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51.
Yoshiyuki Uchiyama Takahiro Hayasaka Noritaka Masaki Yoshiko Watanabe Kazuma Masumoto Tetsuji Nagata Fuminori Katou Mitsutoshi Setou 《Analytical and bioanalytical chemistry》2014,406(5):1307-1316
Most oral cancers are oral squamous cell carcinoma (OSCC). The anatomical features of OSCC have been histochemically evaluated with hematoxylin and eosin. However, the border between the cancer and stromal regions is unclear and large portions of the cancer and stromal regions are resected in surgery. To reduce the resected area and maintain oral function, a new method of diagnosis is needed. In this study, we tried to clearly distinguish the border on the basis of biomolecule distributions visualized by imaging mass spectrometry (IMS). In the IMS dataset, eleven signals were significantly different in intensity (p?<?0.01) between the cancer and stromal regions. Two signals at m/z 770.5 and m/z 846.6 were distributed in each region, and a clear border was revealed. Tandem mass spectrometric (MS/MS) analysis identified these signals as phosphatidylcholine (PC) (16:0/16:1) at m/z 770.5 in the cancer region and PC (18:1/20:4) at m/z 846.6 in the stromal region. Moreover, the distribution of PC species containing arachidonic acid in the stromal region suggests that lymphocytes accumulated in response to the inflammation caused by cancer invasion. In conclusion, the cancer and stromal regions of OSCCs were clearly distinguished by use of these PC species and IMS analysis, and this molecular identification can provide important information to elucidate the mechanism of cancer invasion. 相似文献
52.
Tomohiro Kuwabara Takahiro Takayama Kenichiro Todoroki Koichi Inoue Jun Zhe Min Toshimasa Toyo’oka 《Analytical and bioanalytical chemistry》2014,406(11):2641-2649
Mass spectrometry has become a popular analytical tool because of its high sensitivity and specificity. The use of a chiral derivatization reagent for the mass spectrometry (MS) detection seems to be efficient for the enantiomeric separation of racemates. However, the number of chiral reagents for the liquid chromatography (LC)–MS/MS analysis is very limited. According to these observations, we are currently in the process of developing novel labeling reagents for chiral molecules in MS/MS analysis. The derivatization reagent that is effective for enhancing not only the electrospray ionization–MS/MS sensitivity but also the reversed-phase LC resolution of carboxylic acid enantiomers should have a highly proton-affinitive moiety and an asymmetric structure near the reactive functional group. Furthermore, the resulting derivative has to provide a characteristic product ion suitable for the selected reaction monitoring. Based upon these considerations, a series of prolylamidepyridines ((S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-2-yl)amide (PCP2), (S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-3-yl)amide, and (S)-N-pyrrolidine-2-carboxylic acid N-(pyridine-4-yl)amide) was synthesized as ideal labeling reagents for the enantioseparation of chiral carboxylic acids and evaluated in terms of separation efficiency and detection sensitivity by ultra-performance LC (UPLC)–MS/MS. Among the synthesized reagents, PCP2 was the most efficient chiral derivatization reagent for the enantioseparation of carboxylic acid. The Rs values and the detection limits of the derivatives of non-steroidal anti-inflammatory drugs, which were selected as the representative carboxylic acids, were in the range of 2.52–6.07 and 49–260 amol, respectively. The sensitive detection of biological carboxylic acids (detection limits, 32–520 amol) was also carried out by the proposed method using PCP2 and UPLC–MS/MS. The PCP2 was applied to the determination of carboxylic acids in human saliva. Several biological carboxylic acids, such as lactic acid (LA), 3-hydroxybutylic acid, maric acid, succinic acid, α-ketoglutalic acid, and citric acid, were clearly identified in the saliva of healthy persons and diabetic patients. Furthermore, the ratio of d-LA in diabetic patients was higher than that in normal subjects. Judging from these results, PCP2 seems to be a useful chiral derivatization reagent for the determination not only of chiral, but also achiral, carboxylic acids in real samples. Figure
Labeling reagent for carboxylic acids in chiral metabolomics study 相似文献
53.
Journal of Mathematical Chemistry - The arrangements of invariant tori that resemble rod packings with cubic symmetries are considered in three-dimensional solenoidal vector fields. To find them... 相似文献
54.
We present a sophisticated optical design method for reducing the number of photodetectors for a specific sensing task. The chosen design parameter is the point spread function, and the selected task is object recognition. The point spread function is optimized iteratively with a genetic algorithm for object recognition based on a neural network. In the experimental demonstration, binary classification of face and non-face datasets was performed with a single measurement using two photodetectors. A spatial light modulator operating in the amplitude modulation mode was provided in the imaging optics and was used to modulate the point spread function. In each generation of the genetic algorithm, the classification accuracy with a pattern displayed on the spatial light modulator was fed-back to the next generation to find better patterns. The proposed method increased the accuracy by about 30 % compared with a conventional imaging system in which the point spread function was the delta function. This approach is practically useful for compressing the cost, size, and observation time of optical sensors in specific applications, and robust for imperfections in optical elements. 相似文献
55.
Shimoda K Tobu Y Shimoikeda Y Nemoto T Saito K 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,186(1):156-159
We here show the (43)Ca 5QMAS NMR spectra at high field (16.4 T) and the first 7QMAS spectrum at ultra-high field (21.8 T) for geologically important Ca-containing glasses. The high-resolution MQMAS spectra present a clear evidence of multiple Ca sites in the amorphous structures that have never been identified by other analytical methods. The present study suggests that the Ca(2+) ions are mainly in 7- and 8-fold coordination sites. This will offer valuable insights for dynamic properties of magmatic liquids. The MQMAS NMR technique at high magnetic field is a unique tool to understand the detailed structural information on a specific element in solids including organic and inorganic compounds. 相似文献
56.
57.
Synergistic Spin Transition between Spin Crossover and Spin‐Peierls‐like Singlet Formation in the Halogen‐Bonded Molecular Hybrid System: [Fe(Iqsal)2][Ni(dmit)2]⋅CH3CN⋅H2O 下载免费PDF全文
Kappei Fukuroi Prof. Dr. Kazuyuki Takahashi Prof. Dr. Tomoyuki Mochida Dr. Takahiro Sakurai Prof. Dr. Hitoshi Ohta Dr. Takashi Yamamoto Prof. Dr. Yasuaki Einaga Prof. Dr. Hatsumi Mori 《Angewandte Chemie (International ed. in English)》2014,53(7):1983-1986
To introduce halogen‐bond interactions between a cation and an anion, a novel FeIII complex from iodine‐substituted ligands involving a paramagnetic nickel dithiolene anion was prepared and characterized. The compound exhibited the synergy between a spin‐crossover transition and a spin‐Peierls‐like singlet formation. The halogen‐bond interactions between the iodine and the sulfur atoms stabilized the paramagnetic state of π‐spins and played a crucial role in the synergistic magnetic transition between d‐ and π‐spins. In addition, the compound showed the light‐induced excited spin state trapping effect. 相似文献
58.
Manganese‐Corrole Complexes as Versatile Catalysts for the Ring‐Opening Homo‐ and Co‐Polymerization of Epoxide 下载免费PDF全文
Dr. Carine Robert Takahiro Ohkawara Prof. Dr. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4789-4795
Manganese‐corrole complexes in combination with a co‐catalyst [PPN]X ([PPN]+=bis(triphenylphosphoranylidene)iminium) were found to be new versatile catalysts for the polymerization of epoxides, copolymerization of epoxides with CO2, and copolymerization of epoxides with cyclic anhydrides affording a wide range of polymeric materials. This work should allow the synthesis of new types of improved innovative (co)polymers with original properties and would clearly increase the number of applications for polyesters, polycarbonates, and polyethers. 相似文献
59.
Facile Synthesis of Dibenzopentalene Dianions and Their Application as New π‐Extended Ligands 下载免费PDF全文
Takuya Kuwabara Dr. Kazuya Ishimura Prof. Dr. Takahiro Sasamori Prof. Dr. Norihiro Tokitoh Prof. Dr. Masaichi Saito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7571-7575
Reduction of phenyl(silyl)ethynes with potassium followed by quenching with iodine gave dibenzopentalenes in moderate yields. The intermediates of the reactions, dipotassium dibenzopentalenides, were isolated. The first dibenzopentalene–transition‐metal complex was successfully synthesized. The ruthenium atoms are located above the six‐membered rings. However, X‐ray diffraction analysis and theoretical calculations revealed that the aromatic nature of the five‐membered rings was retained. The cyclic voltammetry of the Ru complex revealed two oxidation waves with relatively large separation. 相似文献
60.
Takahiro Gunji Kengo Hirama Satoru Tsukada Yoshimoto Abe 《Journal of Sol-Gel Science and Technology》2014,72(1):80-84
An organic–inorganic hybrid was prepared by simply mixing a fullerene derivative with polymethoxysiloxane. First, C60 was subjected to a radical addition reaction with 4,4′-azobis(4-cyanovaleric acid) to provide a C60 derivative. Polymethoxysiloxane was prepared by a controlled hydrolytic condensation of tetramethoxysilane. These two compounds were mixed and heated to provide hybrid bulk body. The hybrid bulk body showed high mechanical strength and elastic modulus compared with polymethoxysiloxane or the C60/polymethoxysiloxane hybrid. The formation of a dense siloxane network was established by a homogeneous mixing of the C60 derivative with polymethoxysiloxane. 相似文献