全文获取类型
收费全文 | 1341篇 |
免费 | 38篇 |
国内免费 | 5篇 |
专业分类
化学 | 914篇 |
晶体学 | 3篇 |
力学 | 33篇 |
数学 | 192篇 |
物理学 | 242篇 |
出版年
2021年 | 6篇 |
2020年 | 10篇 |
2019年 | 16篇 |
2018年 | 12篇 |
2017年 | 22篇 |
2016年 | 30篇 |
2015年 | 34篇 |
2014年 | 35篇 |
2013年 | 83篇 |
2012年 | 55篇 |
2011年 | 79篇 |
2010年 | 46篇 |
2009年 | 45篇 |
2008年 | 90篇 |
2007年 | 80篇 |
2006年 | 80篇 |
2005年 | 86篇 |
2004年 | 79篇 |
2003年 | 51篇 |
2002年 | 49篇 |
2001年 | 23篇 |
2000年 | 21篇 |
1999年 | 12篇 |
1998年 | 9篇 |
1997年 | 16篇 |
1996年 | 22篇 |
1995年 | 15篇 |
1994年 | 13篇 |
1993年 | 10篇 |
1992年 | 13篇 |
1991年 | 5篇 |
1990年 | 12篇 |
1989年 | 8篇 |
1988年 | 7篇 |
1987年 | 11篇 |
1986年 | 13篇 |
1985年 | 11篇 |
1984年 | 24篇 |
1983年 | 23篇 |
1982年 | 13篇 |
1981年 | 11篇 |
1980年 | 9篇 |
1979年 | 8篇 |
1978年 | 7篇 |
1977年 | 9篇 |
1976年 | 10篇 |
1975年 | 6篇 |
1973年 | 10篇 |
1967年 | 4篇 |
1954年 | 4篇 |
排序方式: 共有1384条查询结果,搜索用时 218 毫秒
11.
The investigation of europium(III) sulphate hydrate and samarium(III) sulphate hydrate was performed by thermal analysis (TG-DTG) and simultaneous infrared evolved gas analysis-Fourier transformed infrared (EGA-FTIR) spectroscopy. The TG, DTG and DTA curves were recorded at the 25–1400 °C in the dynamic air atmosphere by TG/DTA analyser. The infrared evolved gas analysis was obtained on the FTIR spectrometer. Eu2(SO4)3·nH2O (n = 3.97) and Sm2(SO4)3·nH2O (n = 8.11) were analysed, the dehydration and decomposition steps were investigated and the water content was calculated. The formation of different oxysulphates was studied.
The trace rare earth elements in Eu and Sm sulphates were determined by ICP-MS. The concentration of trace Eu, Sm, La, Gd, Y and Ce ranged from 3.9 × 10−6 to 1.5 × 10−4% (m/m). 相似文献
12.
Pelmenschikov V Blomberg MR Siegbahn PE Crabtree RH 《Journal of the American Chemical Society》2002,124(15):4039-4049
The mechanism for methane formation in methyl-coenzyme M reductase (MCR) has been investigated using the B3LYP hybrid density functional method and chemical models consisting of 107 atoms. The experimental X-ray crystal structure of the enzyme in the inactive MCR(ox1)(-)(silent) state was used to set up the initial model structure. The calculations suggest a mechanism not previously proposed, in which the most remarkable feature is the formation of an essentially free methyl radical at the transition state. The reaction cycle suggested starts from a Michaelis complex with CoB and methyl-CoM coenzymes bound and with a squareplanar coordination of the Ni(I) center in the tetrapyrrole F(430) prosthetic group. In the rate-limiting step the methyl radical is released from methyl-CoM, induced by the attack of Ni(I) on the methyl-CoM thioether sulfur. In this step, the metal center is oxidized from Ni(I) to Ni(II). The resulting methyl radical is rapidly quenched by hydrogen-atom transfer from the CoB thiol group, yielding the methane molecule and the CoB radical. The estimated activation energy is around 20 kcal/mol, which includes a significant contribution from entropy due to the formation of the free methyl. The mechanism implies an inversion of configuration at the reactive carbon. The size of the inversion barrier is used to explain the fact that CF(3)-S-CoM is an inactive substrate. Heterodisulfide CoB-S-S-CoM formation is proposed in the final step in which nickel is reduced back to Ni(I). The suggested mechanism agrees well with experimental observations. 相似文献
13.
When α-halo sulfides are reacted with ambident 2-pyrimidinones, the major product is due to N-alkylation, the minor product to O-alkylation. N-Alkylation is favoured by the presence of a tertiary amine in a solvent of low dielectric constant and also by a change of the α-halo sulfide substituent from chlorine to iodine. Complete selectivity can be achieved. The course of the reaction is rationalized in terms of the HSAB-principle. 相似文献
14.
Bassan A Blomberg MR Siegbahn PE Que L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):692-705
The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane. 相似文献
15.
Philip Wormald Kristina Wickholm Per Tomas Larsson Tommy Iversen 《Cellulose (London, England)》1996,3(1):141-152
An investigation into the effects of mechanical treatment and hydration on the order of cellulose substrates (microcrystalline cellulose and Cladophora cellulose) was performed by the use of ball milling followed by cyclic wetting and drying. The results, monitored by13C-CP/MAS NMR-spectroscopy, were evaluated by calculation of the crystallinity indices and principal component analysis of the NMR data acquired. The results showed that a large part of the disorder induced by the mechanical treatment of cellulose by ball milling is reversible and reordering upon hydration leads to the cellulose I form initially present. The C4 signals corresponding to the reversibly disordered cellulose chains are observed in the amorphous region between 79 and 86 ppm in the13C-CP/MAS NMR-spectra together with signals from cellulose chains on the surface of ordered regions. The peak cluster which contains the C2, C3 and C5 ring carbons can be divided into two specific spectral regions; one between 74 and 77 ppm largely originates from ring carbons within disordered cellulose structures, and one between 70 and 74 ppm contains larger contributions from ordered cellulose. The behaviour of the celluloses upon milling is in accordance with a concept of ordered cellulose fibrils containing amorphous cellulose mainly as surface layers and induced reversible lattice distortions. 相似文献
16.
Westerlund F Wilhelmsson LM Nordén B Lincoln P 《Journal of the American Chemical Society》2003,125(13):3773-3779
Detergent sequestration using micelles as a hydrophobic sink for dissociated drug molecules is an established technique for determination of dissociation rates. The anionic surfactant molecules are generally assumed not to interact with the anionic DNA and thereby not to affect the rate of dissociation. By contrast, we here demonstrate that the surfactant molecules sodium dodecyl sulfate (SDS), sodium decyl sulfate, and sodium octyl sulfate all induce substantial rate enhancements of the dissociation of intercalators from DNA. Four different cationic DNA intercalators are studied with respect to surfactant-induced dissociation. Except for the smallest intercalator, ethidium, the dissociation rate constants increase monotonically with surfactant concentration both below cmc and (more strongly) above cmc, much more than expected from electrostatic effects of increased counterion concentration. The rate enhancement, most pronounced for the bulky, multicationic, hydrophobic DNA ligands in this study, indicates a reduction of the activation energy for the ligand to pass out from a deeply penetrating intercalation site of DNA. The discovery that surfactants enhance the rate of dissociation of cationic DNA-intercalators implies that rate constants previously determined by micelle-sequestered dissociation may have been overestimated. As an alternative, more reliable method, we suggest instead the addition of excess of dummy DNA as an absorbent for dissociated ligand. 相似文献
17.
The in vivo biotransformation of dynorphin A(1-17) (Dyn A) was studied in the striatum of hemiparkinsonian rats by using microdialysis in combination with nanoflow reversed-phase liquid chromatography/electrospray time-of-flight mass spectrometry. The microdialysis probes were implanted into both hemispheres of unilaterally 6-hydroxydopamine (6-OHDA) lesioned rats. Dyn A (10 pmol microl(-1)) was infused through the probes at 0.4 microl min(-1) for 2 h. Samples were collected every 30 min and analyzed by mass spectrometry. The results showed for the first time that there was a difference in the Dyn A biotransformation when comparing the two corresponding sides of the brain. Dyn A metabolites 1-8, 1-16, 5-17, 10-17, 7-10 and 8-10 were detected in the dopamine-depleted striatum but not in the untreated striatum. Dyn A biotransformed fragments found in both hemispheres were N-terminal fragments 1-4, 1-5, 1-6, 1-11, 1-12 and 1-13, C-terminal fragments 2-17, 3-17, 4-17, 7-17 and 8-17 and internal fragments 2-5, 2-10, 2-11, 2-12, and 8-15. The relative levels of these fragments were lower in the dopamine-depleted striatum. The results imply that the extracellular in vivo processing of the dynorphin system is being disturbed in the 6-OHDA-lesion animal model of Parkinson's disease. 相似文献
18.
The catalytic mechanism of molybdenum containing CO dehydrogenase has been studied using hybrid DFT methods with quite large chemical models. The recent high-resolution X-ray structure, showing the surprising presence of copper linked to molybdenum, was used as a starting point. A pathway was initially found with a low barrier for C-O bond formation and CO2 release. However, this pathway did not include the formation of any S-CO2 species, which had been suggested by experiments with an n-butylisocyanide inhibitor. When these SCO2 structures were studied they were found to lead to deep minima, making CO2 release much more difficult. A large effort was spent, including investigations of other spin states, varying the number of protons and electrons, adding water, etc., until a plausible pathway for S-C bond cleavage was found. In this pathway a water molecule is inserted in between molybdenum and the SCO2 group. Full catalytic cycles, including electron and proton transfers, are constructed both with and without S-C bond formation. When these pathways are extended to two full catalytic cycles it can be understood why the formation of the S-C bond actually makes catalysis faster, even though the individual step of CO2 release becomes much more difficult. These results agree well with experimental findings. 相似文献
19.
Yasser M. Loksha Per T. Jrgensen Erik B. Pedersen Mahmoud A. El‐Badawi Ahmed A. El‐Barbary Claus Nielsen 《Journal of heterocyclic chemistry》2002,39(2):375-382
5‐Alkyl‐4‐benzyl‐1,3‐dihydroimidazol‐2‐ones ( 3a‐d ) and 5‐alkyl‐4‐benzyl‐1,3‐dihydroimidazole‐2‐thiones (7a‐d) were prepared via Dakin West reaction on DL‐phenylalanine with the appropriate aliphatic acid anhydrides followed by hydrolysis and reaction with potassium cyanate or potassium thiocyanate. Compounds 3a‐d were alkylated with ethoxymethyl chloride to give the alkylated imidazoles 5a‐d which were considered analogues of Emivirine with deletion of carbonyl group at the 4‐position. Alkylation of 7a‐d afforded the corresponding S‐alkylated derivatives 8a‐p which in a similar way were considered analogues of S‐DABO. However all the imidazole derivatives were devoid of activity against HIV. 相似文献
20.
A number of 4-allylic substituted 3,5-diphenyl-4H-1,2,4-triazoles were thermolyzed at 315–320° in evacuated glass ampoules. The main reaction in the melt was rearrangement to the corresponding 1-substituted triazoles, which appeared to proceed via competing SN2 and SN2′ mechanisms. The allylic systems were observed to undergo [2,3]-allyl walk reactions between the 1- and 2-ring positions. Allyl to vinyl isomerization also took place. Substitution of the allylic moiety increased the rate of reaction but decreased the rate of isomerization of allylic to the vinylic substituted triazoles. The 4-vinyl substituted triazoles were inert under the reaction conditions. Some triazoles were converted into substituted pyridines. This was proposed to proceed via nitrogen extrusion and formation of a 1,3-dipolar intermediate (nitrile ylide) which added intramolecularly to the allyl moiety and subsequently aromatized to the pyridine. 相似文献