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151.
Silica particles have been used as supports for the preparation of three different propazine-imprinted polymer formats. First format refers to grafting of thin films of molecularly imprinted polymers (MIPs) using an immobilised iniferter-type initiator (inif-MIP). The other two new formats were obtained by complete filling of the silica pores with the appropriate polymerisation mixture leading to a silica-MIP composite material (c-MIP) followed by the dissolution of the silica matrix resulting in spherical MIP beads (dis-MIP). These techniques offer a mean of fine-tuning the particle morphology of the resulting MIP particles leading to enhanced capacity in chromatographic applications. Porous silica (specific surface area S = 380 m2 g−1, particle size ps = 10 μm, pore volume Vp = 1.083 ml g−1 and pore diameter dp = 10.5 nm), methacrylic acid and ethylenglycol dimethacrylate were used for the preparation of the materials. All the MIP formats imprinted with propazine have been characterised by elemental analysis, FT-IR spectroscopy, nitrogen adsorption and scanning electron microscopy. Further, the materials were assessed as stationary phases in HPLC. Capacity factors, imprinting factors and theoretical plate numbers were calculated for propazine and other related triazines in order to compare the chromatographic properties of the three different stationary phases. For the inif-MIPs the column efficiency depended strongly on the amount of grafted polymer. Thus, only the polymers grafted as thin films of ca. 1.3 nm average thickness show imprinting effects and the highest column efficiency giving plate numbers (N) of 1600 m−1 for the imprinted propazine. The performance of the c-MIP stationary phase decreases as result of the complete pore filling after polymerisation and increases again after the removal of the silica matrix due to a better mass transfer in the porous mirror-image resulting polymer. From this study can be concluded that the inif-MIP shows the best efficiency for use as stationary phase in HPLC for the separation of triazinic herbicides. 相似文献
152.
Two ligand exchange chiral stationary phases (CSPs) based on (S)-leucinol derivative, sodium N-((S)-1-hydroxymethyl-3-methylbutyl)-N-undecylaminoacetate, and (R)-phenylglycinol derivative, sodium N-((R)-2-hydroxy-1-phenylethyl)-N-undecylaminoacetate, covalently bonded to silica gel have been successfully applied in the resolution of nine -hydroxycarboxylic acids. The latter was more effective than the former, the separation factors () being 1.05 to 2.12 while the resolution factors (RS) varying from 0.18 to 5.29 on the latter. The chromatographic resolution behaviors were dependent on the type and the content of organic modifier and the content of CuSO4 in aqueous mobile phase and the column temperature. A possible chiral recognition mechanism was also proposed based on the chromatographic resolution behaviors. 相似文献
153.
Efficient Separation of Hydrophobic Molecules by Molecularly Imprinted Cyclodextrin Polymers 总被引:2,自引:0,他引:2
Hiroyuki Asanuma Takayuki Hishiya Makoto Komiyama 《Journal of inclusion phenomena and macrocyclic chemistry》2004,50(1-2):51-55
Cyclodextrins were cross-linked with toluene 2,4-diisocyanate in dimethyl sufoxide in the presence of hydrophobic biomolecules as templates, and the imprinted polymers were applied to the stationary phases of high performance liquid chromatography. Molecular imprinting efficiently promoted the binding-affinity and substrate-selectivity towards the template molecule, compared with the control polymers prepared in their absence. When cholesterol (template molecule) was complexed with cyclodextrins prior to the polymerization, for example, the imprinted polymer retained cholesterol more strongly than other steroids. Upon the polymerization without a template molecule, the binding towards steroids was much weaker. Besides steroids, imprinting was effective for various hydrophobic and rigid template molecules. Since binding of the guest molecule was based on inclusion complex formation with cyclodextrins, separation could be achieved in the solvents containing water. These polymeric receptors are also applicable to selective recognition of biologically important molecules or removal of toxic molecules from aqueous media. Thus, imprinting of cyclodextrins is useful for the preparation of synthetic tailor-made receptors for various kinds of hydrophobic guest molecules. 相似文献
154.
Uniform-sized molecularly imprinted polymer (MIP) beads were prepared using a one-step swelling and polymerization method. The obtained sulfamethazine (SMZ)-imprinted polymer showed high affinity and selectivity toward SMZ and other structurally related sulfonamides in acetonitrile or water-acetonitrile mobile phases, particularly in high aqueous systems. The column performance of the MIPs for SMZ and its analogues could be improved by elevating the column temperature and optimizing the flow rate. The hydrogen-bonding effect plays a significant role in the recognition process of SMZ-imprinted polymer systems in organic media, while the ion-exchange effect, as well as hydrophobic effect, dominates the retention mechanism in aqueous-rich media, in addition to shape recognition. 相似文献
155.
This paper concerns the application of excess adsorption isotherms, measured for solvent mixture/adsorbent systems, to the characterization of TLC data. For this purpose the excess adsorption isotherms for three liquid mixtures: cyclohexane/ benzene, benzene/acetone, and carbon tetrachloride/ethyl acetate on silica gel at 20°C have been measured. These mixtures have been used as binary mobile phases in TLC measurements. It has been shown for a given solute in binary mobile phase that the quantity RM is a simple function of the excess adsorption. Parameters of this function have been used to characterize chromatographic systems with binary mobile phases. 相似文献
156.
157.
The effects of cholesterol, a lipid mostly found in the sarcolemmal membranes, on the interaction of amiodarone with synthetic
models of dimyristoylphosphatidylcholine (DMPC) and with native models of mitochondria and brain microsomes was studied. Alterations
on the structural order of lipids were assessed by fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) probing
the bilayer core, and of the propionic acid derivative 3-(p-(6-phenyl)-1,3,5-hexatrienyl)phenylpropionic acid (DPH-PA) probing the outer regions of the bilayer. As detected by the probes
and according to classic observations, cholesterol progressively increased the molecular order in the fluid phase of DMPC.
Additionally, it modulated the type and extension of amiodarone effects. For low cholesterol concentrations (≤10–15 mol%),
amiodarone (50 μM) ordered DMPC bilayers and the effects were almost identical to those observed in pure DMPC. For higher cholesterol concentrations,
amiodarone ordering effects decreased slightly and faded for cholesterol concentrations as high as 25 and 30 mol%, when detected
by DPH-PA and DPH, respectively. Above these high cholesterol concentrations, a crossover from ordering to disordering effects
of amiodarone was apparent, either in the upper region of the bilayer or the hydrophobic core. The effects of amiodarone in
native membranes of mitochondria and brain microsomes, in which "native" cholesterol accounts for about 0 and 25 mol%, respectively,
correlated reasonably with the results in models of synthetic lipids. There is a close relationship between cholesterol concentration
and amiodarone effects, in either synthetic models or native model membranes. Therefore, it may be predicted that the lipid
physicochemical properties regulated by cholesterol concentration will also modulate the effects of amiodarone in sarcolemma. 相似文献
158.
This review article describes some general comments on micellar electrokinetic chromatography (MEKC) from the viewpoint of pseudo-stationary phases and presents a compiled list of surfactants used for MEKC, prepared from published papers. We tried to give comments on some typical surfactants from the practical point of view. 相似文献
159.
Summary Two new cyclodextrin (CD) derivatives, heptakis{2,6-di-O-pentyl-3-O-[3′-(2″-chloro-4″,5″-dioxylmethene)-phenyl-5′-iso-oxazolylmethyl]}-β-CD
(CD I) and heptakis{2,6-di-O-methyl-3-O-[3′-(2″-chloro)-phenyl-5′-iso-oxazolylmethyl]}-β-CD (CD II) were synthesized and coated
on fused-silica capillary columns. Their chromatographic characteristics, including column efficiency, polarity, selectivity
and phase transition were studied and compared with similar β-CD stationary phases. It was found that the heterocycle group
has a significant effect on the selectivity of the CD stationary phases. Both stationary phases can be successfully used to
separate many di- and trisubstituted benzene positional isomers and show stronger separation ability in separating low-polarity
benzene positional isomers than other β-CD stationary phases. 相似文献
160.
Summary Chirally substituted Si–H-containing polysiloxanes were synthesized, which can be immobilized on small particle silica gel as well as on the smooth surfaces of fused silica capillaries. Immobilization is achieved either by crosslinking or by chemical bonding to the surfaces via silanol groups; both reactions can only be performed by addition of H2PtCl6, which acts as catalyst for hydrosilylation and as stoichiometric reagent for crosslinking. Chiral substituents of systematically varied chemical structure were introduced into the polysiloxanes by hydrosilylation. The mechanism of immobilization was investigated by spectroscopic methods, notably29Si-NMR. Homogenous stationary-phase coatings of variable film thickness and corresponding retentivity can easily be achieved. The enantioselectivity of the phase systems was characterized in dependency on the chemical structure of the chiral selectors attached to the polysiloxane chain of the chiral stationary phases and also in terms of the functional groups introduced into the solutes by derivatisation. 相似文献