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111.
Masahiro Kojima Prof. Dr. Motomu Kanai 《Angewandte Chemie (International ed. in English)》2016,55(40):12224-12227
Catalytic acceptorless dehydrogenation is an environmentally benign way to desaturate organic compounds. This process is traditionally accomplished with transition‐metal‐based catalysts. Herein, a borane‐catalyzed, metal‐free acceptorless dehydrogenation of saturated N‐heterocycles is disclosed. Tris(pentafluorophenyl)borane was identified as a versatile catalyst, which afforded several synthetically important N‐heteroarenes in up to quantitative yield. Specifically, the present metal‐free catalytic system exhibited a uniquely high tolerance toward sulfur functionalities, and demonstrated superior reactivity in the synthesis of benzothiazoles compared to conventional metal‐catalyzed systems. This protocol can thus be regarded as the first example of metal‐free acceptorless dehydrogenation in synthetic organic chemistry. 相似文献
112.
Masahito Segi Katsuhiko Tanno Masumi Kojima Mitsunori Honda Tadashi Nakajima 《Tetrahedron letters》2007,48(13):2303-2306
1,3-Dipolar cycloaddition between aromatic selenoaldehydes, generated by thermal retro Diels-Alder reaction of anthracene cycloadducts, and nitrile oxides or nitrile imines proceeded efficiently to give the corresponding [3+2] cycloadducts as a single isomer in good yields, being 1,4,2-oxaselenazoles or 1,3,4-selenadiazoles, respectively. 相似文献
113.
Masaru Kojima 《Tetrahedron letters》2007,48(25):4431-4436
A new fluorous benzylidene acetal protecting group was regioselectively introduced into carbohydrates, deprotected under acidic conditions, and reused. Oligosaccharides were synthesized via regioselective conversion of the fluorous acetal group to the benzyl group by traditional reaction conditions. The fluorous compounds were easily separated from non-fluorous by-products by fluorous solid phase extraction. 相似文献
114.
Using temperature-modulated
differential scanning calorimetry, the melting behaviour of poly(oxytetramethylene)-alt-(aromatic oligoamide) (POTM-alt-AOA)
has been studied in comparison with that of polyoxytetramethylene glycohols
(POTMGs). The apparent melting temperature of the block copolymers is found
to be less than that of the corresponding POTMGs by approximately 30°C.
The relaxation time of melting of a POTM segment has been estimated and compared
with that of POTMG. The relaxation time of POTM-alt-AOA
is slightly shorter than that of POTMG when the molar mass of the POTM segment
is 2900; however, it is longer when the molar mass is 1400. 相似文献
115.
The public and governmental awareness regarding more sustainable products have gained significant momentum in the last decade and are directing the future research of the next generation of materials and processes. In such a setting, biodegradable polymers are regarded as one of the technologies driving the innovation and current market growth because they provide an additional end of life option. Tracing the evolving trends of these emerging technologies will help researchers, investors, and policy makers to better evaluate the opportunities of the technology as well as to understand the technology's changing characteristics. Therefore, within this study, we perform bibliographic analyses based on patent information to delineate the current research landscape and to anticipate the future development trends by focusing on the cases of poly(lactic acid) (PLA), poly(hydroxyalkanoates) (PHAs), polycaprolactone (PCL), poly(butylene succinate) (PBS), and poly(butylene adipate-co-terephthalate) (PBAT). The following findings were made: First, PLA gets the highest attention from both academia and industry. Second, the overall international presence of biodegradable polymer patents is high, especially in the field of PHAs. Third, technology maturity and technology strength show that PLA is the most promising technology at present in technological terms, whereas PHAs, PCL, and PBS are uncertain technologies and PBAT has a rather low development potential. 相似文献
116.
N-Benzyl-D-glucamine dithiocarbamate (BGD), N-p-hydroxymethylbenzyl-D-glucamine dithiocarbamate (HBGD), and N-p-carboxybenzyl-D-glucamine dithiocarbamate (CBGD) were compared for their relative efficacies in the distribution and excretion of cadmium in mice exposed to cadmium. Mice were injected intraperitoneally with 109CdCl2 (1 mg of Cd/kg and 2 microCi of 109Cd/one animal). Three days later, they were injected with chelating agents (400 mumol/kg) every other day for 2 weeks. After injections of BGD and HBGD, cadmium was excreted mainly in the feces through the bile, and the fecal excretion of cadmium by HBGD was significantly higher than that by BGD or CBGD. These chelating agents increased the urinary excretion of cadmium to a small extent. The hepatic cadmium content was decreased only after HBGD injection. Also, the injection of HBGD caused a much greater decrease in renal cadmium content than did BGD or CBGD. These chelating agents did not result in the redistribution of cadmium to the brain, testes, or heart. The growth of mice was only slightly retarded by injections of these chelating agents. The results of this study indicate that the injection of HBGD to mice pretreated with cadmium can remove cadmium from the body, mainly through fecal excretion, without redistribution of cadmium to other tissues such as the brain, testes, and heart, more effectively than BGD or CBGD. 相似文献
117.
Hideo Kojima Kazuyoshi Ozaki Noboru Matsumura Hiroo Inoue 《Journal of heterocyclic chemistry》1990,27(6):1845-1846
7-Substituted 2,3-bis(isopropylthio)naphth[1,8-bc]azepines 3a-c were synthesized in good yields by the reactions of 5-substituted 1-naphthylamines 2a-c with tris(isopropylthio)cyclopropenylium perchlorate ( 1 ) in acetonitrile under reflux. This reaction proceeds through the facile ring opening of 1 , followed by the intermediary formation of iminium salts 5a-c and then intramolecular cyclization. 相似文献
118.
T. Nakamura S. Kojima T. Ohta M. Nishida A. Rakowski A. Ikeda H. Oda E. Niu 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(2):327-332
14C variations of atmospheric CO2 as well as carbonaceous fraction of living materials, such as collagen from tooth and bone, tissue, skin, hair, nail, etc.,
of modern humans are influenced by 14C produced artificially by nuclear bomb tests in the atmosphere from late 1950s to early 1960s. By careful investigation of
14C concentration of tree rings and human body samples formed in this time intervals, we can establish a relationship of their
14C concentrations with calendar year. By applying this relation to a sample whose 14C concentration can be measured, we can estimate the formation age of the sample. In addition, sources of the chemicals that
were used in some criminal cases can be possibly identified, by their carbon isotope ratios (13C/12C and 14C/12C). This method of age determination has been applied to a forensic study, i.e., two criminal cases of murder. For each case,
by comparing the measured 14C abundances of several pieces of hair and one tooth (the third molar) from the body with the annual change on concentrations
of bomb-produced 14C, the time of death of the body and the age of the victim were estimated. The estimated values were consistent with the real
ones that were revealed by the confession of the real murderers. 相似文献
119.
Fluorescence excitation, multiphoton ionization, and dispersed fluorescence spectra of bare and hydrogen-bonded 2-fluoropyridine with water were measured in a supersonic free jet. For bare 2-fluoropyridine, fluorescence quantum yield decrease in the higher vibronic levels was observed even under collision-free conditions. The inter-system crossing channel was probed experimentally by two color R2PI and found to be negligible. The non-radiative relaxation process of 2-fluoropyridine is mainly governed by the relaxation to the electronic ground state. Electronic spectra of 2-fluoropyridine-(water)(n) (n=1 approximately 3) were also obtained. The hydrogen bond formation with water increases the quantum yield in the higher vibronic levels. Rather low frequency vibrations were observed in the hole burning spectrum of bare 2-fluoropyridine; however, these vibronic bands disappeared with the hydrogen bond formation with water. The appearance of low frequency vibronic bands observed for bare 2-fluoropyridine is ascribed to the existence of closely lying (n,pi) state. 相似文献
120.
1. Introduction As an effective utilization of methane, the methane dehydro-aromatization was focused in the last decade [1-28]. Over the Mo/HZSM-5 bi- functional catalyst at high reaction temperature, methane can be converted into light aromatics (ben- zene and naphthalene) and hydrogen. Mo active species can activate the C—H bond of methane; and HZSM-5 supplies the acid sites for the oligomeriza- tion and cyclization of hydrocarbons to form aromat- ics, and suppresses the deeper condens… 相似文献