4-triazine), and R = Me or Et), undergo slow Pt-N7 bond rotation. NMR evidence indicated four conformers (HH1, HH2, ΔHT1, and ΛHT2); these have different combinations of guanine base orientation (head-to-head, HH, or head-to-tail, HT) and sugar-phosphodiester backbone propagation relative to the 5'-G* (the same, 1, or opposite, 2, to the direction in B DNA). In previous work on LPt(d(G*pG*)) adducts, Pt-N7 rotation was too rapid to resolve conformers (small L with bulk similar to that in active drugs) or L was too bulky, allowing formation of only two or three conformers; ΛHT2 was not observed under normal conditions. The (R(4)dt)Pt(d(G*pG*)) results support our initial hypothesis that R(4)dt ligands have Goldilocks bulk, sufficient to slow G* rotation but insufficient to prevent formation of the ΛHT2 conformer. Unlike the (R(4)dt)Pt(5'-GMP)(2) adducts, ROESY spectra of (R(4)dt)Pt(d(G*pG*)) adducts showed no EXSY peaks, a result providing clear evidence that the sugar-phosphodiester backbone slows conformer interchange. Indeed, the ΛHT2 conformer formed and converted to other conformers slowly. Bulkier L (Et(4)dt versus Me(4)dt) decreased the abundance of the ΛHT2 conformer, supporting our initial hypothesis that steric crowding disfavors this conformer. The (R(4)dt)Pt(d(G*pG*)) adducts have a low abundance of the ΔHT1 conformer, consistent with the proposal that the ΔHT1 conformer has an energetically unfavorable phosphodiester backbone conformation; its high abundance when L is bulky is attributed to a small d(G*pG*) spatial footprint for the ΔHT1 conformer. Despite the Goldilocks size of the R(4)dt ligands, the bases in the (R(4)dt)Pt(d(G*pG*)) adducts have a low degree of canting, suggesting that the ligand NH groups characteristic of active drugs may facilitate canting, an important aspect of DNA distortions induced by active drugs. 相似文献
86.
Chong HS Song HA Kang CS Le T Sun X Dadwal M Lee H Lan X Chen Y Dai A 《Chemical communications (Cambridge, England)》2011,47(19):5584-5586
A novel bifunctional ligand (3p-C-NETA) for antibody-targeted radioimmunotherapy (RIT) of β-emitting radioisotopes (90)Y and (177)Lu was efficiently synthesized via an unexpected regiospecific ring opening of an aziridinium ion. 3p-C-NETA instantly formed a very stable complex with (90)Y or (177)Lu. 3p-C-NETA is an excellent bifunctional ligand for RIT. 相似文献
87.
The mechanism of biocidal action of nano titania on Escherichia coli and Staphylococcus aureus has been evaluated by various biochemical techniques like lipid peroxidation, hydrolysis of orthonitrophenol β-D-galactopyranoside, estimation of protein-amino acid and bacterial nucleic acids leakage into solution, in addition to morphology studies by electron microscopy (TEM and SEM) and K(+) ion leakage by inductively coupled plasma optical emission spectrometry. The active anatase phase of nano titania has been synthesized by sol-gel and pulverization techniques to obtain particle sizes averaging around 11 nm. The nano semiconductor with a bandgap of 3.2 eV responds well to the UV source to liberate reactive oxygen species (ROS). Gram negative bacteria easily succumb to the ROS at a faster rate than gram-positive bacteria with an observable difference in the mode of attack. The use of analytical techniques revealed the release of peroxidized lipid (26 nmol mL(-1) ) and protein content (370 μg mL(-1)) with a K(+) ion concentration of 22 000 ppb on complete destruction of E. coli. 相似文献
88.
Sharma SK Prakash J Sudarshan K Maheshwari P Sathiyamoorthy D Pujari PK 《Physical chemistry chemical physics : PCCP》2012,14(31):10972-10978
The phenol-formaldehyde-carbon nanotube composites were characterized for their free volume properties and interfacial interactions between nanotubes and the polymer matrix. The base polymeric material was a novolac type phenol-formaldehyde (PF) condensation resin cross-linked with para-toluene sulfonic acid. Multi-wall carbon nanotubes (MWCNTs) were synthesized using a catalytical chemical vapor deposition method and characterized using high-resolution transmission electron microscopy. The PF resin-carbon nanotubes composites having 2, 5, 10 and 20% (w/w%) MWCNTs were prepared. The crystallinity and morphology of the samples were characterized using X-ray diffraction and scanning electron microscopy. The free volume size in the polymer nanocomposites was observed to increase with the increase in nanotube content. Positron age momentum correlation (AMOC) studies revealed the electronic environment around different positron annihilation sites. The studies showed that ortho-positronium principally annihilates from interfacial regions of polymer and nanotubes in the nanocomposite. The positron lifetime studies together with AMOC measurements indicate an increase in the free volumes at the interface of polymer and MWCNTs in the composite. The free positron intensities showed that the polymer and nanotubes are weakly interacting in this system. 相似文献
89.
Satyendra N. Shukla Pratiksha Gaur Mamta Prasad Mahender Prasad Ripul Mehrotra Sheela Mathews 《中国化学会会志》2012,59(4):485-493
The reaction of a new heterocyclic bidentate N containing spacer, (ligand) 5,5′‐methylenebis(pyridine) with ruthenium sulphoxide precursors resulted, dinuclear complexes. We herein report three formulations; [{cis,fac‐RuCl2(so)3}2(μ‐mbp)].3so; [{trans,mer‐RuCl2(so)32}2(μ‐mbp)].3so and [{trans‐RuCl4(so)}2(μ‐mbp)]2?[X]2+; where so = dimethyl‐sulfoxide/tetramethylenesulfoxide; mbp = 5,5′‐methylenebis(pyridine) and [X]+ = [(dmso)2H]+, Na+ or [(tmso)H]+. These complexes were characterized on the basis of elemental analyses, molar conductance measurement, magnetic susceptibility, FT‐IR, 1H‐NMR, 13C{1H}‐NMR, electronic spectroscopy and FAB‐Mass spectrometry. Catalytic activity of these complexes has been investigated in hydrolysis of benzonitrile. All the complexes exhibit good antibacterial activity against gram‐negative bacteria Escherichia coli in comparison to Chloramphenicol. 相似文献
90.
G. N. Sashi Kumar N. K. Maheshwari 《International Journal of Computational Fluid Dynamics》2018,32(1):19-34
A numerical scheme for simulating multi-species shock accelerated flows using lattice Boltzmann approach has been proposed. It uses the moment conservation approach of Yang, Shu, and Wu and extends it to multi-species fluid problems. The multi-species method of Wang et al. has been modified by use of a predictor–corrector approach. This has helped in preventing the pressure oscillations while handling multi-species. Simulation of 2D shock cylinder interaction with this solver has shown good agreement with the experimental data and could capture material discontinuity and unsteady shocks. The simulation of a single mode Richtmyer–Meshkov instability showed that the solver is able to capture the development of spike and bubble as per the experimental findings of Aure and Jacobs. The dissipation in the proposed scheme was further reduced by the use of fifth-order weighted essentially non-oscillatory (WENO). Validated with multiple problems, this method has been found to capture shock instability with good accuracy with a check on pressure oscillations. 相似文献