全文获取类型
收费全文 | 915篇 |
免费 | 33篇 |
国内免费 | 5篇 |
专业分类
化学 | 692篇 |
晶体学 | 6篇 |
力学 | 19篇 |
数学 | 78篇 |
物理学 | 158篇 |
出版年
2023年 | 4篇 |
2022年 | 5篇 |
2021年 | 20篇 |
2020年 | 13篇 |
2019年 | 20篇 |
2018年 | 16篇 |
2017年 | 14篇 |
2016年 | 21篇 |
2015年 | 20篇 |
2014年 | 22篇 |
2013年 | 40篇 |
2012年 | 49篇 |
2011年 | 69篇 |
2010年 | 37篇 |
2009年 | 21篇 |
2008年 | 59篇 |
2007年 | 47篇 |
2006年 | 60篇 |
2005年 | 56篇 |
2004年 | 61篇 |
2003年 | 64篇 |
2002年 | 41篇 |
2001年 | 12篇 |
2000年 | 13篇 |
1999年 | 10篇 |
1998年 | 9篇 |
1997年 | 8篇 |
1996年 | 7篇 |
1995年 | 8篇 |
1994年 | 5篇 |
1993年 | 4篇 |
1992年 | 9篇 |
1991年 | 3篇 |
1990年 | 8篇 |
1989年 | 9篇 |
1988年 | 8篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 9篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1979年 | 11篇 |
1978年 | 8篇 |
1977年 | 9篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1970年 | 1篇 |
1968年 | 2篇 |
排序方式: 共有953条查询结果,搜索用时 15 毫秒
11.
Kazuaki Ito Akane Suzuki Naoto Ito Hiroyuki Teraura Yoshihiro Ohba 《Journal of heterocyclic chemistry》2003,40(3):405-410
Dithia‐tetrahomodiaza‐calix[4]arenes were synthesized by the cyclization reactions of bis(3‐(chloro‐methyl)‐2‐hydroxyphenyl)sulfide with cystine peptides in moderate yields. Conformational analysis of the macrocycles by using nmr spectroscopy reveled that the cyclophanes adopt a cone‐like form as a preferable conformation and the cystine bridge moiety is incorporated in the cavity. The calixarene analogs can extract transion metals such as Zn2+ and Cu2+ ions from an aqueous phase into chloroform. 相似文献
12.
2,3,7,8-Substituted polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) and non-ortho-substituted polychlorinated biphenyls (PCBs) account for almost all of the total toxic equivalents (TEQ) in environmental samples. Activated carbon columns are used to fractionate the samples for GC-MS analysis or bioassay. Micropore-free surface-activated carbon is highly selective for PCDD/Fs and non-ortho-PCBs and can improve the conventional activated carbon column clean-up. Along with sulfuric acid-coated diatomaceous earth columns, micropore-free surface-activated carbon provides a rapid, robust, and high-throughput sample preparation method for PCDD/Fs and non-ortho-PCBs analysis. 相似文献
13.
The photoisomerization properties of tris(bipyridine)cobalt complexes containing six or three azobenzene moieties, namely, [Co(II)(dmAB)3](BF4)2 [dmAB = 4,4'-bis[3'-(4'-tolylazo)phenyl]-2,2'-bipyridine], [Co(III)(dmAB)3](BF4)3, [Co(II)(mAB)3](BF4)2 [mAB = 4-[3' '-(4' '-tolylazo)phenyl]-2,2'-bipyridine], and [Co(III)(dmAB)3](BF4)3, derived from the effect of gathering azobenzenes in one molecule and the effect of the cobalt(II) or cobalt(III) ion were investigated using UV-vis absorption spectroscopy, femtosecond transient spectroscopy, and 1H NMR spectroscopy. In the photostationary state of these four complexes, nearly 50% of the trans-azobenzene moieties of the Co(II) complexes were converted to the cis isomer, and nearly 10% of the trans-azobenzene moieties of the Co(III) complexes isomerized to the cis isomer, implying that the cis isomer ratio in the photostationary state upon irradiation at 365 nm is controlled not by the number of azobenzene moieties in one molecule but rather by the oxidation state of the cobalt ions. The femtosecond transient absorption spectra of the ligands and the complexes suggested that the photoexcited states of the azobenzene moieties in the Co(III) complexes were strongly deactivated by electron transfer from the azobenzene moiety to the cobalt center to form an azobenzene radical cation and a Co(II) center. The cooperation among the photochemical structural changes of six azobenzene moieties in [Co(II)(dmAB)3](BF4)2 was investigated with 1H NMR spectroscopy. The time-course change in the 1H NMR signals of the methyl protons indicated that each azobenzene moiety in [Co(II)(dmAB)3](BF4)2 isomerized to a cis isomer with a random probability of 50% and without interactions among the azobenzene moieties. 相似文献
14.
Kakiuchi F Tsuchiya K Matsumoto M Mizushima E Chatani N 《Journal of the American Chemical Society》2004,126(40):12792-12793
Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes involving triethyl-, dimethylphenyl-, tert-butyldimethyl-, and triphenylsilanes can be used as a silylating reagent. Coordination of an sp2 nitrogen atom to the ruthenium complex is important for achieving this silylation reaction. 相似文献
15.
Danuta Frackowiak Mamoru Minuro Iwao Yamazaki† Naoto Tamai† Yoshihiko Fujita 《Photochemistry and photobiology》1989,50(4):563-570
–Time-resolved fluorescence spectra in the ps time range were measured on phycobilisome (PBS) embedded in poly(vinyl alcohol) films. The cyanobacterium Tolypothrix tenuis was used as a source of PBS because the pigment composition and the structure of the PBS are well defined. Isotropic PBS in the unstretched film and PBS uniaxially oriented in the stretched film were investigated. Diameters of PBS hemidiscs were oriented parallel to the film-stretching direction. The time-resolved fluorescence spectra of the unstretched sample and of the two polarized components in the stretched samples showed several differences in the rise and decay. The delay time, estimated from the time span between the maximum laser pulse and maximal intensity of the phycocyanin and allophycocyanin fluorescence, was much longer than that reported in the aqueous media. This suggests occurrence of a higher thermal deactivation of PBS in polymer film than in aqueous media. The excitation energy transfer from excited phycocrythrin to allophycocyanin was more efficient in the unstretched than in the stretched samples, and it was greater in the parallel polarized component of the stretched sample than in the perpendicular component. The present results are in agreement with a previous suggestion which states that there are two independent pathways of excitation energy transfer in PBS and that there is more than one final emitter of fluorescence. The molecules taking part in various pathways of energy transfer differ in their orientation within PBS. 相似文献
16.
Ishikawa N Sugita M Tanaka N Ishikawa T Koshihara SY Kaizu Y 《Inorganic chemistry》2004,43(18):5498-5500
An alternating-current (ac) magnetic susceptibility measurement for the [(Pc)(2)Tb(III)](0) complex (Pc = phthalocyaninato) has shown that ligand oxidation of the anionic [(Pc)(2)Tb(III)](-) complex gives rise to a significant upward shift of the temperature range where the magnetization response shows a phase lag behind the time-varying external magnetic field. The peaks of the out-of-phase component of the ac susceptibility of the pi-radical [(Pc)(2)Tb(III)](0) were observed at 50, 43, and 36 K with ac magnetic fields of 10(3), 10(2), and 10 Hz, respectively, which were more than 10 K higher than the corresponding values of the anionic complex with a closed-shell pi-system. The ac susceptibility measurements on the complex with octa(dodecoxy)-substituted Pc ligand, which is readily dilutable in diamagnetic media, proved that the significant rise of the temperatures occurs as an intrinsic single-molecular property of the complex possessing both J = 6 and S = (1)/(2) systems, and is not due to long-range magnetic order or interactions between adjacent unpaired pi-electrons. 相似文献
17.
Kazuharu Sugawara Tatsuya Shirotori Naoto Kamiya Shunitz Tanaka 《Analytica chimica acta》2004,523(1):75-80
Formation of avidin-biotin complex was investigated using bisbiotinyl thionine (BBT) by means of voltammetric techniques. Thionine is an electroactive compound and has two amino groups that are necessary for the reaction with a biotinylation reagent. The biotinylation of thionine produces a new reagent with two biotin moieties at each end of thionine. Three BBTs of different lengths of the spacer that connects the biotin moiety to the thionine moiety were prepared. The avidin-biotin binding assay was achieved by measuring the electrode response of the thionine moiety in BBT. The binding affinity and the conformation of complex, which depended on the length of spacer, are discussed. BBT in which the spacer is shortest (BBT-S, distance between carbonyl group of the two biotin moieties: 11 Å) binds with only one avidin molecule. BBT with medium length of spacer (BBT-M, 28.8 Å) forms the complex with two avidin molecules. BBT with the longest spacer (BBT-L, 46.6 Å) allows binding with two avidin molecules as well as intramolecular binding within one avidin molecule. The affinity constants of BBT-S, BBT-M and BBT-L for avidin were estimated to be 7.0 × 1012 M−1, 3.2 × 1012 M−1 and 4.0 × 1012 M−1, respectively. 相似文献
18.
Chatani N Amako K Tobisu M Asaumi T Fukumoto Y Murai S 《The Journal of organic chemistry》2003,68(4):1591-1593
The reaction of benzofuran-2,3-dione derivatives 1 with CO and alkenes (or alkynes) results in a carbonylative [2+2+1] cycloaddition in which the ester-carbonyl group is incorporated into a two-atom assembling unit to give spirolactone derivatives 2. This reaction provides the first example of an ester-carbonyl group participating in a carbonylative cycloaddition reaction. 相似文献
19.
The dispersive component
s
d
of the surface free energy of glass fibers and its interaction energy with alkanes, benzene, 1-nitropropane, ethyleneglycol, glycerol, formamide, and water were quantitatively determined by the tensiometric method within two liquids. The values of nondispersive interaction energy I
SL
p
were found to be a linear function of the square root of the nondispersive component of the surface free energy of liquids. This suggests that the nondispersive interaction energy may be represented by the geometric mean of the nondispersive component of the surface free energy of a solid and a liquid. The slope gave the nondispersive component
s
p
of the surface free energy. The
s
p
values are 33 and 14 mJ/m2 for the untreated and aminosilane-treated fibers, respectively, suggesting that organophilic character has developed on the surface after aminosilane treatment. The
s
p
value was almost similar after the treatment, probably because of the polar characteristics of amino groups. 相似文献
20.
The reaction of alpha,beta-unsaturated imines with CO and alkenes in the presence of Ru(3)(CO)(12) as a catalyst results in a three-component coupling reaction that gives alpha,alpha-disubstituted beta,gamma-unsaturated gamma-butyrolactams. The reaction proceeds via a two-step sequence involving the initial formation of ketone derivatives by catalytic carbonylation at the beta-olefinic C-H bonds of alpha,beta-unsaturated imines, followed by the (uncatalyzed) intramolecular nucleophilic attack of the imine nitrogen on the ketonic carbon to generate a tetrahedral intermediate, which then undergoes a 1,2-ethyl migration. The reaction of a cyclic unsaturated imine, derived from the reaction of (1R)-(-)-myrtenal with tert-butylamine, gives a beta-aminocyclopentene derivative, which is formed by an aldol-type condensation of the initially formed ketone, indicating the initial formation of ethyl ketone. 相似文献