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61.
A brief treatment of 2-thiopyrimidine nucleosides (s2U∗) with trans-2-phenylsulfonyl-3-phenyloxaziridine (PSO) results in efficient substrate desulfurization leading to the corresponding 4-pyrimidinone analogues (H2U∗). The key transformation proceeds through oxidation of the 2-thiocarbonyl group to a sulfur oxyacid derivative and subsequent elimination of sulfur dioxide. 4-Pyrimidinone 1-β-d-riboside (H2U) has been transformed into the respective phosphoramidite, a ready-to-use monomer for the introduction of a modified nucleoside into an oligonucleotide chain. Moreover, the effective desulfurization of the 2-thiouridine nucleotide could be achieved directly at the oligonucleotide level, by treatment of the TdA(s2U)dGdC oligonucleotide with PSO, as verified by MALDI-TOF mass spectrometry. 相似文献
62.
Lee HJ Kim JH Jung HJ Kim KY Kim EJ Choi YS Yoon CJ 《Journal of computational chemistry》2004,25(2):169-178
The effect of thioamide substitution on the conformational stability of an azaglycine-containing peptide, For-AzaGly-NH2 (1), was investigated for the sake of finding possible applications by using ab initio and DFT methods. As model compounds, For-[psiCSNH]-AzaGly-NH2 (2), For-AzaGly-[psiCSNH]-NH2 (3), and For-[psiCSNH]-AzaGly-[psiCSNH]-NH2 (4) were used. Two-dimensional phi-psi potential energy surfaces (PESs) for 2-4 were calculated at the B3LYP/6-31G*//HF/6-31G* level in gas (epsilon = 1.0) and in water (epsilon = 78.4) by applying the isodensity polarizable continuum model (IPCM) method. On the basis of these PESs, the minimum energy conformations for 2-4 were characterized at the B3LYP level with 6-31G*, 6-311G**, and 6-31+G** basis sets. The remarkable structural effect of thioamide substitution for 2-4 is that beta-strand structure is observed as a global or local minimum. The minima of 2-4 are also compared with those for glycine and thioamide-containing glycine peptides. Our theoretical results demonstrate that compounds 2-4 would be used to design controllable secondary structures. 相似文献
63.
轻度交联环糊精聚合物包结诱导自组装胶束的研究 总被引:1,自引:0,他引:1
合成了含β-环糊精的多取代单体(GMA)x-CD,经自由基聚合得到轻度交联的或高度支化的聚合物P(GMA)x-CD;同时由自由基共聚得到含有金刚烷侧基的疏水聚合物PtBA-ADA.研究表明,他们可在碱性水中通过β-CD和ADA间的包结络合作用形成胶束.当改变聚合物浓度比时,胶束尺寸在150~300 nm范围变化.TEM和AFM研究表明胶束具有核壳结构,核为疏水PtBA-ADA,壳为亲水(GMA)x-CD.通过对胶束壳CD基的化学交联,将胶束结构进一步固定化. 相似文献
64.
一种新型两性表面活性剂的合成 总被引:2,自引:0,他引:2
两性表面活性剂分子既含有阳离子亲水基,又含有阴离子亲水基,因而有其它表面活性剂所不具备的优异性能。本文将月桂酸和N-(2-羟乙基)乙二胺热缩合脱水,得到2-十一烷基-1-(2-羟乙基)-2-咪唑啉(1)。接着在还原剂的作用下,咪唑啉环碳氮双键还原并开环得到一般方法难以合成的N,N-二取代乙二胺(2)。(2)通过甲酰化(3)季铵化,引入两性离子,得到 相似文献
65.
The reaction of (α-trimethylsilanylmethyl)cyclohexylidene esters with NsONHCO2Et and CaO produces the N-(ethoxycarbonyl)spiroaziridines which, after ring-opening, gives the corresponding β,β-disubstituted β-amino ester derivatives. The stereochemical outcome of the reaction is influenced by substituents on the cyclohexyl group. 相似文献
66.
67.
Pina Romaniello 《Journal of fluorine chemistry》2004,125(2):145-149
The effect of fluorine atoms on the second-order optical nonlinear response of 4-nitro-4′-methoxy-trans-stilbene and polyene derivatives containing up to three double bonds (n=1, 2, 3) has been investigated within a semiempirical context (PM3 Hamiltonian). Experimental data reported in literature indicate a βvec(SHG) value of 34, 47 and 76 (×10−30 esu) for n=1, 2, 3, respectively, at 0.65 eV in CHCl3 solutions. Our calculations show that fluorinating the nitrophenyl group the βvec(SHG) is doubled. Further increase in the second-order nonlinear response can be obtained fluorinating the CC bond linkers between the aromatic moieties.Besides, the effect of different donor-acceptor pairs has been studied and the results interpreted in the two-state model context.Some results concerning the third-harmonic generation (THG), γ (THG), are presented, and a possible interpretation proposed. 相似文献
68.
Vanessa Gouge 《Tetrahedron letters》2004,45(4):773-776
2,2-Difluoro-3-(2-hydroxy-1 R-phenylethylamino)-3 S-phenylpropionic acid 3, obtained by a Reformatsky-type reaction of ethyl bromodifluoroacetate with (4R)-2,4-diphenyloxazolidine, was used as a classical carboxylic acid in the Ugi reaction to prepare various difluorinated pseudopeptides 5a-n. Compounds 5 were then deprotected by hydrogenolysis to furnish difluorinated pseudopeptides 6. 相似文献
69.
Tetrabutylammonium cyanide has been used as non-metallic catalyst for the diastereoselective cyanosilylation of α-hydroxyketones derived from the chiral pool. This affords α-substituted-α,β-dihydroxynitriles with high levels of asymmetric induction. 相似文献
70.
Four new chiral stationary phases based on mono-(6A-allylcarbamido-6A-deoxy)-arylcarbamoylated β-cyclodextrin were synthesized. The chiral stationary phase of phenylcarbamoylated β-cyclodextrin exhibited excellent separation capability for a variety of chiral compounds. Compared with the previous work, it was found that the spacer remained on the surface of the silica gel and decreased the enantioseparation capability. 相似文献