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991.
Thomas Marmin Prof. Yves L. Dory 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(27):6707-6711
Cyclohexane and cyclotri-β-alanyl have been used as scaffolds for the design of new C3-symmetric rings incorporating conjugated alkenes and dienes. All three C3-symmetric lactams share the same triangular shape and their crystal system is trigonal. They all belong to the R3 space group, R3m, R3 and R3c, for the increasingly large 12-, 18- and 24-membered rigid rings, respectively. All lactams stack on top of each other, through H-bonds and van der Waals noncovalent interactions, leading to endless supramolecular cylinders and tubes. The largest member of the family leads to tubes, the central pores of which is wide enough to let water in. A common feature of all the lactams is their very large dipole, of around 9 D, according to DFT calculations. Surprisingly, all the resulting cylinders and tubes pack side by side in the crystals, with all the dipoles pointing to the same direction. As a result, all three crystals are anisotropic and appear to be the first members of a new kind of highly polar crystals. 相似文献
992.
Dr. Mick Hornum Julie Stendevad Dr. Pawan K. Sharma Dr. Pawan Kumar Rasmus B. Nielsen Dr. Michael Petersen Dr. Poul Nielsen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7387-7395
Nucleotides that contain two nucleobases (double-headed nucleotides) have the potential to condense the information of two separate nucleotides into one. This presupposes that both bases must successfully pair with a cognate strand. Here, double-headed nucleotides that feature cytosine, guanine, thymine, adenine, hypoxanthine, and diaminopurine linked to the C2′-position of an arabinose scaffold were developed and examined in full detail. These monomeric units were efficiently prepared by convergent synthesis and incorporated into DNA oligonucleotides by means of the automated phosphoramidite method. Their pairing efficiency was assessed by UV-based melting-temperature analysis in several contexts and extensive molecular dynamics studies. Altogether, the results show that these double-headed nucleotides have a well-defined structure and invariably behave as functional dinucleotide mimics in DNA duplexes. 相似文献
993.
Dr. Soichiro Ogi Natsumi Fukaya Dr. Arifin Bastian Bjerkem Skjelstad Dr. Yuh Hijikata Prof. Dr. Shigehiro Yamaguchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7303-7307
The self-assembly of an amide-functionalized dithienyldiketopyrrolopyrrole (DPP) dye in aqueous media was achieved through seed-initiated supramolecular polymerization. Temperature- and time-dependent studies showed that the spontaneous polymerization of the DPP derivative was temporally delayed upon cooling the monomer solution in a methanol/water mixture. Theoretical calculations revealed that an amide-functionalized DPP derivative adopts an energetically favorable folded conformation in the presence of water molecules due to hydration. This conformational change is most likely responsible for the trapping of monomers in the initial stage of the cooperative supramolecular polymerization in aqueous media. However, the monomeric species can selectively interact with externally added fragmented aggregates as seeds through concerted π-stacking and hydrogen-bonding interactions. Consequently, the time course of the supramolecular polymerization and the morphology of the aggregated state can be controlled, and one-dimensional fibers that exhibit a J-aggregate-like bathochromically shifted absorption band can be obtained. 相似文献
994.
Dr. Ritesh Haldar Kamal Batra Stefan Michael Marschner Dr. Agnieszka B. Kuc Dr. Stefan Zahn Prof. Dr. Roland A. Fischer Prof. Dr. Stefan Bräse Prof. Dr. Thomas Heine Prof. Dr. Christof Wöll 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7847-7851
In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties. 相似文献
995.
Anwar Jacintomoreno Dr. Hemant K. Sharma Dr. Alejandro Metta-Magaña Prof. Dr. Keith H. Pannell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(48):11302-11307
The reactions of the Mannich reagent Et3SiOCH2NMe2 ( 1 ) with a variety of anilines (mono-substituted RC6H4NH2, R=H, 4-CN, 4-NO2, 4-Ph, 4-Me, 4-MeO, 4-Me2N; di-substituted R2C6H3NH2, R2=3,5-(CH3)2, 3,5-(CF3)2; tri-substituted R3C6H2NH2, R3=3,5-Me2-4-Br and a “super bulky” aniline (Ar*NH2) [Ar*=2,6-bis(diphenylmethyl)-4-tert-butylphenyl]) led to the formation of a range of products dependent upon the substituent. With electron-withdrawing substituents, previously unknown diamines, RC6H4NH(CH2NMe2) [R=CN ( 2 a ), NO2 ( 2 b )] and R2C6H3NH(CH2NMe2) [R2=3,5-(CF3)2 ( 2 c) ] were formed. Further reaction of 2 a , b , c with 1 yielded the corresponding triamines RC6H4N(CH2NMe2)2 (R=CN ( 3 a ), NO2 ( 3 b ) and R2C6H3N(CH2NMe2)2, R2=3,5-(CF3)2 ( 3 c ). The new polyamines were characterized by NMR spectroscopy, and for 2 a , 2 c , and 3 c , by single crystal XRD. In the case of electron-donating groups, R=4-OMe, 4-NMe2, 4-Me, 3,5-Me2, 3,5-Me2-4-Br, and for R=4-Ph, the reactions with 1 immediately led to the formation of the related 1,3,5-triazines, R=4-MeO ( 5 a ), 4-Me2N ( 5 b ), 4-Me ( 5 c ), 3,5-Me2 ( 5 d ), 3,5-Me2-4-Br ( 5 e ), 4-Ph ( 5 f ), 4-Cl ( 5 g ). The “super bulky” aniline rapidly produced a single product, namely the corresponding imine Ar*N=CH2 ( 4 ) which was also characterized by single crystal XRD. Imine 4 is both thermally and oxidatively stable. All reactions are very fast, thus based upon the presence of Si we are tempted to denote the reactions of 1 as examples of “Silick” chemistry. 相似文献
996.
Dr. Masaru Kondo Dr. Shinobu Takizawa Yuzhao Jiang Prof. Dr. Hiroaki Sasai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(42):9866-9869
The Mills reaction and cyclization of readily available 2-aminobenzyl alcohols and nitrosobenzenes using thionyl bromide provided 2H-indazoles in up to 88 % yields. In the metal-free process, acetic acid played a crucial role for the both Mills reaction and cyclization. A brominated 2H-indazole could also be obtained through the one-pot sequence. 相似文献
997.
Richard Böser Lars Denker Dr. René Frank 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(45):10575-10579
Benzyl-substituted boronates and borates are widely employed as mild sources in radical or anionic transfer reactions of benzyl entities. In this process the B−C bond to the benzyl moiety is essentially ruptured. In contrast, reactions with retention of the B−C bond are poorly investigated although several other reactive sites in benzyl–boron systems are clearly inherent. In this respect, the novel reactivity of the representative borane adduct IiPr−BH2Bn [IiPr=:C{N(iPr)CH}2, Bn=CH2C6H5] is demonstrated. Dihalogenation of the BH2 entity is observed with BCl3 and BBr3, whereas BI3 either affords IiPr−BHI2 or proceeds with borylation of the aromatic phenyl ring to give a hydride-bridged bisborylated species. The photochemical mono- and dihalogenation of the benzylic CH2 group was demonstrated with elemental bromine Br2. The brominated product IiPr−BBr2−CHBr−C6H5 was borylated at the benzylic carbon atom in an umpolung event with BI3 to afford the zwitterion IiPr−BI−CH(BI3)−C6H5. 相似文献
998.
Martín Soto Dr. Raquel G. Soengas Prof. Artur M. S. Silva Prof. Vicente Gotor-Fernández Prof. Humberto Rodríguez-Solla 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(57):13104-13108
In this work, the first example of a radical stereodivergent reaction directed towards the stereoselective synthesis of both (R*,R*)- and (R*,S*)-2,2′-biflavanones promoted by samarium diiodide is reported. Control experiments showed that the selectivity of this reaction was exclusively controlled by the temperature. It was possible to generate a variety of 2,2′-biflavanones bearing different substitution patterns at the aromatic ring in good-to-quantitative yields, being both stereoisomers of the desired compounds obtained with total or high control of selectivity. A mechanism that explains both the generation of the corresponding 2,2′-biflavanones and the selectivity is also discussed. The structure and stereochemistry determination of each isomer was unequivocally elucidated by single-crystal X-ray diffraction experiments. 相似文献
999.
Junko Hirota Dr. Kazuteru Usui Dr. Yasufumi Fuchi Masaomi Sakuma Shota Matsumoto Ryusuke Hagihara Prof. Dr. Satoru Karasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(65):14943-14952
Water-soluble donor–acceptor-type fluorophore 15Nap-Cl having two trifluoromethyl groups and a Cl group on a 1,5-aminonaphthyridine framework was prepared. Fluorophore 15Nap-Cl showed strong solvatochromic fluorescence, and, as the solvent polarity increased, a bathochromic shift was observed accompanied by an increase in the fluorescence quantum yield. In addition, in the presence of amines such as ethylamine, diethylamine, and aniline, further considerable bathochromic shifts in the fluorescence were observed. Density functional calculations identified the source of the fluorescence behavior as exciplex formation between 15-Nap-Cl and the corresponding amine. The fluorescence behavior was exploited to fabricate a sensor that can identify various primary, secondary, and tertiary amines. 相似文献