Concerted and Selective Electrooxidation of Polyethylene-Terephthalate-Derived Alcohol to Glycolic Acid at an Industry-Level Current Density over a Pd−Ni(OH)2 Catalyst

Electro-reforming of Polyethylene-terephthalate-derived (PET-derived) ethylene glycol (EG) into fine chemicals and H₂ is an ideal solution to address severe plastic pollution. Here, we report the electrooxidation of EG to glycolic acid (GA) with a high Faraday efficiency and selectivity (>85 %) even at an industry-level current density (600 mA cm⁻² at 1.15 V vs. RHE) over a Pd−Ni(OH)₂ catalyst. Notably, stable electrolysis over 200 h can be achieved, outperforming all available Pd-based catalysts. Combined experimental and theoretical results reveal that 1) the OH* generation promoted by Ni(OH)₂ plays a critical role in facilitating EG-to-GA oxidation and removing poisonous carbonyl species, thereby achieving high activity and stability; 2) Pd with a downshifted d-band center and the oxophilic Ni can synergistically facilitate the rapid desorption and transfer of GA from the active Pd sites to the inactive Ni sites, avoiding over-oxidation and thus achieving high selectivity.     

Diastereoselective Synthesis, Spectroscopy, and Electrochemistry of Ruthenium(II) Complexes of Substituted Pyrazolylpyridine Ligands

We report the synthesis of the hetero- and homoleptic ruthenium(II) complexes Ru(bpy)(2)L(2+), Ru(bpy)L(2)(2+) (bpy is 2,2'-bipyridine), and RuL(3)(2+) of six new bidentates L, the substituted pyrazolylpyridines 1-6 (1-substituted-3-(2-pyridinyl)-4,5,6,7-tetrahydroindazoles with substituents R = H, CH(3), Ph, or C(6)H(4)-4"-COOX where X = H, CH(3), or C(2)H(5)). These were fully characterized by (1)H- and (13)C-NMR spectroscopy and elemental analysis. The UV-visible spectra and redox properties of the complexes, some in the ruthenium(III) and reduced bipyridine oxidation states, are also discussed. The substituents R played a role in determining the stereochemistry of the Ru(bpy)L(2)(2+) and RuL(3)(2+) products. The reaction of Ru(DMSO)(4)Cl(2) with 3 equiv of L bearing aromatic substituents gave only meridional RuL(3)(2+) isomers. The one-step reaction of Ru(bpy)Cl(3).H(2)O with 2 equiv of L provided a mixture of the three possible Ru(bpy)L(2)(2+) isomers, from which one symmetric isomer (labeled beta) was isolated pure. A trans arrangement of the pyrazole groups was deduced by (1)H-NMR and confirmed by X-ray crystallography for one such stereomer (beta-[Ru(bpy)(5)(2)](PF(6))(2), R = C(6)H(4)-4"-COOC(2)H(5)). In contrast, Ru(DMSO)(4)Cl(2) reacted with 2 equiv of L and then 1 equiv of bpy to selectively form the other symmetric isomer (labeled alpha) where the pyridine groups of L are trans. Crystal data for beta-[Ru(bpy)(5)(2)](PF(6))(2) (C(52)H(50)N(8)O(4)F(12)P(2)Ru) with Mo Kalpha (lambda = 0.710 73 ?) radiation at 295 K: a = 28.442(13) ?, b = 18.469(15) ?, c = 23.785(9) ?, beta = 116.76(0) degrees, monoclinic, space group C2/c, Z = 8. Fully anisotropic (except for H and disordered F atoms), full-matrix, weighted least-squares refinement on F(2) gave a weighted R on F(2) of 0.2573 corresponding to R on F of 0.1031 for data where F > 4sigma(F ).     

滞止旋流火焰合成纳米TiO_2颗粒的实验研究

湍流效应是火焰合成纳米TiO2颗粒工业化规模放大的一个重要影响因素.本文基于一种新提出的滞止旋流火焰开展了合成TiO2纳米颗粒的实验研究.在旋流数0.26的条件下,可成功获得比表面积300㎡/g以上,粒径最小达5nm的锐钛矿型TiO2颗粒,这可归因于本文滞止旋流火焰具有贫燃稳定性、速度高反应快、温度梯度大等特点.实验还...     

Temperature dependence of the sensitivity of a long-range surface plasmon optical sensor

The temperature dependence of the sensitivity of an optical sensor based on long-range surface plasmon resonance (LRSPR) is studied via theoretical modeling. Both the ‘angular interrogation’ and the ‘wavelength interrogation’ modes of operation are studied. In addition, the variation of the full width at half maximum of the LRSPR ‘reflectance dip’ is also studied as a function of temperature, which ultimately determines the temperature dependence of the sensitivity of the sensor when the reflectance is monitored at a fixed incident angle (‘reflectance interrogation’). It is found that while most of the time only the ‘reflectance interrogation’ mode leads to improved sensitivity for the LRSPR sensor compared to a conventional SPR sensor, the temperature stability of the operation of the LRSPR sensor is generally higher than (or at least comparable to) that of the SPR sensor. PACS 73.20.Mf; 07.07.Df     

The cumulative quantile regression function with censored and truncated covariate

In this paper, we consider the empirical estimator of the cumulative quantile regression (CQR) functionwhen the covariate is subjected to random truncation and censorship. Strong Gaussian approximations for the associated CQR process are established under appropriate assumptions. A functional law of the iterated logarithm for the CQR process is also derived. These results provide a foundation for the asymptotic theory of functional statistics based on these processes.     

参数共振微扰法在Boost变换器混沌控制中的实现及其优化

参数共振微扰法是一种简单的非反馈混沌控制方法，它十分适合非自治系统的混沌控制.研究了这种方法在电流模式控制Boost变换器混沌控制中的应用，并通过对扰动相位进行优化 ，达到最优的混沌控制结果.同时对参数共振微扰法及其优化方法在Boost变换器混沌控制中的作用进行了理论分析，推导并计算了各种电路参数变化对有效的混沌控制所需的扰动的影响. 关键词： Boost变换器 混沌 混沌控制 参数共振微扰法     

Complex network structure of musical compositions: Algorithmic generation of appealing music

In this paper we construct networks for music and attempt to compose music artificially. Networks are constructed with nodes and edges corresponding to musical notes and their co-occurring connections. We analyze classical music from Bach, Mozart, Chopin, as well as other types of music such as Chinese pop music. We observe remarkably similar properties in all networks constructed from the selected compositions. We conjecture that preserving the universal network properties is a necessary step in artificial composition of music. Power-law exponents of node degree, node strength and/or edge weight distributions, mean degrees, clustering coefficients, mean geodesic distances, etc. are reported. With the network constructed, music can be composed artificially using a controlled random walk algorithm, which begins with a randomly chosen note and selects the subsequent notes according to a simple set of rules that compares the weights of the edges, weights of the nodes, and/or the degrees of nodes. By generating a large number of compositions, we find that this algorithm generates music which has the necessary qualities to be subjectively judged as appealing.     

Liquid chromatography/atmospheric pressure chemical ionization tandem mass spectrometry enantiomeric separation of dl-threo-methylphenidate, (Ritalin) using a macrocyclic antibiotic as the chiral selector.

Vancomycin, a macrocyclic antibiotic, is an amphoteric glycopeptide produced by Streptomyces orientalis which has proven to be a viable chiral selector for high performance liquid chromatograph (HPLC) (D. W. Armstrong, Y. Tang, S. Chen, Y. Zhou, C. Bagwill and J-R. Chen, Anal. Chem. (1994; 66: 1473). While it is related to other glycopeptide antibiotics, vancomycin has a number of unique structural features, including 18 stereogenic centers, five aromatic rings, and two side chains one of which is a carbohydrate dimer. Therefore, a vancomycin-based stationary phase appears to be multimodal in that it can be utilized in both normal-phase and reversed-phase liquid chromatography. Consequently, the enantiomeric separation may be operative via several mechanisms, including pi-pi complexation, dipole stacking, inclusion, hydrogen bonding, or combinations of these interactions. LC/MS/MS is a powerful tool for quantitative analysis when evaluated on the basis of speed, specificity, reliability and sensitivity. For these reasons, the present paper explored the feasibility of bonded macrocyclic glycopeptide phases for chiral LC/MS/MS quantitative analysis. Methylphenidate was used as a model compound. A rapid chiral bioanalytical method (<7.5 min) for the determination of the enantiomers of methylphenidate was developed. A lower limit of quantification (LLOQ) of 87 pg/mL was attained for the human plasma assay. This is to our knowledge the first example of enantioselective reversed-phase LC/MS/MS for methylphenidate. The chiral column was relatively cost effective and exhibited excellent performance with no separation deterioration observed after approximately 2500 injections.     

Synthesis of Eburnamine,Isoeburnamine, and Eburnamonine via a Spirocyclic Intermediate

Racemic eburnamonine ( 1 ) was synthesized via 6 , an intermediate possessing local symmetry. Cleavage of the cyclopentene subunit led to pentacyclic aldehydes 8a / 8b which on subsequent borohydride and Wolff–Kishner reductions gave 12 . The final steps included a RuCl₃‐catalyzed periodate oxidation and pyridinium chlorochromate (PCC) oxidation. The penultimate intermediates were racemic eburnamine ( 2 ) and racemic isoeburnamine ( 3 ).