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101.
Attempts to use alkylation to introduce a positive charge at the nitrogen atom of the 4‐pyridyl ring in the bis(bidentate) triazole ligand N4‐(4‐pyridyl)‐3,5‐di(2‐pyridyl)‐1,2,4‐triazole ( pydpt ) were made to ascertain what effect a strongly electron‐withdrawing group would have on the magnetic properties of any subsequent iron(II) complexes. Alkylation of pydpt under relatively mild conditions led in some cases to unexpected rearrangement products. Specifically, when benzyl bromide is used as the alkylating agent, and the reaction is carried out in refluxing acetonitrile, the N4 substituent moves to the N1 position. However, when the same reaction is performed in dichloromethane at room temperature, the rearrangement does not occur and the desired product containing an alkylated N4 substituent is obtained. Heating a pure sample of N4‐Bzpydpt?Br to reflux in MeCN resulted in clean conversion to N1Bzpydpt.Br . This is consistent with N4‐Bzpydpt.Br being the kinetic product whereas N1Bzpydpt.Br is the thermodynamic product. When methyl iodide is used as the alkylating agent, the N4 to N1 rearrangement occurs even at room temperature, and at reflux pydpt is doubly alkylated. The observation of the lowest reported temperatures for an N4 to N1 rearrangement is due to this particular rearrangement involving nucleophilic aromatic substitution: a possible mechanism for this transformation is suggested. 相似文献
102.
Mansell D Rattray N Etchells LL Schwalbe CH Blake AJ Bichenkova EV Bryce RA Barker CJ Díaz A Kremer C Freeman S 《Chemical communications (Cambridge, England)》2008,(41):5161-5163
Natural myo-inositol phosphate antioxidants containing the 1,2,3-trisphosphate motif bind Fe(3+) in the unstable penta-axial conformation. 相似文献
103.
Michel R Subramaniam V McArthur SL Bondurant B D'Ambruoso GD Hall HK Brown MF Ross EE Saavedra SS Castner DG 《Langmuir : the ACS journal of surfaces and colloids》2008,24(9):4901-4906
Planar supported lipid bilayers that are stable under ambient atmospheric and ultra-high-vacuum conditions were prepared by cross-linking polymerization of bis-sorbylphosphatidylcholine (bis-SorbPC). X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were employed to investigate bilayers that were cross-linked using either redox-initiated radical polymerization or ultraviolet photopolymerization. The redox method yields a more structurally intact bilayer; however, the UV method is more compatible with incorporation of transmembrane proteins. UV polymerization was therefore used to prepare cross-linked bilayers with incorporated bovine rhodopsin, a light-activated, G-protein-coupled receptor (GPCR). A previous study (Subramaniam, V.; Alves, I. D.; Salgado, G. F. J.; Lau, P. W.; Wysocki, R. J.; Salamon, Z.; Tollin, G.; Hruby, V. J.; Brown, M. F.; Saavedra, S. S. J. Am. Chem. Soc. 2005, 127, 5320-5321) showed that rhodopsin retains photoactivity after incorporation into UV-polymerized bis-SorbPC, but did not address how the protein is associated with the bilayer. In this study, we show that rhodopsin is retained in supported bilayers of poly(bis-SorbPC) under ultra-high-vacuum conditions, on the basis of the increase in the XPS nitrogen concentration and the presence of characteristic amino acid peaks in the ToF-SIMS data. Angle-resolved XPS data show that the protein is inserted into the bilayer, rather than adsorbed on the bilayer surface. This is the first study to demonstrate the use of ultra-high-vacuum techniques for structural studies of supported proteolipid bilayers. 相似文献
104.
Abstract Two 36-membered (2+2) Schiff-base macrocycles have been prepared and characterised without the use of template ions or high dilution techniques. Rather, intramolecular hydrogen-bonding and π-π interactions promote the isolation of these “figure-of-eight” products in good yields. Two cobalt(III) complexes of the 18-membered (1+1) Schiff-base macrocycles are formed when cobalt(II) is used as a template. The structures of one “figure-of-eight' metal-free (2+2) macrocycle and of one dicobalt(III) complex of a (1+1) macrocycle, in which the cobalt centres are octahedral, are presented. [H4L1tBu]2: C70H70N8O9, space group P-1, a=7.747(1), b=17.106(3), c=23.662(4) å, α=104.83(3), β=95.86(3), γ=97.80(3)°, U=2972.4(8) å3, Z=2, Dc=1.30 g cm?3, T=100K, 554 parameters, R1=0.072 [for 4137 reflections having F>4[(F)], wR2=0.191 and goodness of fit 0.97 (for all 8343 independent F2 data). [Co2(L1tBu)(OAc)2(pyridine)] 1.5DMF 0.5MeCN, C47.5H49N7O9.5Co2, space group P2(1)/n, a=13.067(2), b=26.071(4), c=14.023(3) å, β=93.02(1)°, U=4770.6(15) å3, Z=4, Dc=1.38 g cm?3, T=168 K, 622 parameters, R1=0.075 [for 5233 reflections having F > 4[?F?], wR2=0.133 and good ness of fit 1.08 (for all 8512 independent F2 data). 相似文献
105.
Sally A. Peyman Er Yee KwanOliver Margarson Alexander IlesNicole Pamme 《Journal of chromatography. A》2009,1216(52):9055-9062
We report the exploration of diamagnetic repulsion forces for the selective manipulation of microparticles inside microfluidic devices. Diamagnetic materials such as polymers are repelled from magnetic fields, an effect greatly enhanced by suspending a diamagnetic object in a paramagnetic Mn2+ solution. The versatility of diamagnetic repulsion is demonstrated for the trapping, focussing and deflection of polystyrene particles for three example applications. Firstly, magnet pairs with unlike poles facing each other were arranged along a microcapillary to trap plugs of differently functionalised particles for a simultaneous surface-based assay in which biotin was selectively bound to a plug of streptavidin coated particles utilising only 22 nL of reagent. Secondly, by slightly modifying the magnetic field design, the rapid focussing of particles into a narrow central stream at a flow rate of 650 μm s−1 was accomplished for particle pre-concentration. In a third application, 5 and 10 μm polystyrene particles were separated from each other in continuous flow by passing the particle mixture through a microfluidic chamber with a perpendicular magnetic field, a method termed diamagnetophoresis. The separation was investigated between flow rates of 20–100 μL h−1, with full resolution of the particle populations being achieved at 20 μL h−1. These experiments show the potential of diamagnetic repulsion for simple, label-free manipulation of particles and other diamagnetic objects such as cells for a range of bioanalytical techniques. 相似文献
106.
Inflammasomes are protein complexes which are important in several inflammatory diseases. Inflammasomes form part of the innate immune system that triggers the activation of inflammatory cytokines interleukin (IL)-1β and IL-18. The inflammasome most studied in sterile inflammation and non-communicable disease is the NLRP3 inflammasome. Upon activation by diverse pathogen or disease associated signals, NLRP3 nucleates the oligomerization of an adaptor protein ASC forming a platform (the inflammasome) for the recruitment and activation of the protease caspase-1. Active caspase-1 catalyzes the processing and release of IL-1β and IL-18, and via cleavage of the pore forming protein gasdermin D can drive pyroptotic cell death. This review focuses on the structural basis and mechanism for NLRP3 inflammasome signaling in the context of drug design, providing chemical structures, activities, and clinical potential of direct inflammasome inhibitors. A cryo-EM structure of NLRP3 bound to NEK7 protein provides structural insight and aids in the discovery of novel NLRP3 inhibitors utilizing ligand-based or structure-based approaches. 相似文献
107.
A family of five new bis-bidentate azole–triazole Rat ligands (1,3-bis(5-(azole)-4-isobutyl-4H-1,2,4-triazol-3-yl)benzene), varying in choice of azole (2-imidazole, 4-imidazole, 1-methyl-4-imidazole, 4-oxazole and 4-thiazole), and the corresponding family of spin-crossover (SCO) and redox active triply bridged dinuclear helicates, [FeII2L3]4+, has been prepared and characterised. X-ray crystal structures show all five Fe(ii) helicates are low spin at 100 K. Importantly, DOSY NMR confirms the intactness of these SCO-active dinuclear helicates in D3-MeCN solution, regardless of HS fraction: γHS(298 K) = 0–0.81. Variable temperature 1H NMR Evans and UV-vis studies reveal that the helicates are SCO-active in MeCN solution. Indeed, the choice of azole in the Rat ligand used in [Fe2L3]4+ tunes: (a) solution SCO T1/2 from 247 to 471 K, and (b) reversible redox potential, Em(FeII/III), from 0.25 to 0.67 V for four helicates, whilst one has an irreversible redox process, Epa = 0.78 V, vs. 0.01 M AgNO3/Ag. For the four reversible redox systems, a strong correlation (R2 = 0.99) is observed between T1/2 and Epa. Finally, the analogous Ni(ii) helicates have been prepared to obtain Δo, establishing: (a) the ligand field strength order of the ligands: 4-imidazole (11 420) ∼ 1-methyl-4-imidazole (11 430) < 2-imidazole (11 505) ∼ 4-oxazole (11 516) < 4-thiazole (11 804 cm−1), (b) that Δo ([NiII2L3]4+) strongly correlates (R2 = 0.87) with T1/2 ([FeII2L3]4+), and (c) interestingly that Δo strongly correlates (R2 = 0.98) with Epa for the four helicates with reversible redox, so the stronger the ligand field strength, the harder it is to oxidise the Fe(ii) to Fe(iii).Choice of non-coordinated diazole heteroatom in five robust triply bridged dinuclear helicates tunes Δo, spin crossover and redox potential. Regardless of fraction high spin (0–0.81), DOSY NMR confirms the helicates are intact in solution. 相似文献
108.
Christopher M Timperley Sally A Saunders Josef Szpalek Matthew J Waters 《Journal of fluorine chemistry》2003,119(2):161-171
The reactivity of bis(fluoroalkyl) phosphorochloridates to nucleophiles is summarised. Previous data and the results described here indicate that reactivities decrease in the order: amines>alcohols>thiols. The synthesis of CF3CH2OP(O)(SEt)2 in 30% yield was accomplished by treating CF3CH2OP(O)Cl2 with two molar equivalents of EtSH and Et3N in ether. The chloridates (CF3CH2O)2P(O)Cl and (C2F5CH2O)2P(O)Cl did not react with MeSH in ether at −78 °C or when heated with Pb(SMe)2 in benzene. Ethanethiol and propanethiol reacted with fluorinated chloridates in the presence of triethylamine to give thiolates (RFO)2P(O)SR in 13-41% yield where RF was CF3CH2, C2F5CH2, C3F7CH2 or (CF3)2CH and R was Et or n-Pr. Similarly, reaction of phosphorobromidates (RFCH2O)2P(O)Br, made by brominating the corresponding bis(fluoroalkyl) H-phosphonates, with benzenethiol gave derivatives (RFCH2O)2P(O)SPh in 43 and 46% yield where RF was CF3 and C2F5, respectively. Treatment of the chloridothiolate Cl(EtO)P(O)SMe, prepared in two steps from triethyl phosphite, with fluoroalcohols and triethylamine in ether gave species RFO(EtO)P(O)SMe in 62-74% yield where RF was CF3CH2, C2F5CH2, C3F7CH2 or (CF3)2CH. The reactions of bis(trifluoroethyl) phosphorochloridate with 2-mercaptoethanol, 3-mercaptopropanol and ethane-1,2-dithiol gave several unexpected products whose structures were tentatively assigned. 相似文献
109.