Stereo-controlled anti-hydromagnesiation of aryl alkynes by magnesium hydrides

A concise protocol for anti-hydromagnesiation of aryl alkynes was established using 1 : 1 molar combination of sodium hydride (NaH) and magnesium iodide (MgI₂) without the aid of any transition metal catalysts. The resulting alkenylmagnesium intermediates could be trapped with a series of electrophiles, thus providing facile accesses to stereochemically well-defined functionalized alkenes. Mechanistic studies by experimental and theoretical approaches imply that polar hydride addition from magnesium hydride (MgH₂) is responsible for the process.

Anti-hydromagnesiation of aryl alkynes was facilitated solely by magnesium hydride. The resulting alkenylmagnesium intermediates were functionalized with various electrophiles to afford stereochemically defined tri-substituted alkenes.     

Carbodicarbene: geminal-Bimetallic Coordination in Selective Manner

The reaction of Pd(OAc)₂ with free carbodicarbene (CDC) generates a Pd acetate trinuclear complex 1 via intramolecular C(sp³)−H bond activation at one of the CDC methyl side arms. The solid structure of 1 reveals the capability of CDC to facilitate a double dative bond with two palladium centers in geminal fashion. This is attributed to the chelating mode of CDC, which can frustrate π-conjugation within the CDC framework. Such effect maybe also amplified by ligand-ligand interaction. The formation of other gem-bimetallic Pd−Pd, Pd−Au, and Ni−Au provides further structural evidence for this proof-of-concept in selective installation. Structural analysis is supported by computational calculations based on state-of-the-art energy decomposition analysis (EDA) in conjunction with natural orbitals for chemical valence (NOCV) method.     

多晶Sr2Fe1－xAlxMoO6的晶粒内低场磁电阻效应

用传统的固相反应法合成了Fe位掺杂Al的双钙钛矿型氧化物Sr2Fe1-xAlxMoO6 (x=00，005，010，015，03)多晶材料. x射线衍射和扫描电子显微分析显示，在Fe位掺杂Al既没有引入杂相，也没有明显改变Sr2FeMoO6多晶材料的晶粒尺寸和晶界状态. 非磁性Al离子的掺杂使晶粒内部磁有序区细化成更小的区域，同时使反铁磁区内的磁耦合作用变弱. 这一方面提高了亚铁磁区磁化方向的磁场灵敏度；另一方面也降低了反铁磁区对自旋相关电子的散射；两方面的共同作用使Sr2FeMoO6的低场磁电阻效应明显增强，但这种尺寸效应也使材料的磁电阻在高温下下降得更快. 关键词： 低场磁电阻 掺杂 自旋极化电子     

When is the range of a normal operator invariant?

It is proved that if an operator (or a set of operators) leaves the ranges of the spectral projections corresponding to certain subsets of the spectrum of a normal operator, then the operator (respectively, set of operators) leaves the range of the normal operator invariant. This strengthens a result of Peligrad [4].     

Mechanical anisotropy in rolled nylon 66

The nine independent stiffness constants C_pq for rolled nylon 66 at thickness reduction ratios λt = 2.4, 4.9, 7.6 have been measured from ?40 to 50°C by an ultrasonic method at 10 MHz. Analysis of x-ray pole figures indicates that at high λt the material has a uniplanar-axial texture, with hydrogen-bonded (010) planes parallel to the roll plane and the molecular chains along the roll direction. The mechanical behavior is determined not only by the alignment of molecular chains and hydrogen bonds but also by the microfibrillar morphology. On the basis of this idea the magnitudes of the tensile moduli along the three principal axes can be understood in terms of the Takayanagi model. The effects of water absorption have also been investigated.     

Pressurized liquid extraction of berberine and aristolochic acids in medicinal plants

Berberine and aristolochic acids I and II present naturally in medicinal plants were extracted using a laboratory-made pressurized liquid extraction (PLE) system in the dynamic mode. As the target analytes were present naturally in the medicinal plants, spiking was not done and comparison with ultrasonic extraction and Soxhlet extraction was performed to assess the method accuracy. The effect of temperature, volume of solvent required and particle size were investigated. Method precision (RSD, n=5) between 1.98 and 3.4% was achieved for the extraction of berberine and aristolochic acids I and II in medicinal plants and lower than 8% for lower levels of aristolochic acid II in medicinal plants.     

Trace analysis of vanadium as pentavalent vanadium using differential pulse polarography with a coupled catalytic homogeneous reaction

The differential pulse polarographic determination of the vanadium (V) ion coupled with a catalytic homogeneous reaction was carried out in a system containing the vanadium (V)-PAR complex and an oxidant in acetic/acetate buffer. On addition of the powerful oxidant, sodium bromate, the peak current for the reduction of the vanadium (V) complex was increased significantly by about 21 times. A calibration plot was found to be linear in the concentration range 0.05–0.25 g/ml and the detection limit was 5 ng/ml.