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181.
Joseph H. Chan David P. Baccanari Robert L. Tansik Christine M. Boytos Sharon K. Rudolph Andrew D. Brown Jean S. Hong Lee F. Kuyper Michael L. Jones 《Journal of heterocyclic chemistry》1997,34(1):145-151
A series of novel 1,3-diamino-7,8,9,10-tetrahydropyrido[3,2-f]quinazolines were synthesized starting from 6-amino-5-cyanoquinoline (4). These compounds inhibited Candida albicans dihydrofolate reductase with Ki values of ≤0.60 aM. One analogue exhibited moderate in vivo efficacy in a C. albicans-infected mouse model. 相似文献
182.
A series of eight dimethoxybenziporphyrins were prepared in three steps from 1,3-dimethoxybenzene or 2,6-dimethoxytoluene. Dibromination, followed by lithium-halogen exchange and reaction with benzaldehyde gave dicarbinol intermediates. These reacted with pyrrole and aryl aldehydes in the presence of BF3.Et2O in chloroform, followed by oxidation with DDQ, to give the benziporphyrins in 15-25% yield. These compounds readily gave nickel(II) and palladium(II) organometallic derivatives and could be selectively reduced with sodium borohydride to give unstable benziphlorins. Regioselective oxidation with silver acetate afforded the related 22-acetoxybenziporphyrins in 52-64% yield. The dimethoxybenziporphyrins showed chemical shifts by proton NMR spectroscopy that were consistent with weakly diatropic macrocycles. However, addition of TFA gave dications that showed far more significant shifts that are attributed to the presence of a more substantial diatropic ring current. The internal CH for 11H2(2+) was observed at 3.5 ppm, but this effect was diminished for the 3-methylbenziporphyrins 12H2(2+) where this resonance appears at 4.7 ppm. Even in the absence of the methoxy substituents, the dication derived from tetraphenylbenziporphyrin 8H2(2+) shows an upfield shift for this resonance to 5.5 ppm. The dications of the 22-acetoxybenziporphyrins also show similar effects despite the presence of an internal ester moiety. These results demonstrate that a spectrum of diatropic character can manifest even in highly crowded benziporphyrin derivatives. 相似文献
183.
Rosseto R Bibak N DeOcampo R Shah T Gabrielian A Hajdu J 《The Journal of organic chemistry》2007,72(5):1691-1698
A new stereoselective synthesis of lysophosphatidylcholines is reported. The synthesis is based upon (1) the use of 3-p-toluenesulfonyl-sn-glycerol to provide the stereocenter for construction of the optically active lysophospholipid molecule, (2) tetrahydropyranylation of the secondary alcohol function to achieve orthogonal protection of the sn-2- and sn-3-glycerol positions, and (3) elaboration of the phosphodiester headgroup using a 2-chloro-1,3,2-dioxaphospholane/trimethylamine sequence. In the course of developing the synthesis it has been discovered that methoxyacetate displacement of the sn-3-p-toluenesulfonate yields a reactive methoxyacetyl ester, which in turn can be selectively cleaved with methanol/tert-butylamine, while the ester group at the sn-1-position remains unaffected. The sequence has been shown to be suitable for preparation of spectroscopically labeled lysophosphatidylcholines. One of these compounds was readily converted to a double-labeled mixed-chain phosphatidylcholine applicable for real-time fluorescence resonance energy transfer (FRET) assay of lipolytic enzymes. In addition, the work led to new synthetic strategies based on chemoselective manipulation of the tosyl group in the presence of other base-labile groups such as FMOC derivatives that are often used for the protection of amino and hydroxyl groups in syntheses. 相似文献
184.
Sametband M Shweky I Banin U Mandler D Almog J 《Chemical communications (Cambridge, England)》2007,(11):1142-1144
Two different types of nanoparticles dissolved in organic solution, gold stabilized by n-alkanethiols and CdSe/ZnS stabilized by n-alkane-amine, adhere preferentially to the ridges of latent fingerprints; the gold deposits catalyze silver electroless deposition from "Silver Physical Developer" (Ag-PD), an aqueous solution containing silver colloids stabilized by cationic surfactants, to form dark impressions of the ridge details; the hydrophobic capped gold nanoparticles significantly improve the intensity and clarity of the developed prints compared with Ag-PD alone; finger marks treated with CdSe/ZnS nanoparticles can be viewed directly, due to their fluorescence under UV illumination. 相似文献
185.
186.
Surface modification of cetyltrimethylammonium bromide-capped gold nanorods to make molecular probes
Yu C Varghese L Irudayaraj J 《Langmuir : the ACS journal of surfaces and colloids》2007,23(17):9114-9119
A chemical procedure to replace the cetyltrimethylammonium bromide (CTAB) cap on gold nanorods (GNRs) fabricated through seed-mediated growth with organothiol compounds [3-animo-5-mercapto-1,2,4-triazole (AMTAZ) and 11-mercaptoundecaonic acid (MUDA)] was developed to reduce the cytotoxity of GNRs and facilitate further biofunctionalization. Compared to phosphatidylcholine (PC) modification, our procedure yields stable GNRs that are biocompatible and suitable for whole-cell studies. The PC-, AMTAZ-, and MUDA-activated GNRs all showed low cytotoxicity. By choosing different organothiols, net positive or negative charges could be created on the nanorod surface, for different applications. Gold nanorod molecular probes (GNrMPs) were fabricated by subsequent attachment of antibodies to the activated GNRs and were used to visualize and detect cell surface biomarkers in normal and transformed human breast epithelial cells, demonstrating the potential of developing novel biosensors using gold nanorods. The sensitivity of GNrMPs made from organothiol-activated GNRs is considerably higher than that of CTAB/PC-activated GNRs, demonstrating that the protocol reported here is favored in developing molecular probes using GNRs. 相似文献
187.
Bla Ivn Joseph P. Kennedy Tibor Kelen Ferenc Tüdos 《Journal of polymer science. Part A, Polymer chemistry》1981,19(3):679-685
Colorless poly(vinyl chloride)s (PVC) containing up to 1.6 allylic chlorines per molecule have been prepared by controlled random dehydrochlorination with a strong base. The effect of temperature in the ?50 to +24°C range on the number of allylic chlorines and color of PVC has been investigated by ozonization experiments and UV–visible spectroscopy. A two-parameter kinetic model has been developed which quantitatively accounts for the observations and points the way for further research. 相似文献
188.
The thermal decomposition of peroxy acetyl nitrate (PAN) is investigated by low pressure flash thermolysis of PAN highly diluted in noble gases and subsequent isolation of the products in noble gas matrices at low temperatures and by density functional computations. The IR spectroscopically observed formation of CH3C(O)OO and H2CCO (ketene) besides NO2, CO2, and HOO implies a unimolecular decay pathway for the thermal decomposition of PAN. The major decomposition reaction of PAN is bond fission of the O-N single bond yielding the peroxy radical. The O-O bond fission pathway is a minor route. In the latter case the primary reaction products undergo secondary reactions whose products are spectroscopically identified. No evidence for rearrangement processes as the formation of methyl nitrate is observed. A detailed mapping of the reaction pathways for primary and secondary reactions using quantum chemical calculations is in good agreement with the experiment and predicts homolytic O-N and O-O bond fissions within the PAN molecule as the lowest energetic primary processes. In addition, the first IR spectroscopic characterization of two rotameric forms for the radical CH3C(O)OO is given. 相似文献
189.
Larkin JD Fossey JS James TD Brooks BR Bock CW 《The journal of physical chemistry. A》2010,114(47):12531-12539
o-(N,N-Dialkylaminomethyl)arylboronate systems are an important class of compounds in diol-sensor development. We report results from a computational investigation of fourteen o-(N,N-dialkylaminomethyl)arylboronates using second-order M?ller-Plesset (MP2) perturbation theory. Geometry optimizations were performed at the MP2/cc-pVDZ level and followed by single-point calculations at the MP2/aug-cc-pVDZ(cc-pVTZ) levels. These results are compared to those from density functional theory (DFT) at the PBE1PBE(PBE1PBE-D)/6-311++G(d,p)(aug-cc-pVDZ) levels, as well as to experiment. Results from continuum PCM and CPCM solvation models were employed to assess the effects of a bulk aqueous environment. Although the behavior of o-(N,N-dialkylaminomethyl) free acid and ester proved to be complicated, we were able to extract some important trends from our calculations: (1) for the free acids the intramolecular hydrogen-bonded B-O-H···N seven-membered ring conformers 12 and 16 are found to be slightly lower in energy than the dative-bonded N→B five-membered ring conformers 10 and 14 while conformers 13 and 17, with no direct boron-nitrogen interaction, are significantly higher in energy than 12 and 16; (2) for the esters where no intramolecular B-O-H···N bonded form is possible, the N→B conformers 18 and 21 are significantly lower in energy than the no-interaction forms 20 and 23; (3) H(2)O insertion reactions into the N→B structures 10, 14, 18, and 21 leading to the seven-membered intermolecular hydrogen-bonded B···OH(2)···N ring structures 11, 15, 19, and 22 are all energetically favorable. 相似文献
190.
Dynamics of ice nucleation on water repellent surfaces 总被引:3,自引:0,他引:3
Alizadeh A Yamada M Li R Shang W Otta S Zhong S Ge L Dhinojwala A Conway KR Bahadur V Vinciquerra AJ Stephens B Blohm ML 《Langmuir : the ACS journal of surfaces and colloids》2012,28(6):3180-3186
Prevention of ice accretion and adhesion on surfaces is relevant to many applications, leading to improved operation safety, increased energy efficiency, and cost reduction. Development of passive nonicing coatings is highly desirable, since current antiicing strategies are energy and cost intensive. Superhydrophobicity has been proposed as a lead passive nonicing strategy, yet the exact mechanism of delayed icing on these surfaces is not clearly understood. In this work, we present an in-depth analysis of ice formation dynamics upon water droplet impact on surfaces with different wettabilities. We experimentally demonstrate that ice nucleation under low-humidity conditions can be delayed through control of surface chemistry and texture. Combining infrared (IR) thermometry and high-speed photography, we observe that the reduction of water-surface contact area on superhydrophobic surfaces plays a dual role in delaying nucleation: first by reducing heat transfer and second by reducing the probability of heterogeneous nucleation at the water-substrate interface. This work also includes an analysis (based on classical nucleation theory) to estimate various homogeneous and heterogeneous nucleation rates in icing situations. The key finding is that ice nucleation delay on superhydrophobic surfaces is more prominent at moderate degrees of supercooling, while closer to the homogeneous nucleation temperature, bulk and air-water interface nucleation effects become equally important. The study presented here offers a comprehensive perspective on the efficacy of textured surfaces for nonicing applications. 相似文献