PtII-Catalyzed Hydroxylation of Terminal Aliphatic C(sp3)−H Bonds with Molecular Oxygen

The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing Pt^IV with a more economically viable oxidant, particularly O₂. We report the potential of employing FeCl₂ as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O₂ in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O₂ in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt⁰ was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N₂ in the gaseous atmosphere. Finally, stability tests revealed the involvement of Pt^II and FeCl₂ in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O₂ is presented.     

Directing-Group-Free C7-Alkylations of N-Alkylindoles Mediated by Cationic Zirconium Complexes: Role of Brønsted Acid for Catalytic Manifold

Highly position selective alkylations of N-alkylindoles at C7-positions have been enabled by cationic zirconium complexes. The strategy provides a straightforward access to install alkyl groups at C7-positions of indoles without a complex directing group. Mechanistic studies provided support for the importance of Brønsted acids in the catalytic manifold.     

Patterns and Symmetries in the Visual Cortex and in Natural Images

As borders between different entities, lines are an important element of natural images. Indeed, the neurons of the mammalian visual cortex are tuned to respond best to lines of a given orientation. This preferred orientation varies continuously across most of the cortex, but also has vortex-like singularities known as pinwheels. In attempting to describe such patterns of orientation preference, we are led to consider underlying rotation symmetries: Oriented segments in natural images tend to be collinear; neurons are more likely to be connected if their preferred orientations are aligned to their topographic separation. These are indications of a reduced symmetry requiring joint rotations of both orientation preference and the underlying topography. This is verified by direct statistical tests in both natural images and in cortical maps. Using the statistics of natural scenes we construct filters that are best suited to extracting information from such images, and find qualitative similarities to mammalian vision. PACS84.35+i 89.70.+c 87.57.Nk     

增湿活化反应器内喷水脱硫试验研究

本文介绍在热态脱硫试验台上进行的生石灰和消石灰的喷水活化脱硫试验,研究了Ca/S比、饱和温距、入口烟气SO2浓度、烟气速度及水喷嘴雾化风对脱硫效率和钙利用率的影响规律,对两种脱硫剂的脱硫活性进行了比较,并对喷水增湿提高脱硫效率的机理进行了分析。研究表明,喷水增湿使两种脱硫剂的活性都有明显提高,生石灰具有价格优势。     

强流脉冲高斯分布束在磁四极透镜中的非线性传输

用李代数方法分析了高斯分布下强流脉冲束在磁四极透镜中的非线性传输.在高斯分布下,束流的空间电荷势可利用Green函数算出,进而可以得到包含束流自场的粒子运动的Hamilton函数.再施加李变换,就可以得到粒子运动的各级近似解.本文给出二级近似下的结果,根据需要,还可以扩展到更高级近似.计算过程需要进行迭代,即根据每次算出的轨迹值,确定束团在三维实空间中的大小,然后再进行迭代,直到满足精度要求为止.     

Radiochemical proton activation analysis for the determination of cadmium and lead in sediment reference materials

Proton activation analysis was used for the determination of cadmium and lead in three sediment reference materials. The method is based on the^111,112Cd(p, xn)¹¹¹ In and the^206,207,208Pb(p, xn)²⁰⁶Bi reactions.¹¹¹In and²⁰⁶Bi were chemically separated by anion exchange. The results obtained were taken into account for the certification of the materials and are in the excellent agreement with the certified values.     

Cyclic permutations and evolutionary trees

Given a tree with leaf set X, there are certain ways of arranging the elements of X in a circular order so that can be embedded in the plane and ‘preserve’ this ordering. We investigate some new combinatorial properties of these ‘circular orderings.’ We then use these properties to establish two results concerning dissimilarity maps on X that are induced by edge-weighted trees with leaf set X.     

Regular Balanced Cayley Maps for Cyclic, Dihedral and Generalized Quaternion Groups

A Cayley map is a Cayley graph embedded in an orientable surface such that. the local rotations at every vertex are identical. In this paper, balanced regular Cayley maps for cyclic groups, dihedral groups, and generalized quaternion groups are classified.     

A novel tridentate nitrogen donor as ligand in copper catalyzed ATRP of methyl methacrylate

A tridentate ligand, BPIEP: 2,6‐bis[1‐(2,6‐diisopropyl phenylimino) ethyl] pyridine, having central pyridine unit and two peripheral imine coordination sites was effectively employed in controlled/“living” radical polymerization of MMA at 90°C in toluene as solvent, Cu^IBr as catalyst, and ethyl‐2‐bromoisobutyrate (EBiB) as initiator resulting in well‐defined polymers with polydispersities M_w/M_n ≤ 1.23. The rate of polymerization follows first‐order kinetics, k_app = 3.4 × 10^?5 s^?1, indicating the presence of low radical concentration ([P*] ≤ 10^?8) throughout the reaction. The polymerization rate attains a maximum at a ligand‐to‐metal ratio of 2:1 in toluene at 90°C. The solvent concentration (v/v, with respect to monomer) has a significant effect on the polymerization kinetics. The polymerization is faster in polar solvents like, diphenylether, and anisole, as compared to toluene. Increasing the monomer concentration in toluene resulted in a better control of polymerization. The molecular weights (M_n,SEC) increased linearly with conversion and were found to be higher than predicted molecular (M_n,Cal). However, the polydispersity remained narrow, i.e., ≤1.23. The initiator efficiency at lower monomer concentration approaches a value of 0.7 in 110 min as compared to 0.5 in 330 min at higher monomer concentration. The aging of the copper salt complexed with BPIEP had a beneficial effect and resulted in polymers with narrow polydispersitities and higher conversion. PMMA obtained at room temperature in toluene (33%, v/v) gave PDI of 1.22 (M_n = 8500) in 48 h whereas, at 50°C the PDI is 1.18 (M_n = 10,300), which is achieved in 23 h. The plot of lnk_app versus 1/T gave an apparent activation energy of polymerization as (ΔE^≠_app) 58.29 KJ/mol and enthalpy of equilibrium (ΔH⁰_eq) to 28.8 KJ/mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4996–5008, 2005     

Dynamics of the periodic type-K competitive Kolmogorov systems

For time-periodic dissipative and irreducible type-K competitive Kolmogorov systems, it is proved that there is a canonically defined countable family F of unordered, disjoint invariant sets with the property that, for every persistent trajectory whose ω-limit set is not a cycle, there exists a unique trajectory in some element of F such that these two trajectories are asymptotic and the corresponding points in these two trajectories are K-related.