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991.
1H‐NMR relaxometric studies of interaction between apoptosis specific MRI paramagnetic contrast agents and micellar models of apoptotic cells
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Aurore Van Koninckxloo Céline Henoumont Sophie Laurent Robert N. Muller Luce Vander Elst 《Magnetic resonance in chemistry : MRC》2016,54(7):568-574
1H‐NMR was previously used to analyze the interaction between peptides (E3 and R826) selected by phage display to target apoptotic cells and phospholipidic models of these cells. In order to avoid the use of apoptotic cells and to obtain a fast evaluation of the efficiency of the potential MRI contrast agents obtained by grafting these peptides and their scramble analogs on a paramagnetic gadolinium complex, their proton relaxometric behavior was investigated in the presence of micelles mimicking healthy and apoptotic cells. Their preferential interaction with 1,2‐dipalmitoyl‐sn‐glycero‐3‐phospho‐l ‐serine micelles mimicking apoptotic cells as compared with 1,2‐dipalmitoyl‐sn‐glycero‐3‐phosphocholine micelles modeling healthy cells was shown by nuclear magnetic relaxation dispersion profiles and the enhancement of the transverse proton relaxation rates at 60 MHz. The association constant values confirm the stronger interaction of the selected conjugated peptides (Ka Gd‐PMN‐E3(gadolinium 2,2′,2′′,2′′′‐[((4‐carboxy)pyridine‐2,6‐diyl)bis(methylenenitrilo)]‐tetrakis acetate) grafted with E3 peptide): 2.43 104 m ?1; Ka Gd‐DTPA‐R826(gadolinium ((1‐p‐isothiocyanatobenzyl)‐diethylenetriaminepentaacetate) grafted with R826 peptide): 2.91 104 m ?1) as compared with their conjugated scrambles (Ka Gd‐PMN‐E3sc(gadolinium 2,2′,2′′,2′′′‐[((4‐carboxy)pyridine‐2,6‐diyl)bis(methylenenitrilo)]‐tetrakis acetate) grafted with E3 scramble peptide): 0.18 104 m ?1; Ka Gd‐DTPA‐R826sc(gadolinium ((1‐p‐isothiocyanatobenzyl)‐diethylenetriaminepentaacetate) grafted with R826 scramble peptide): 0.32 104 m ?1) even if the conjugation of E3 and R826 seems to decrease their interaction. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
992.
Hanna Ayoub Virginie Lair Sophie Griveau Philippe Brunswick José H. Zagal Fethi Bedioui Michel Cassir 《Electroanalysis》2012,24(2):386-391
We have studied the electrochemical kinetics of anodic Ni dissolution as a function of chloride ion concentration, at pH 5, 6 and 7, in order to mimic the conditions of sweat samples. Our results show that the rate‐determining step for Ni dissolution in the mentioned pH range is the transfer of one first electron, as suggested by the Tafel slopes close to 0.120 V/decade. However, the reaction order in chloride ion varies from ca. 2 at pH 7 to values close to unity for pH values between 5 and 6. This finding is very important for sensor applications in sweat fluids since the sensitivity of the Ni electrode to chloride ions is higher in neutral solutions (pH ca. 7) compared to that in slightly acid solutions (pH between 5 and 6). Small variations in pH in real samples are expected so this change in sensitivity should be considered when sensing chloride ions in sweat fluids. 相似文献
993.
Stéphane Bouchonnet Sophie Bourcier Yasmine Souissi Christophe Genty Michel Sablier Pascal Roche Véronique Boireau Valérie Ingrand 《Journal of mass spectrometry : JMS》2012,47(4):439-452
The degradation of the chloracetamide herbicide acetochlor has been studied under simulated ozonation treatment plant conditions. The degradation of acetochlor included the formation of several degradation products that were identified using GC/ion‐trap mass spectrometry with EI and CI and HPLC/electrospray‐QqTOF mass spectrometry. Thirteen ozonation products of acetochlor have been identified. Ozonation of the deuterated herbicide combined to MSn and high‐resolution mass measurement allowed effective characterization of the degradation products. At the exception of one of them, the product B (2‐chloro‐2', ethyl‐6', methyl‐acetanilide), none of the identified degradation products has been already reported in the literature. Post‐ozonation kinetics studies revealed that the concentrations of most degradation products evolved noticeably with time, particularly during the first hours following the ozonation treatment. This raises concerns about the fate of degradation products in the effluents of treatment plants and suggests the need for a better control on these products if their toxicity was demonstrated. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
994.
Dr. Pierre Brignou Dr. Sophie M. Guillaume Dr. Thierry Roisnel Dr. Didier Bourissou Prof. Jean‐François Carpentier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(30):9360-9370
We describe herein an original approach for the efficient immortal ring‐opening polymerization (iROP) of trimethylene carbonate (TMC) under mild conditions using dual‐catalyst systems combining a discrete cationic metal complex with a tertiary amine. A series of new zinc and magnesium cationic complexes of the type [{NNO}M]+[anion]? ({NNO}?=2,4‐di‐tert‐butyl‐6‐{[(2′‐dimethylaminoethyl)methylamino]methyl}phenolate; M=Zn, [anion]?=[B(C6F5)4]? ( 2 ), [H2N‐ {B(C6F5)3}2]? ( 3 ), and [EtB(C6F5)3]? ( 4 ); M=Mg, [anion]?=[H2N{B(C6F5)3}2]? ( 7 )) have been prepared from the corresponding neutral compounds [{NNO}ZnEt] ( 1 ) and [{NNO}‐ Mg(nBu)] ( 6 ). Compounds 2 – 4 and 7 exist as free ion pairs, as revealed by 1H, 13C, 19F, and 11B NMR spectroscopy in THF solution, and an X‐ray crystallographic analysis of the bis(THF) adduct of compound 7 , 7? (THF)2. The neutral complexes 1 and 6 , in combination with one equivalent or an excess of benzyl alcohol (BnOH), initiate the rapid iROP of TMC, in bulk or in toluene solution, at 45–60 °C (turnover frequency, TOF, up to 25–30 000 mol(TMC)?mol(Zn)?h?1 for 1 and 220–240 000 mol(TMC)?mol(Mg)?h?1 for 6 ), to afford H‐PTMC‐OBn with controlled macromolecular features. ROP reactions mediated by the cationic systems 2 /BnOH and 7 /BnOH proceeded much more slowly (TOF up to 500 and 3 000 mol(TMC)?mol(Zn or Mg)?h?1 at 110 °C) than those based on the parent neutral compounds 1 /BnOH and 6 /BnOH, respectively. Use of original dual organic/organometallic catalyst systems, obtained by adding 0.2–5 equiv of a tertiary amine such as NEt3 to zinc cationic complexes [{NNO}Zn]+[anion]? ( 2 – 4 ), promoted high activities (TOF up to 18 300 mol(TMC)?mol(Zn)?h?1 at 45 °C) giving H‐PTMC‐OBn with good control over the Mn and Mw/Mn values. Variation of the nature of the anion in 2 – 4 did not significantly affect the performance of these catalyst systems. On the other hand, the dual magnesium‐based catalyst system 7 /NEt3 proved to be poorly effective. 相似文献
995.
996.
Paillat Lionel Périchet Christine Lavoine Sophie Meierhenrich Uwe Fernandez Xavier 《平面色谱法杂志一现代薄层色谱法》2012,25(1):23-29
JPC – Journal of Planar Chromatography – Modern TLC - A new, simple, sensitive, selective, precise, and robust high-performance thin-layer chromatography (HPTLC) method was developed... 相似文献
997.
Sanae Abrakhi Sébastien Péralta Sophie Cantin Odile Fichet Dominique Teyssié 《Colloid and polymer science》2012,290(5):423-434
The photochemical behavior of photosensitive materials obtained by spin-coating or network synthesis of a cellulosic polymer
bearing photo-cross-linkable cinnamate groups was investigated. First, cinnamate groups were grafted on a cellulose acetate
butyrate polymer, with different grafting densities. The photochemical properties of the polymers were studied in solution
by UV–visible and 1H NMR spectroscopy. Then spin-coated films and networks were prepared and characterized as a function of the number of cinnamate
groups per cellulosic unit. The water-wetting properties of both surfaces were studied by dynamic contact angle measurements,
before and after photoirradiation, and subsequent heating. The surfaces obtained by the two methods have significantly different
behaviors that can be assigned to the distinct photochemical pathways of the cinnamate groups upon irradiation depending on
the sample preparation. Indeed, dimerization reaction is evidenced as the main process in the spin-coated films while the
expected isomerization is predominant at the surface of the polymer networks. 相似文献
998.
Dehaen G Eliseeva SV Kimpe K Laurent S Vander Elst L Muller RN Dehaen W Binnemans K Parac-Vogt TN 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(1):293-302
A ditopic chelating ligand (H(6)4) that bears catechol and diethylenetriamine-N,N,N',N',N'-pentaacetate (DTPA) has been designed and shown to specifically bind lanthanide(III) ions at the DTPA core ([Ln(H(2)4)(H(2)O)](-)) and further self-assemble with titanium(IV), thereby giving rise to the formation of a supramolecular metallostar complex with a lanthanide(III)-to-titanium(IV) ratio of 3:1, [(Ln4)(3)Ti(H(2)O)(3)](5-) (Ln=La, Eu, Gd). The efficacy of the metallostar complex as a potential bimodal optical/magnetic resonance imaging (MRI) agent has been evaluated. Nuclear magnetic relaxation dispersion (NMRD) measurements for the [(Gd4)(3)Ti(H(2)O)(3)](5-) complex have demonstrated an enhanced r(1) relaxivity that corresponds to 36.9 s(-1) mM(-1) per metallostar molecule at 20 MHz and 310 K, which is a result of a decreased tumbling rate. The ability of the complex to bind to human serum albumin (HSA) was also examined by relaxometric measurements. In addition, upon UV irradiation the [(Gd4)(3)Ti(H(2)O)(3)](5-) complex exhibits broad-band green emission in the range 400-750 nm with a maximum at 490 nm. Taking into account the high relaxivity and luminescence properties, the [(Gd4)(3)Ti(H(2)O)(3)](5-) complex is a good lead compound for the development of efficient bimodal contrast agents. 相似文献
999.
Jason Adamson Sophie Hughes David Azzopardi John McAughey Marianna D Ga?a 《Chemistry Central journal》2012,6(1):1-11
Background
Recently, an increased interest in the identification of valuable possibilities for preserving the antioxidant properties of products obtained by thermal processing of fruits rich in bioactive compounds can be noticed. In this regard, an extensive analysis is necessary in terms of thermal processed products behavior in relation to various factors. The purpose of the present study was to assess the effect which processing and storage at 20°C has on the antioxidant properties and color quality of low-sugar bilberry jam with different low-methoxyl pectin (LMP) concentrations.Results
For all measured parameters, it should be noted that thermal processing induced significant alterations reported to the values registered for fresh fruit. Most important losses due to thermal processing were recorded for total monomeric anthocyanins (TMA) (81-84%), followed by L-ascorbic acid (L-AsAc) content (53-58%), total phenolics (TP) content (42-51%) and FRAP (ferric reducing antioxidant power) values (36-47%). Moreover, depreciation of the investigated compounds occurred during storage at 20°C. Jam storage for 7 months resulted in severe losses in TMA content in the range 58-72% from the value recorded one day after processing. This coincided with marked increases in polymeric color percent of these products after 7 months of storage. Also, bilberry jam storage for 7 months resulted in a decrease in L-AsAc content of 40-53% from the value recorded one day after processing, 41-57% in TP content and 33-46% from the value recorded one day after processing for FRAP values. By decreasing of LMP concentration in the jam recipe from 1 to 0.3% there has been an increase in losses of investigated compounds.Conclusion
Overall, the results indicated that bilberry jams can also represent a good source of antioxidant compounds, although compared to the fruit, important losses seem to occur. Practical application of this work is that this kind of information will be very useful in optimizing the jam processing technology and storage conditions, in order to improve the quality of these products. 相似文献1000.
Sophie Ayciriex Anne Regazzetti Mathieu Gaudin Elise Prost Delphine Dargère France Massicot Nicolas Auzeil Olivier Laprévote 《Analytical and bioanalytical chemistry》2012,404(10):3049-3059
Cholesterol and oxysterols are involved as key compounds in the development of severe neurodegenerative diseases and in neuroinflammation processes. Monitoring their concentration changes under pathological conditions is of interest to get insights into the role of lipids in diseases. For numerous years, liquid chromatography coupled to mass spectrometry has been the method of choice for metabolites identification and quantification in biological samples. However, sterols and oxysterols are relatively apolar molecules poorly adapted to electrospray ionization (ESI). To circumvent this drawback, we developed a novel and robust analytical method involving derivatization of these analytes in cholesteryl N-4-(N,N-dimethylamino)phenyl carbamates under alkaline conditions followed by ultra-performance liquid chromatography–high resolution mass spectrometry analysis (UPLC-HRMS). Optimized UPLC conditions led to the separation of a mixture of 11 derivatized sterols and oxysterols especially side chain substituted derivatives after 6?min of chromatographic run. High sensitivity time-of-flight mass analysis allowed analytes to be detected in the nanomolar range. The method was validated for the analysis of oxysterols and sterols in mice brain in respect of linearity, limits of quantification, accuracy, precision, analyte stability, and recovery according to the Food and Drug Administration (FDA) guidelines. The developed method was successfully applied to investigate the impact of lipopolysaccharide (LPS) treatment on the rat cerebral steroidome. 相似文献