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351.
Anderson RF Shinde SS Hay MP Gamage SA Denny WA 《Organic & biomolecular chemistry》2005,3(11):2167-2174
Revealing the free radical mechanism by which the anticancer drug tirapazamine (3-amino-1,2,4-benzotriazine 1,4-dioxide) induces hypoxia-selective cytotoxicity, is seen as a way forward to develop clinically useful bioreductive drugs against chemo- and radiation-resistant hypoxic tumor cells. Our previous studies point to the formation of an active benzotriazinyl radical following the one-electron reduction of tirapazamine and its elimination of water from the initial reduction intermediate, and have suggested that this species is a cytotoxin. In this paper we have used pulse radiolysis to measure the one-electron reduction potentials of the benzotriazinyl radicals E(B*,H(+)/B) of 30 analogues of tirapazamine as well as the one-electron reduction potentials of their two-electron reduced metabolites, benzotriazine 1-oxides E(B/B*-). The redox dependencies of the back-oxidation of the one-electron reduced benzotriazine 1,4-dioxides by oxygen, their radical prototropic properties and water elimination reactions were found to be tracked in the main by the one-electron reduction potentials of the benzotriazine 1,4-dioxides E(A/A*-). Multiple regression analysis of published aerobic and hypoxic clonogenic cytotoxicity data for the SCCVII murine tumor cell line with the physical chemistry parameters measured in this study, revealed that hypoxic cytotoxicity is dependent on E(B*, H(+)/B) thus providing strong evidence that the benzotriazinyl radicals are the active cytotoxic species in hypoxia, while aerobic cytotoxicity is dependent on E(B/B*-). It is concluded that maximizing the differential ratio between these two controlling parameters, in combination with necessary pharmacological aspects, will lead to more efficacious anticancer bioreductive drugs. 相似文献
352.
Rajeshwari Tiwari Prashant S. Shinde Sreejesh Sreedharan Anik Kumar Dey Katherine A. Vallis Santosh B. Mhaske Sumit Kumar Pramanik Amitava Das 《Chemical science》2021,12(7):2667
Controlled and efficient activation is the crucial aspect of designing an effective prodrug. Herein we demonstrate a proof of concept for a light activatable prodrug with desired organelle specificity. Mertansine, a benzoansamacrolide, is an efficient microtubule-targeting compound that binds at or near the vinblastine-binding site in the mitochondrial region to induce mitotic arrest and cell death through apoptosis. Despite its efficacy even in the nanomolar level, this has failed in stage 2 of human clinical trials owing to the lack of drug specificity and the deleterious systemic toxicity. To get around this problem, a recent trend is to develop an antibody-conjugatable maytansinoid with improved tumor/organelle-specificity and lesser systematic toxicity. Endogenous CO is recognized as a regulator of cellular function and for its obligatory role in cell apoptosis. CO blocks the proliferation of cancer cells and effector T cells, and the primary target is reported to be the mitochondria. We report herein a new mitochondria-specific prodrug conjugate (Pro-DC) that undergoes a photocleavage reaction on irradiation with a 400 nm source (1.0 mW cm−2) to induce a simultaneous release of the therapeutic components mertansine and CO along with a BODIPY derivative (BODIPY(PPH3)2) as a luminescent marker in the mitochondrial matrix. The efficacy of the process is demonstrated using MCF-7 cells and could effectively be visualized by probing the intracellular luminescence of BODIPY(PPH3)2. This provides a proof-of-concept for designing a prodrug for image-guided combination therapy for mainstream treatment of cancer.Simultaneous release of two therapeutic reagents, mertansine and CO through photo-induced cleavage of a mitochondria-specific prodrug with improved drug efficacy. 相似文献
353.
Separation of bismuth from beryllium, lead, iron(III), indium, scandium, lanthanum, antimony(III), zirconium, titanium, thorium, vanadium(V), molybdenum(VI), uranium (VI) and chromium(VI) is achieved by selective extraction of bismuth from 0.1M sodium salicylate solution (adjusted to pH 7) into mesityl oxide (MeO). The extracted species is Bi (HOC(6)H(4)COO)(3).3MeO. The results are accurate within +/- 0.5%, with a standard deviation of 0.8%. The separation and determination of bismuth takes only 15 min. 相似文献
354.
Summary A rapid and sensitive method is developed for the solvent extraction of chromium(VI) with mesityl oxide. Chromium(VI) is extracted with pure mesityl oxide from 1 M HCl containing 2.5 M KCl as salting-out agent. The metal from the organic phase is stripped with dilute ammonia and determined photometrically as its dephenylcarbazide complex at 540 nm. Chromium(VI) can be extracted in presence of a large number of ions. Only 30 min are required for complete separation and determination. Average recovery was 98.6 ± 1.4%, the standard deviation ± 1.3% (14.9 g of Cr).
Extraktion von Chrom(VI) mit 4-Methyl-3-penten-2-on und anschlieende photometrische Bestimmung als Diphenylcarbazidkomplex
Zusammenfassung Chrom wird mit reinem Mesityloxid aus 1 M salzsaurer, 2,5 M KCl enthaltender Lösung extrahiert, mit Ammoniaklösung aus der organischen Phase entfernt und photometrisch als Diphenylcarbazidkomplex bei 540 nm bestimmt. Zahlreiche Fremdionen stören die Extraktion nicht. Für Abtrennung und Bestimmung werden 30 min benötigt. Im Durchschnitt wurden 98,6 ± 1,4 % wiedergefunden. Die Standard-abweichung betrug ± 1,3% (für 14,9 g Cr).相似文献
355.
356.
Mukund G. Kulkarni Attrimuni P. Dhondge Ajit S. Borhade Dnyaneshwar D. Gaikwad Sanjay W. Chavhan Yunnus B. Shaikh Vijay B. Ningdale Mayur P. Desai Deekshaputra R. Birhade Mahadev P. Shinde 《Tetrahedron letters》2009,50(20):2411-6599
Application of the Wittig olefination-Claisen rearrangement protocol for the total synthesis of (±)-physostigmine. 相似文献
357.
Boric acid (BO3H3) is an inexpensive, efficient and mild catalyst for the synthesis of 1,1-diacetate (acylal) from the various aromatic and heteroaryl aldehydes with acetic anhydride at room temperature under solvent-free condition. The present method does not involve any hazardous organic solvents or catalysts. This method gives notable advantages such as excellent chemoselectivity, mild reaction condition, short reaction times and excellent yield. 相似文献
358.
Synthesis of three novel phenyl(1H-benzoimidazol-5-yl)methanone based fluorescent monoazo disperse dyes and their characterization by spectroscopic methods (1H NMR, 13C NMR, IR and MS) are presented. Insertion of phenyl(1H-benzoimidazol-5-yl)methanone moiety bring about induced fluorescence properties and enhanced photostability as compared to the previously reported analogues (CI Solvent Yellow 14, 4-diethylamino-2-hydroxy-1-diazobenzene and 7-(diethylamino)-4-hydroxy-3-(phenyldiazenyl)-2H-chromen-2-one). Synthesized phenyl(1H-benzoimidazol-5-yl)methanone based dyes exhibited red-shifted absorption maxima (497–516 nm), high molar extinction coefficients and are emitting in the far-red region (565–627 nm). Moreover, naphthalene-comprising dyes showed negative solvatochromism while N,N-diethylamine comprising dyes showed positive solvatochromism and are in good agreement with solvent polarity graphs and the computed energy levels of highest occupied and lowest unoccupied molecular orbitals. Synthesised dyes have better photostability (light fastness) and sublimation fastness on dyed polyester and nylon compared to reported analogues. DFT calculated energies, electrophilicity index and Frontier Molecular Orbitals (FMO’s) enabled to evaluate the stabilities of azo and hydrazone forms of the dyes. 相似文献
359.
The effect of residual oxygen impurity on ionization processes of Si+ and Si2+ has been studied quantitatively. In this study, ion sputtering experiments were carried out for a Si(1 1 1)-7 × 7 surface, irradiated with 9-11 keV Ar0 and Kr0 beam. Even if the oxygen concentration is less than the detection limit of Auger electron spectrometry, SiO+ and SiO2+ ions have been appreciably observed. Moreover, as the SiO+ and SiO2+ yields increases, the Si+ yield is slightly enhanced, whereas the Si2+ yield is significantly reduced. From the incidence angle dependence of secondary ion yields, it is confirmed that Si+* (Si+ with a 2p hole) created in the shallow region from the surface exclusively contributes to Si2+ formation. By assuming that the SiO+ and SiO2+ yields are proportional to the residual oxygen concentration, these observations are reasonably explained: The increase of Si+ with the increase of residual oxygen is caused by a similar effect commonly observed for oxidized surfaces. The decrease of Si2+ yield can be explained by the inter-atomic Auger transition between the residual oxygen impurity and Si+*, which efficiently interferes the Si2+ formation process. 相似文献
360.
Rashmi Mahajan Mona Rouhi Sudhirkumar Shinde Thomas Bedwell Anil Incel Liliia Mavliutova Sergey Piletsky Ian A. Nicholls Brje Sellergren 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(3):737-740
We report an approach integrating the synthesis of protein‐imprinted nanogels (“plastic antibodies”) with a highly sensitive assay employing templates attached to magnetic carriers. The enzymes trypsin and pepsin were immobilized on amino‐functionalized solgel‐coated magnetic nanoparticles (magNPs). Lightly crosslinked fluorescently doped polyacrylamide nanogels were subsequently produced by high‐dilution polymerization of monomers in the presence of the magNPs. The nanogels were characterised by a novel competitive fluorescence assay employing identical protein‐conjugated nanoparticles as ligands to reversibly immobilize the corresponding nanogels. Both nanogels exhibited Kd<10 pM for their respective target protein and low cross‐reactivity with five reference proteins. This agrees with affinities reported for solid‐phase‐synthesized nanogels prepared using low‐surface‐area glass‐bead supports. This approach simplifies the development and production of plastic antibodies and offers direct access to a practical bioassay. 相似文献