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41.
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Pd‐initiated polymerization of diazo compounds bearing dialkoxyphosphinyl group and hydrolysis of the resulting polymers and oligomers to afford phosphonic acid‐containing products
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Hiroaki Shimomoto Akira Oda Motoki Kanayama Tomoya Sako Tomomichi Itoh Eiji Ihara Naohiro Hoshikawa Akihiko Koiwai Naoki Hasegawa 《Journal of polymer science. Part A, Polymer chemistry》2016,54(12):1742-1751
Pd‐initiated polymerization and oligomerization of diazo compounds containing a dialkoxyphosphinyl group are described. Polymerization of 2‐dialkoxyphosphinylethyl diazoacetates with π‐allylPdCl‐based initiating systems afforded C? C main chain polymers bearing phosphonate on each main chain carbon atom. The quantitative transformation of the side chain phosphonate to phosphonic acid resulted in the formation of water soluble polymers having the acid groups accumulated around their main chains, although the carbonyl ester linkage in the side chain was cleaved via intramolecular acid‐assisted hydrolysis in water at 80 °C. Pd‐initiated oligomerization of diethyl diazomethylphosphonate yielded an oligomeric product bearing diethoxyphosphiny groups directly attached to its main chain carbons, with unexpected incorporation of azo group in the main chain framework. Hydrolysis of the phosphonate of the oligomer afforded a water‐soluble product, which was revealed to show higher proton conductivity than poly(vinylphosphonic acid) under certain conditions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1742–1751 相似文献
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Mitsuji Yamashita Lakonda Nagaprasada Rao Valluru Krishna Reddy Motoki Maeda Tatsuo Oshikawa Masaki Takahashi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1661-1665
Novel pentofuranose analogs of phospha sugar derivatives were synthesized starting from 1-phenyl-2-phospholene 1-oxide ( 1 ). First, the allylic oxidation of 1-phenyl-2-phospholene 1-oxide ( 1 ) with CrO 3 in Ac 2 O-AcOH or 3-hydroxy-1-phenyl-2-phospholene ( 2 ) with MnO 2 afforded 1-phenyl-4-oxo-2-phospholene 1-oxide ( 3 ). The C-5 alkylation of 3 in the presence of NaH by using benzyl bromide or methyl iodide as electrophiles afforded the target title compounds. 相似文献
46.
The formation of carbon-carbon bond by sulfur extrusion such as pyrolysis of cyclic sulfones is well known as an important synthetic method, especially for the synthesis of cyclophane framework.1) Little is known about selenium extrusion as the counterpart, though organoseleniums have been properly appreciated as a useful tool for manipulating a functional group.2) Lardon reported that the thermal decomposition of dibenzyl diselenide led to a mixture of dibenzyl selenide and polyselenides.3) In contrast, recent reports showed that at 210°C, heating bis(diphenylmethyl) diselenide resulted in ready selenium extrusion to 1,1,2,2-tetraphenylethane4), and dianthrylmethyl mono- and diselenides to 1,2-dianthrylethane.5) Therefore,- it is worthwhile to study the thermal behavior of dibenzyl selenide itself. 相似文献
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Despite the fact that many transition-metal-catalyzed reactions of organosulfur compounds with internal alkynes are ineffective, cobalt carbonyl (Co2(CO)8) is an excellent catalyst for carbonylative cyclization of internal alkynes with carbon monoxide. When Co2(CO)8-catalyzed reactions of internal alkynes with organic thiols are conducted in acetonitrile under 4 MPa pressure of carbon monoxide, thiolative lactonization of internal alkynes successfully takes place with incorporation of two molecules of CO. This carbonylation provides a useful tool to prepare the corresponding α,β-unsaturated γ-thio-γ-lactones (butenolide derivatives) in good yields. In the cases of unsymmetrical alkynes, such as 2-octyne and 6-methyl-2-heptyne, the thiolative lactonization proceeds with moderate regioselectivity to give the butenolide derivatives on which the carbonyl group preferentially bonds to the less hindered acetylenic carbon. Mechanistic pathways about the present thiolative lactonization are also discussed. 相似文献
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The anomalous temperature dependence of the sign of the spontaneous polarization in a biphenyl ester series of ferroelectric liquid crystals is reported. The reversal of the sign of the spontaneous polarization in the chiral smectic C phase of 2MBNCBC ((S)-2′-methylbutyl-4′-n- nonylcarbonyloxy-(l,l′-biphenyl)-l-carboxylate) is observed at T m. This anomaly is studied in detail as functions of the length of the terminal alkyl chain, the applied electric field, the frequency and the applied hydrostatic pressure. T m has been confirmed to depend on the length of the terminal chain and the applied pressure. However, it is independent of the applied field and the measuring frequency. In the mixture of these compounds, this anomaly is also observed. 相似文献
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Based on the fact that anthracene (Anth) possesses much higher similarity in electron-releasing ability to porphyrin nucleus than the other polyacenes, the dimeric octaethylporphyrin (OEP) derivatives 4 and 5 (OEP–Anth–OEP) were synthesized and their structure–property relationships were examined, as compared with related OEP dimers 1–3. Among them, the derivative 4 showed enormously high electronic communication between two terminal OEP rings, potentially providing a suitable unit of the electronic structure for molecular design of the OEP devices operating with less energy and with higher sensitivity to outside stimuli. 相似文献
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Drutskoy A Abe K Abe K Adachi I Aihara H Anipko D Arinstein K Aulchenko V Aushev T Banerjee S Barberio E Barbero M Bedny I Belous K Bitenc U Bizjak I Blyth S Bondar A Bozek A Bracko M Brodzicka J Browder TE Chang P Chao Y Chen A Chen KF Chen WT Cheon BG Chistov R Choi Y Choi YK Chuvikov A Cole S Dalseno J Danilov M Dash M Dragic J Eidelman S Epifanov D Fratina S Gabyshev N Gershon T Go A Gokhroo G Goldenzweig P Golob B Ha H Haba J Hara T Hayasaka K Hayashii H Hazumi M Heffernan D Higuchi T 《Physical review letters》2007,98(5):052001
The inclusive production of D(s), D(0), and J/psi mesons is studied using a 1.86 fb(-1) data sample collected on the Upsilon(5S) resonance with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. The number of bb events in this Upsilon(5S) data sample is determined. We measure the branching fractions B(Upsilon(5S)-->D(s)X)/2=(23.6+/-1.2+/-3.6)%, B(Upsilon(5S)-->D(0)X)/2=(53.8+/-2.0+/-3.4)%, and B(Upsilon(5S)-->J/psiX)/2=(1.030+/-0.080+/-0.067)%. From the D(s) and D(0) inclusive branching fractions the ratio f(s)=(18.0+/-1.3+/-3.2)% of B(s)(*)B(s)(*) to the total bb quark pair production at the Upsilon(5S) energy is obtained in a model-dependent way. 相似文献