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1.
Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides 下载免费PDF全文
Anna Ulmer Dr. Maciej Stodulski Stefanie V. Kohlhepp Christoph Patzelt Dr. Alexander Pöthig Dr. Wolfgang Bettray Dr. Tanja Gulder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1444-1448
A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions. 相似文献
2.
Dr. Amineh Aghabali Sharon Jun Prof. Dr. Marilyn M. Olmstead Prof. Dr. Alan L. Balch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18908-18915
The photochemical reaction of piperazine with C70 produces a mono‐adduct (N(CH2CH2)2NC70) in high yield (67 %) along with three bis‐adducts. These piperazine adducts can combine with various Lewis acids to form crystalline supramolecular aggregates suitable for X‐ray diffraction. The structure of the mono‐adduct was determined from examination of the adduct I2N(CH2CH2)2NI2C70 that was formed by reaction of N(CH2CH2)2NC70 with I2. Crystals of polymeric {Rh2(O2CCF3)4N(CH2CH2)2NC70}n?nC6H6 that formed from reaction of the mono‐adduct with Rh2(O2CCF3)4 contain a sinusoidal strand of alternating molecules of N(CH2CH2)2NC70 and Rh2(O2CCF3)4 connected through Rh?N bonds. Silver nitrate reacts with N(CH2CH2)2NC70 to form black crystals of {(Ag(NO3))4(N(CH2CH2)2NC70)4}n?7nCH2Cl2 that contain parallel, nearly linear chains of alternating (N(CH2CH2)2NC70 molecules and silver ions. Four of these {Ag(NO3)N(CH2CH2)2NC70}n chains adopt a structure that resembles a columnar micelle with the ionic silver nitrate portion in the center and the nearly non‐polar C70 cages encircling that core. Of the three bis‐adducts, one was definitively identified through crystallization in the presence of I2 as 12{N(CH2CH2)2N}2C70 with addends on opposite poles of the C70 cage and a structure with C2v symmetry. In 12{I2N(CH2CH2)2N}2C70, individual 12{I2N(CH2CH2)2N}2C70 units are further connected by secondary I2???N2 interactions to form chains that occur in layers within the crystal. Halogen bond formation between a Lewis base such as a tertiary amine and I2 is suggested as a method to produce ordered crystals with complex supramolecular structures from substances that are otherwise difficult to crystallize. 相似文献
3.
《Mendeleev Communications》2022,32(3):395-396
A new method for assembling 1,3-selenazolines by the iodine- mediated reaction of the simplest building blocks such as elemental selenium, alkenes and acetonitrile has been discovered. A proposed mechanism includes the addition of the intermediate selenium iodides to alkene with subsequent solvent interception by the formed seleniranium ion. 相似文献
4.
Xiao-Guang Yang Feng-Huan Du Jun-Jie Li Prof. Dr. Chi Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(27):e202200272
The development of convenient new methods for the synthesis of organic azides is highly desirable. Herein, we report a practical method for dehydroxyazidation of alcohols via an SN2 pathway involving PPh3 and trifunctional benziodazolone-based hypervalent azido-iodine(III) reagents, which function as an electrophilic center, an azido source, and a base. This mild, chemoselective method was used for late-stage azidation of structurally complex alcohols, as well as for a new synthetic route to the antiepileptic drug rufinamide. The reaction mechanism was also investigated both experimentally and computationally. 相似文献
5.
Dr. Huaiyuan Zhang Prof. Dr. Rodrigo A. Cormanich Prof. Dr. Thomas Wirth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(5):e202103623
Several novel binaphthyl-based chiral hypervalent iodine(III) reagents have been prepared and structurally analysed. Various asymmetric oxidative reactions were applied to evaluate the reactivities and stereoselectivities of those reagents. Moderate to excellent yields were observed; however, very low stereoselectivities were obtained. NMR experiments indicated that these reagents are very easily hydrolysed in either chloroform or DMSO solvents leading to the limited stereoselectivities. It is concluded that the use of chiral ligands is an unsuccessful way to prepare efficient stereoselective iodine(III) reagents. 相似文献
6.
7.
Romain Tessier Raj Kumar Nandi Brendan G. Dwyer Daniel Abegg Charlotte Sornay Javier Ceballos Stphane Erb Sarah Cianfrani Alain Wagner Guilhem Chaubet Alexander Adibekian Jerome Waser 《Angewandte Chemie (International ed. in English)》2020,59(27):10961-10970
Current approaches to introduce terminal alkynes for bioorthogonal reactions into biomolecules still present limitations in terms of either reactivity, selectivity, or adduct stability. We present a method for the ethynylation of cysteine residues based on the use of ethynylbenziodoxolone (EBX) reagents. The acetylene group is directly introduced onto the thiol group of cysteine and can be used for copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) without further processing. Labeling proceeded with reaction rates comparable to or higher than the most often used iodoacetamide on peptides or maleimide on the antibody trastuzumab, and high cysteine selectivity was observed. The reagents were also used in living cells for cysteine proteomic profiling and displayed improved coverage of the cysteinome compared to previously reported iodoacetamide or hypervalent iodine reagents. Fine‐tuning of the EBX reagents allows optimization of their reactivity and physical properties. 相似文献
8.
针对我国氧碘化学激光器输出能量不断提高的情况下,主要限制光束质量的因素之一是出光过程中的光腔失调,提出了一种基于图像处理的光学谐振腔自准直研究方法。该研究方法利用氦氖穿腔光通过凹腔镜中心孔,并在凸腔镜后方放置工业相机,在屏幕上方形成一个干涉同心圆环。通过借助OpenCV库中二值化、霍夫圆检测等图像处理的方法,获得干涉同心圆环的圆心坐标,再通过以圆心为中心将图像分成上下左右四个部分,通过判断这四部分亮点像素的数量差值来预估干涉同心圆环的偏移状态,进而获得空腔条件下光学谐振腔发生变化的理论判据。实验结果表明,该方法可以获得相当精准的光学谐振腔失调判据,其失调判据选取左右亮点像素差值30000,上下亮点像素差值45000,为今后失调判据与步进电机自动调腔的结合做好充足的准备。 相似文献
9.
Guillaume Pisella Alec Gagnebin Prof. Dr. Jérôme Waser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(45):10199-10204
Multicomponent reactions provide efficient means to access molecular complexity. Herein, we report a copper-catalyzed three-component reaction of diazo compounds, alcohols and ethynyl benziodoxole (EBX) reagents for the synthesis of propargyl ethers. Extensive variations of the three partners of the reaction is possible, leading to highly functionalized and structurally diverse products under mild conditions. Alkynylation of a copper ylide intermediate is postulated as key step for this transformation. 相似文献
10.
Honghua Zhang Huihong Wang Yi Jiang Fei Cao Weiwei Gao Longqing Zhu Yuhang Yang Xiaodong Wang Yongqiang Wang Jinhong Chen Yiyue Feng Xuemei Deng Yingmei Lu Xiaoling Hu Xiangxiang Li Juan Zhang Tao Shi Prof. Zhen Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17289-17317
Sulfur-containing scaffold, as a ubiquitous structural motif, has been frequently used in natural products, bioactive chemicals and pharmaceuticals, particularly C−S/N−S bonds are indispensable in many biological important compounds and pharmaceuticals. Development of mild and general methods for C−S/N−S bonds formation has great significance in modern research. Iodine and its derivatives have been recognized as inexpensive, environmentally benign and easy-handled catalysts or reagents to promote the construction of C−S/N−S bonds under mild reaction conditions, with good regioselectivities and broad substrate scope. Especially based on this, several new strategies, such as oxidation relay strategy, have been greatly developed and accelerated the advancement of this field. This review focuses on recent advances in iodine and its derivatives promoted hybridized C−S/N−S bonds formation. The features and mechanisms of corresponding reactions are summarized and the results of some cases are compared with those of previous reports. In addition, the future of this domain is discussed. 相似文献