Cu/Fe‐Cocatalyzed Formation of β‐Ketophosphonates by a Domino Knoevenagel–Decarboxylation–Oxyphosphorylation Sequence from Aromatic Aldehydes and H‐Phosphonates

A domino Knoevenagel–decarboxylation–alkene difunctionalization sequence has been developed for the conversion of benzaldehydes into β‐ketophosphonates, catalyzed by a cooperative Cu/Fe system, whereby C?P and C?O bonds are formed simultaneously in a one‐pot reaction. The reaction proceeds in good yields and with a broad substrate scope and environmentally benign conditions.     

Microwave-accelerated derivatization prior to GC-MS determination of sex hormones

A new microwave-accelerated derivatization method was developed for rapid determination of 13 natural sex hormones in feeds. Sex hormones were isolated from the sample matrix by ultrasonic extraction, followed by solid-phase extraction, derivatized under microwave irradiation, and then analyzed directly by gas chromatography-mass spectrometry (GC-MS) in selective ion monitoring (SIM) mode. The key parameters affecting derivatization efficiency, including microwave irradiation time, microwave power, and reaction solvent were studied. Under microwave power of 360 W and microwave irradiation for 3 min, 13 natural sex hormones were simultaneously derivatized using heptafluorobutyric acid anhydride (HFBA) as derivatization reagent. This method was applied to the determination of 13 natural sex hormones in different feed samples, and the obtained results were compared with those obtained by the traditional thermal derivatization. The recoveries from 58.1 to 111% were obtained at sex hormone concentrations of 10-300 μg/kg with RSDs ≤12.0%. The results showed that the proposed method was fast, simple, efficient and can be applied to the determination of 13 natural sex hormones in different feed samples.     

A new method to calculate corneal ablation depth based on optical individual eye model

The corneal shape, axial lengths and the wavefront aberrations of the eye were all considered to calculate the ablation depth based on the individual eye model. The optimization method for the curves surface replaced the direct calculation from only the optical path difference method (OPD). We analyzed the eye's optical system on its exit pupil and offered the optimum corneal anterior surface. And the ablation depth was the difference between the pre- and post-optimization along the optical axis of the eye. In our experiment, the maximum ablation depth decreases by 8.5% and the mean ablation depth decreases by 8.2% compared with the OPD method.     

Al and/or Ni-doped nanomanganese dioxide with anisotropic expansion and their electrochemical characterisation in primary Li–MnO2 batteries

A variety of MnO₂ nanorods containing one or two transition metals (M) (with M?=?Al and/or Ni) have been successfully synthesised via a facile hydrothermal synthesis route. The physical–chemical properties and electrochemical performance of manganese oxide were analysed by X-ray diffraction (XRD), inductively coupled plasma atomic emission spectrometry (ICP-OES), Fourier transform infrared spectrometer (FT-IR), scanning electron microscopy (SEM), Brunauer–Emmett–Teller method (BET), galvanostatic discharge and cyclic voltammetry (CV). The result indicated that α-type MnO₂ was obtained, and a small quantity of Al and/or Ni were embedded into the crystal lattice of manganese oxide instead of the partial Mn ion, which resulted in anisotropic expansion of the MnO₂ unit cell. The doping of Al can strengthen Mn–O bonds in the [MnO₆] octahedral and increases the specific surface area of the modified material (i.e., Al–MnO₂ is 119 m² g^?1). Interestingly, MnO₂ electrode co-doped with equimolar Al and Ni exhibited the highest specific capacity of 169 mAh g^?1 at 0.05 mA cm^?2. The substantial enhancement of the electrochemical lithium storage capacity was due to the ameliorating of integrative factors, such as high specific surface area, excellent lattice parameters and lower electrical resistance, as well as short Li⁺ and electron transport length. In addition, a more stable host skeleton also guaranteed an endurable Li⁺ intercalation behaviour during the discharge process.     

NOVEL SYNTHESIS OF ULTRAFINE HOURGLASS-SHAPED ALUMINUM HYDROXIDE PARTICLES

In a novel method for synthesizing ultrafine aluminum hydroxide particles presented in this paper, the morphology and crystal structure of the particles were investigated by TEM, XRD, etc. The process consisted of two steps： chemical precipitation by acid and carbonation. The product has an hourglass or half-hourglass morphology with a narrow size distribution of 150-200 nm. Major endothermal peak of decomposition was found at 270℃ by differential thermal analysis. X-ray diffraction identified the product as bayerite. Those properties were compared with those of alusminum hydroxide prepared by carbonization only.     

广义维纳泛函,白噪声分布及实Schwartz广义函数空间上的分布

在实Ｓｃｈｗａｒｔｚ广义函数空间上，证明了复值广义维纳泛函，由Ｋｏｎｄｒａｔｅｖ－Ｓｔｒｅｉｔ及Ｈｉｄａ构造的复值白噪声分布都是由Ｋｈｒｅｎｎｉｋｏｖ构造的分布。利用上述结果进而证明了，一类无穷维伪微分算子是由复值广义维纳泛函空间上的连续线性算子族扩张而成。更进一步，还证明了由Ｋｈｒｅｎｎｉｋｏｖ构造的关于分布的试验函数空间是关于白噪声泛函的Ｍｅｙｅｒ－Ｙａｎ试验函数空间的子空间。     

1-苯基-3-甲基-5-吡唑啉酮衍生中药寡糖的毛细管区带电泳分离

建立了一种可用于中药寡糖分离的毛细管区带电泳(CZE)分析方法。分离条件: 未涂层熔融石英毛细管柱(48 cm×50 μm,有效长度38 cm),紫外检测波长245 nm,采用1-苯基-3-甲基-5-吡唑啉酮(PMP)为寡糖衍生试剂,50 mmol/L磷酸盐溶液(pH 2.5)为运行缓冲液,电压15 kV,重力进样10 cm×2 s。针对中药寡糖实际样品的复杂性,通过添加多种常见单糖进行方法的实用性验证,并且将方法用于板蓝根多糖的控制降解产物的分离。结果表明,板蓝根寡糖组分可按相对分子质量从小到大的顺序分离,分离效果令人满意。该分离方法操作简单、高效,可用于中药寡糖实际样品分析。另外,还对单糖、寡糖PMP衍生物的电泳迁移行为进行了初步的理论探讨。     

Polyphenyl macrocyclic oligophenylenes

The Diels-Alder reaction of tribenzohexadehydro[12]annulene (12) and 3,4-diphenyl-2,5-dimethylcyclopentadienone (13) at 300 degrees C gave the triple adduct 2,3,10,11,18,19-hexaphenyl-1,4,9,12,17,20-hexamethylhexa-o-phenylene (6b) in 13% yield. NMR and X-ray analysis indicated that 6b adopts a screw conformation (C2) rather than a crown conformation (C3), and computational studies seem to rule out any interconversion of the two. Palladium-catalyzed coupling of 1,2-bis(4-bromophenyl)-3,4,5,6-tetraphenylbenzene (17) and the corresponding bis(boronic acid) 18 gave a mixture of linear and cyclic oligomers of hexaphenylbenzene containing two to six hexaphenylbenzene subunits. A macrocyclic tetramer was isolated from this mixture in 5% yield, and X-ray analysis showed it to be the "supertetraphenylene" 7 (C168H112) that contains a large central cavity and packs to form highly solvated, porous crystals. The difficulties encountered in the purification of 7 led to the development of alternative, more highly selective syntheses that give the pure macrocycle more easily but in essentially the same overall yield.     

Sterically congested in-methylcyclophanes

The crowded in-methylcyclophane 9 was prepared by condensation of 1,8,13-tris(bromomethyl)-9-methyltriptycene and 1,3,5-tris(mercaptomethyl)benzene under high dilution conditions. Oxidation of 9 gave the highly crystalline trisulfone 10, and its X-ray structure was determined. The in-methyl carbon atoms of the two independent molecules in the structure are only 2.90 and 2.87 A from the centroid of the basal aromatic ring, the closest such contacts ever observed. In addition, the C-CH3 bonds in these cyclophanes are compressed; the two independent bond distances are 1.475 and 1.495 A, significantly shorter than the ca. 1.54 A distances found in similar but uncongested molecules.     

Stereoselective synthesis of polysubstituted 2,5-dihydrofurans from reaction of 1,4-dilithio-1,3-dienes with aldehydes

[reaction: see text] Reaction of 1,4-dilithio-1,3-diene derivatives with 2 equiv of aldehydes affords polysubstituted 2,5-dihydrofurans in good to high yields with perfect regio- and stereoselectivities. Hexa-2,4-diene-1,6-dialcoholates are proposed as the first intermediates, which undergo a cyclization and subsequent elimination of Li(2)O to generate the 2,5-dihydrofuran derivatives.