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961.
Li B Peet NP Butler MM Burnett JC Moir DT Bowlin TL 《Molecules (Basel, Switzerland)》2011,16(1):202-220
Botulinum neurotoxins (BoNTs) are the most potent of known toxins and are listed as category A biothreat agents by the U.S. CDC. The BoNT-mediated proteolysis of SNARE proteins inhibits the exocytosis of acetylcholine into neuromuscular junctions, leading to life-threatening flaccid paralysis. Currently, the only therapy for BoNT intoxication (which results in the disease state botulism) includes experimental preventative antibodies and long-term supportive care. Therefore, there is an urgent need to identify and develop inhibitors that will serve as both prophylactic agents and post-exposure 'rescue' therapeutics. This review focuses on recent progress to discover and develop small molecule inhibitors as therapeutic countermeasures for BoNT intoxication. 相似文献
962.
Linear, soluble copolymers of vinyl isocyanate with styrene and methyl methacrylate were obtained when the comonomer:vinyl isocyanate ratio in the copolymer was greater than 9:1. When the comonomer to isocyanate ratio was less than 2:1, the copolymers were insoluble. Infrared evidence indicated that spontaneous cross-linking through the isocyanate function occurred by a mechanism similar to the known reaction by which isocyanates undergo dimerization and trimerization. The soluble copolymers retained the reactive isocyanate moeity as was shown by their reactivity with n-butylamine and ethanol to produce, respectively, the corresponding polyurea and polycarbamate, and with ethylenediamine and water to produce cross-linked polymers. The intrinsic viscosity [η] for the 9:1 methyl methacrylate: vinyl isocyanate copolymer was 0.22 dl/g while that for the corresponding ethyl carbamate was 0.24 dl/g. 相似文献
963.
The enhanced rate of cyclopolymerization of divinyl monomers over that of the corresponding monovinyl monomers is considered. The relative polymerization rates of the following monovinyl-divinyl monomer pairs were determined: methyl methacrylate-methacrylic anhydride; 2-cyano-l-heptene-2,6-dicyano-l, 6-heptadiene; and 2-phenyl-l -hepteneh-2,6-diphenyl-1,6-heptadiene. An attempt was made to prepare methacrylic isobutyric anhydride as the monovinyl monomer to compare with methacrylic anhydride but its inherent instability precluded its isolation in pure state. The over-all rate of the divinyl monomer in every case was considerably greater than that of the corresponding monovinyl monomer, the ratios varying from two to ten. From the rate data obtained it was possible to estimate the effective concentration of the intramolecular double bond with respect to the radical, and values greater than 20 M at 50° were obtained in the case of 2,6-dicyano-l,6-heptadiene. This value compares favorably with a concentration of 21.8 M for liquid ethylene at -102°. These results can be interpreted most satisfactorily in terms of a concerted cyclization step which requires considerable preorientation prior to reaction. This favorable preorientation could be interpreted as an electronic interaction between the developing radical cite and the intramolecular double bond. 相似文献
964.
Although ortho-esters constitute a well-known class of organic compounds, the orthoacrylates were unknown prior to a report from these laboratories in 1972. To date, this novel class of acrylic esters has not been investigated as polymerization monomers. We report here polymerization and copolymerization studies of representative members of this class of compounds. Although the orthoacrylates studied did not polymerize in the presence of conventional cationic initiators nor radical initiators, they did respond to radical-initiated copolymerization with a variety of conventional vinyl monomers. Their corresponding reactivity ratios were determined, as well as the Q and e parameters. Monomer syntheses and characterization are reported, as well as structural and properties studies on the copolymers. 相似文献
965.
Abstract The kinetics of the AIBN-initiated copolymerization of divinyl ether (DVE) and ethyl vinyl ether (EVE) with maleic anhydride (MA) was extensively studied in seven different solvents. The yield at 100% conversion as a function of the feed composition when the total monomer concentration is kept constant gave a confirmation of the composition of these copolymers: DVE/MA=½ and EVE/MA=1/1. The study of the initial rate as a function of the feed composition made it possible to determine the relative values of the different propagation rate constants consistent with a mechanism by successive and selective additions: in the EVE-MA system, the addition of EVE is slower than the addition of MA; in the DVE-MA system, the addition of DVE is slower than the addition of the first MA molecule, while the addition of the second MA molecule is slower than the first one. The study of the dependence of the monomer concentration, of the AIBN concentration, and of the efficiency of the initiator, on the rate of polymerization, shows finally that the true order of the monomer concentration is close to 1 while its apparent order varies from 1 to 2. From all the kinetic data it was observed that the mechanism of these co polymerizations can be explained without reliving upon the concept of participation of the charge-transfer complex formed between the monomers. However, participation of the complex in a competing mechanism with the above cannot be completely excluded. 相似文献
966.
The equilibrium constants for charge-transfer (CT) complex formation between divinyl ether (DVE) and several sub-stituted maleic anhydrides and 2-cyclopentene-l,4-dione were measured in CHC13 by use of UV spectroscopy. The copolymerizaticn of DVE with these acceptor monoolefins produced regular cyclocopolymers of constant 1:1 or 1:2 (DVE:monoolefin) composition regardless of the feed composition. Comparison of the CT complexation and the cyciocopolymerization leads to the following conclusions: 1) A strong CT complex gives regular cyclocopolymer of constant 1:1 composition having a copolymer backbone made up of only 1,4-diene units: 2) when a monoolefin is un-reactive (often sterically), the 1:1 cyclocopolymer is pro-duced: and 3) if CT complexation is weak and the monoolefin is reactive toward radicals (but not so reactive as to homo-polymerize easily), a 1:2 alternating cyclocopolymer is produced. A facile and quantitative elimination of hydrogen halides with dilute aqueous NaOH solution was found. 相似文献
967.
Florian Fusseis Holger Steeb Xianghui Xiao Wen‐lu Zhu Ian B. Butler Stephen Elphick Urs Mäder 《Journal of synchrotron radiation》2014,21(1):251-253
A new modular X‐ray‐transparent experimental cell enables tomographic investigations of fluid rock interaction under natural reservoir conditions (confining pressure up to 20 MPa, pore fluid pressure up to 15 MPa, temperature ranging from 296 to 473 K). The portable cell can be used at synchrotron radiation sources that deliver a minimum X‐ray flux density of 109 photons mm?2 s?1 in the energy range 30–100 keV to acquire tomographic datasets in less than 60 s. It has been successfully used in three experiments at the bending‐magnet beamline 2BM at the Advanced Photon Source. The cell can be easily machined and assembled from off‐the‐shelf components at relatively low costs, and its modular design allows it to be adapted to a wide range of experiments and lower‐energy X‐ray sources. 相似文献
968.
Ratiometric Detection of Adenosine Triphosphate (ATP) in Water and Real‐Time Monitoring of Apyrase Activity with a Tripodal Zinc Complex
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Dr. Stephen J. Butler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(48):15768-15774
Two tripodal fluorescent probes Zn?L1 , 2 have been synthesised, and their anion‐binding capabilities were examined by using fluorescence spectroscopy. Probe Zn?L1 allows the selective and ratiometric detection of adenosine triphosphate (ATP) at physiological pH, even in the presence of several competing anions, such as ADP, phosphate and bicarbonate. The probe was applied to the real‐time monitoring of the apyrase‐catalysed hydrolysis of ATP, in a medium that mimics an extracellular fluid. 相似文献
969.
The preparation of styrenes by palladium-catalyzed cross-coupling of aromatic iodides and bromides with divinyltetramethyldisiloxane (DVDS) in the presence of inexpensive silanolate activators has been developed. To facilitate the discovery of optimal reaction conditions, Design of Experiment (DoE) protocols were used. By the guided selection of reagents, stoichiometries, temperatures, and solvents, the vinylation reaction was rapidly optimized with three stages consisting of ca. 175 experiments (of a possible 1440 combinations). A variety of aromatic iodides undergo cross-coupling at room temperature in the presence of potassium trimethylsilanoate using Pd(dba)2 in DMF in good yields. Triphenylphosphine oxide is needed to extend catalyst lifetime. Application of these conditions to aryl bromides was accomplished by the development of two complementary protocols. First, the direct implementation of the successful reaction conditions using aryl iodides at elevated temperature in THF provided the corresponding styrenes in good to excellent yields. Alternatively, the use of potassium triethylsilanolate and a bulky "Buchwald-type" ligand allows for the vinylation reactions to occur at or just above room temperature. A wide range of bromides underwent coupling in good yields for each of the protocols described. 相似文献
970.
Large‐surface‐area diamond (111) crystal plates for applications in high‐heat‐load wavefront‐preserving X‐ray crystal optics
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Stanislav Stoupin Sergey Antipov James E. Butler Alexander V. Kolyadin Andrey Katrusha 《Journal of synchrotron radiation》2016,23(5):1118-1123
Fabrication and results of high‐resolution X‐ray topography characterization of diamond single‐crystal plates with large surface area (10 mm × 10 mm) and (111) crystal surface orientation for applications in high‐heat‐load X‐ray crystal optics are reported. The plates were fabricated by laser‐cutting of the (111) facets of diamond crystals grown using high‐pressure high‐temperature methods. The intrinsic crystal quality of a selected 3 mm × 7 mm crystal region of one of the studied samples was found to be suitable for applications in wavefront‐preserving high‐heat‐load crystal optics. Wavefront characterization was performed using sequential X‐ray diffraction topography in the pseudo plane wave configuration and data analysis using rocking‐curve topography. The variations of the rocking‐curve width and peak position measured with a spatial resolution of 13 µm × 13 µm over the selected region were found to be less than 1 µrad. 相似文献