全文获取类型
收费全文 | 1915篇 |
免费 | 14篇 |
国内免费 | 11篇 |
专业分类
化学 | 1111篇 |
晶体学 | 15篇 |
力学 | 65篇 |
数学 | 442篇 |
物理学 | 307篇 |
出版年
2020年 | 16篇 |
2019年 | 16篇 |
2016年 | 18篇 |
2015年 | 14篇 |
2014年 | 23篇 |
2013年 | 101篇 |
2012年 | 43篇 |
2011年 | 56篇 |
2010年 | 43篇 |
2009年 | 54篇 |
2008年 | 60篇 |
2007年 | 57篇 |
2006年 | 83篇 |
2005年 | 71篇 |
2004年 | 55篇 |
2003年 | 63篇 |
2002年 | 47篇 |
2001年 | 43篇 |
2000年 | 48篇 |
1999年 | 30篇 |
1998年 | 45篇 |
1997年 | 38篇 |
1996年 | 50篇 |
1995年 | 26篇 |
1994年 | 35篇 |
1993年 | 26篇 |
1992年 | 30篇 |
1991年 | 29篇 |
1990年 | 20篇 |
1989年 | 24篇 |
1988年 | 21篇 |
1987年 | 22篇 |
1986年 | 17篇 |
1985年 | 38篇 |
1984年 | 35篇 |
1983年 | 33篇 |
1982年 | 30篇 |
1981年 | 17篇 |
1980年 | 46篇 |
1979年 | 19篇 |
1978年 | 34篇 |
1977年 | 41篇 |
1976年 | 27篇 |
1975年 | 20篇 |
1974年 | 39篇 |
1973年 | 34篇 |
1972年 | 21篇 |
1971年 | 21篇 |
1969年 | 29篇 |
1968年 | 15篇 |
排序方式: 共有1940条查询结果,搜索用时 15 毫秒
11.
12.
Norman S. Allen 《Journal of photochemistry and photobiology. A, Chemistry》1996,100(1-3):101-107
The radiation curing industry is one of the most rapidly developing fields in the entire coatings industry. The low toxicity, cheapness, speed, control and ease of formulation and operation are some of the main advantages of this growing technology. UV and/or visible light radiation is used to induce photochemical polymerization or crosslinking of a monomer, oligomer or prepolymer formulation containing a certain type of unsaturation, such as an acrylic group, and an appropriate initiator. The latter is used to absorb the light energy and transform it into active species, such as radicals or ions, capable of inducing such reactions. Applications extend to general coatings for paper, board, wood, tapes, compact discs and holograms, inks, photoresists for imaging processes and adhesives for welding and sealing in electronic circuit boards. The photoinitiator is the key to the control of these processes and, in recent years, has seen many new developments. These include the need for water-soluble, co-reactive and polymeric structures with low migration rates, as well as cheaper UV/ visible sensitizers with enhanced speed. New and effective cationic systems are also on the scene and, although expensive, are attracting significant academic and commercial interest. 相似文献
13.
The base hydrolysis and spontaneous water hydrolysis of the phosphonate ester 2,4-dinitrophenyl ethyl methylphosphonate (DNPEMP) has been studied in detail and the activation parameters for these processes determined. The catalytic effect of a series of 19 oxygen and nitrogen bases and metal hydroxo complexes has been studied. The Brønsted plot of pK versus logkN has a slope (β) of 0.47, which is fairly typical for phosphate and phosphonate esters. alpha-Effect nucleophiles such as 2-iodosobenzoate, hypochlorite and the hydroperoxide ion (HO-2) exhibit enhanced reactivity, as does fluoride ion and the bifunctional metal complex [Cu(tmen) (OH2)(OH)]+ (tmen = N,N,N',N',-tetramethylethylenediamine). Reactions involving these species appear to take place by a nucleophilic pathway, while the other oxygen and nitrogen bases act as general base catalysts. The solvent deuterium isotope effect for Et3N catalysis, kH2O/kD2O=1.3, is consistent with general base catalysis. The mechanisms of these reactions are discussed in detail. 相似文献
14.
Norman J. Johnston 《Journal of polymer science. Part A, Polymer chemistry》1972,10(9):2727-2750
The solution polymerization of pyromellitic dianhydride with 3,3′-diaminobenzidine to form poly(amide acid amine) was investigated under a variety of reaction conditions. Polymer viscosity and gel formation were highly affected by changes in the order of monomer addition, the type of process (powder or solution), monomer concentration, monomer stoichiometry, and type of solvent. Minor effects were noted with changes in polymerization temperature and the presence of small amounts of water. A limiting intrinsic viscosity of 1.2–1.5 dl/g was observed, regardless of polymerization conditions. The polymerization had a strong tendency to gel at high concentrations and when monomer molar ratios approached 1:1. The conditions which retarded or promoted the formation of macrogel were well-defined, and macrogel but not microgel could be prevented. The polymerization was conducted successfully only in aprotic solvents. No imidazopyrrol-one units were detected in polymer made in polyphosphoric acid at elevated temperatures. 相似文献
15.
Norman S. Allen Alfonso Chirinos-Padron John H. Appleyard 《Polymer Degradation and Stability》1982,4(3):223-237
The photo-stabilising action of three metal chelates—nickel (II) 2,2′ thiobis (4-tert-octylphenylato) n-butylamine and the nickel and calcium derivatives of bis (ethyl-3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, in polypropylene—is examined using normal and second order derivative ultraviolet, infra-red and phosphorescence spectroscopic techniques and hydroperoxide analysis. Whilst all three stabilisers quenched the phosphorescence emission of a powerful photo-sensitiser, benzophenone, there was no protective action during photo-sensitised oxidation of the polymer. In the case of anthraquinone, there was no quenching and no protection. Processing history plays a dominant rôle in controlling the photo-stabilising performance of the chelates. Each stabiliser operates differently, being dependent on its relative stability during processing and photo-oxidation and on the formation and destruction of polymeric and antioxidant hydroperoxides during processing. Metal chelates operate by inhibiting polymer hydroperoxide formation during processing and acting as ultraviolet stable chain terminators or by giving products during the early stages of photo-oxidation which are themselves effective stabilisers. 相似文献
16.
The C-methylation of the potassium salt of 1-t-butyl-2-phenyl-3-(p-phenylbenzoyl)azetidine ( 1a ) with methyl iodide was studied in three solvents, and the stereochemical outcome of the reaction was shown to be dependent upon the solvent used. These results are rationalized in terms of the probable relative rates of the reaction in the various solvents and/or the effect of solvent on the structure of the anionic intermediate. Similar treatment of the potassium salt of 1-t-butyl-2-phenyl-3-benzoylazetidine ( 3a ) in ethyl ether gave a comparable result. The configurations of the epimeric C-methyl products ( 2a and 2b , and 4a ) were assigned on the basis of their spectral properties. With the aid of spectral data for a model compound, l-t-butyl-3-benzoyl-azetidine ( 5 ), several stereostructure-spectra relationships for 3-azetidinyl ketones are presented. 相似文献
17.
Norman S. Allen Alfonso Chirinos-Padron John H. Appleyard 《Polymer Degradation and Stability》1984,6(3):149-176
The interactions of three metal chelates (nickel (II) 2,2′-thiobis (4-tertoctyl-phenolato), n-butylamine (Cyasorb UV 1084) and the nickel and calcium derivatives of bis(ethyl-3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate (Irgastab 2002 and Irganox 1425)) with other commercial additives, in the stabilisation of polypropylene film, are examined using normal and second-order derivative ultraviolet and infra-red spectroscopic techniques. It is shown that the observed behaviour is dependent on the particular additive, the processing history of the polymer and the metal chelate concerned, and is therefore highly complex. All three chelates show antagonism with a hindered piperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin 770), in unprocessed polymer, whereas one of the chelates behaves synergistically with this additive in processed samples. The chelates also show antagonism with a primary antioxidant, tris((3-(3′,5′-di-tert-butyl-4-hydroxybenzyl)-2′'-aceto-ethyl)) isocyanurate (Goodrite 3125), whereas, with a secondary antioxidant, distearyl pent-aerithrityl diphosphite (Weston 618), their behaviour is synergistic in both unprocessed and processed polymer. Two of the chelates show synergism with 2-hydroxy-4-n-octoxybenzophenone (Cyasorb UV 531), the remaining chelate showing antagonism. Mixtures containing a three-additive system show a more complex behaviour. The results are explained in terms of hydroperoxide decomposition, inhibition, stabiliser dispersion, ultraviolet stability and additive compatibility. 相似文献
18.
Tay-Yean Lin Charles A. Kingsbury Jules Adelfang Norman H. Cromwell 《Journal of heterocyclic chemistry》1985,22(4):1017-1020
The synthesis and spectral characteristics of certain bis(1-alkyl-3-phenyl-2-aziridinyl)ketones are reported. The reactions of 1,2,4,5-tetrabromo-1,5-diphenyl-3-pentanone ( 2 ) with primary amines are assumed to have a mechanism similar to that of a simple dibromo-ketone. The so-called cis, cis- or trans, trans-configurations of the bis-aziridinylketones were determined by 1H and 13C nmr spectra. 相似文献
19.
Synthesis of 9-methyl-1H-[1,4]thiazino[3,2-g]quinoline-2,5,10(3H)-trione (4), from N-(4-bromo-2,5-dimethoxyphenyl)acetamide (23) is described. Oxidative cyclisation of 2,2'-disulfanediylbis[N-(2,5-dimethoxyphenyl)acetamide] (19) to 5,8-dimethoxy-2H-1,4-benzothiazin-3(4H)-one (7b) is also reported. 相似文献
20.
Okamura WH Zhu GD Hill DK Thomas RJ Ringe K Borchardt DB Norman AW Mueller LJ 《The Journal of organic chemistry》2002,67(5):1637-1650
Isotope-labeled drug molecules may be useful for probing by NMR spectroscopy the conformation of ligand associated with biological hosts such as membranes and proteins. Triple-labeled [7,9,19-(13)C(3)]-vitamin D(3) (56), its 25-hydroxylated and 1 alpha,25-dihydroxylated metabolites (58 and 68, respectively), and other labeled materials have been synthesized via coupling of [9-(13)C]-Grundmann's ketone 39 or its protected 25-hydroxy derivative 43 with labeled A ring enyne fragments 25 or 26. The labeled CD-ring fragment 39 was prepared by a sequence involving Grignard addition of [(13)C]-methylmagnesium iodide to Grundmann's enone 28, oxidative cleavage, functional group modifications leading to seco-iodide 38, and finally a kinetic enolate S(N)2 cycloalkylation. The C-7,19 double labeling of the A-ring enyne was achieved by the Corey-Fuchs/Wittig processes on keto aldehyde 11. By employing these labeled fragments in the Wilson-Mazur route, the C-7,9,19 triple-(13)C-labeled metabolites 56, 58, and 68 as well as other (13)C-labeled metabolites have been prepared. In an initial NMR investigation of one of the labeled metabolites prepared in this study, namely [7,9,19-(13)C(3)]-25-hydroxyvitamin D(3) (58), the three (13)C-labeled carbons of the otherwise water insoluble steroid could be clearly detected by (13)C NMR analysis at 0.1 mM in a mixture of CD(3)OD/D(2)O (60/40) or in aqueous dimethylcyclodextrin solution and at 2 mM in 20 mM sodium dodecyl sulfate (SDS) aqueous micellar solution. In the SDS micellar solution, a double half-filter NOESY experiment revealed that the distance between the H(19Z) and H(7) protons is significantly shorter than that of the corresponding distance calculated from the solid state (X-ray) structure of the free ligand. The NMR data in micelles reveals that 58 exists essentially completely in the alpha-conformer with the 3 beta-hydroxyl equatorially oriented, just as in the solid state. The shortened distance (H(19Z))-H(7)) in micellar solutions as compared to that in the solid state is most easily rationalized on the basis that the 5(10)-torsion angle in 58 is decreased in micellar solutions as compared to that in the solid state. 相似文献