Rhodium-catalyzed intermolecular amidation of arenes with sulfonyl azides via chelation-assisted C-H bond activation

We report the direct amidation of arene C-H bonds using sulfonyl azides as the amino source to release N(2) as the single byproduct. The reaction is catalyzed by a cationic rhodium complex under external oxidant-free conditions in the atmospheric environment. A broad range of chelate group-containing arenes are selectively amidated with excellent functional group tolerance, thus opening a new avenue to practical intermolecular C-N bond formation.     

Beta‐decomposition for the volume and area of the union of three‐dimensional balls and their offsets

Given a set of spherical balls, called atoms, in three‐dimensional space, its mass properties such as the volume and the boundary area of the union of the atoms are important for many disciplines, particularly for computational chemistry/biology and structural molecular biology. Despite many previous studies, this seemingly easy problem of computing mass properties has not been well‐solved. If the mass properties of the union of the offset of the atoms are to be computed as well, the problem gets even harder. In this article, we propose algorithms that compute the mass properties of both the union of atoms and their offsets both correctly and efficiently. The proposed algorithms employ an approach, called the Beta‐decomposition, based on the recent theory of the beta‐complex. Given the beta‐complex of an atom set, these algorithms decompose the target mass property into a set of primitives using the simplexes of the beta‐complex. Then, the molecular mass property is computed by appropriately summing up the mass property corresponding to each simplex. The time complexity of the proposed algorithm is O(m) in the worst case where m is the number of simplexes in the beta‐complex that can be efficiently computed from the Voronoi diagram of the atoms. It is known in ?³ that m = O(n) on average for biomolecules and m = O(n²) in the worst case for general spheres where n is the number of atoms. The theory is first introduced in ?² and extended to ?³. The proposed algorithms were implemented into the software BetaMass and thoroughly tested using molecular structures available in the Protein Data Bank. BetaMass is freely available at the Voronoi Diagram Research Center web site. © 2012 Wiley Periodicals, Inc.     

Stabilization of Enzyme by Exclusive Volume Effect in Hydrophobically Controlled Polymer Microcapsules

Summary: This communication describes an enzyme stabilization method that allows the use of enzymes irrespective of environmental factors, especially heat, while maintaining their activity for a long time. We have designed enzyme microcapsules that consist of papain enzyme cores, poly(propylene glycol) interlayers, and poly(ε‐caprolactone) walls. By confocal laser scanning microscopy measurements and the thermal stability of papain‐loaded microcapsules, it is demonstrated that the papain is surrounded by a hydrophobic polyol layer and stabilized by the exclusive volume effect. In our study, improved thermal stability can be obtained by using more hydrophobic long‐chained polyols, which is understood to be attributed to the effective formation of a hydrophobic polyol layer between the papain and the polymer wall by means of conformational anchoring in the interface.

(A) A CLSM image of a PCL microcapsule containing FITC‐labeled papain and RBITC‐labeled PPG at the same time. (B) A scheme of the role of hydrophobic polyols in the interface of enzyme and polymer.     

Positive solutions for ratio-dependent predator-prey interaction systems

In this paper, we study the dynamics of predator-prey interaction systems between two species with ratio-dependent functional responses. First we provide sufficient and necessary conditions for positive steady-state solutions, and then we investigate the relationships between positive equilibria and positive solutions of the system over a large domain. Furthermore, we deal with the uniqueness and the stability of positive steady-states solutions with some assumptions. In addition, we discuss the extinction and the persistence results of time-dependent positive solutions to the system.     

Synthesis and characterization of fluorene‐based low‐band gap copolymers containing propylenedioxythiophene and benzothiadiazole derivatives for bulk heterojunction photovoltaic cell applications

The following noble series of soluble π‐conjugated statistical copolymers was synthesized by palladium catalyzed Suzuki polymerization: poly[(9,9‐dioctylfluorene)‐alt‐(4,7‐bis(3′,3′‐dihepyl‐3,4‐propylenedioxythienyl)‐2,1,3‐benzothiadiazole)] (PFO‐PTBT) derived from poly(9,9‐dioctylfluorene) (PFO) and poly[(4,7‐bis(3′,3′‐dihepyl‐3,4‐propylenedioxythienyl)‐2,1,3‐benzothiadiazole)] poly(heptyl₄‐PTBT). The structure and properties of these polymers were characterized using ¹H‐, ¹³C‐NMR, UV–visible spectroscopy, elemental analysis, GPC, DSC, TGA, photoluminescence (PL), and cyclic voltammetry (CV). The statistical copolymers, PFO‐PTBT (9:1, 8.4:1.6, 6.5:3.5), were soluble in common organic solvents and easily spin coated onto indium‐tin oxide (ITO) coated glass substrates. The weight‐average molecular weight (M_w) and polydispersity of the PFO‐PTBT ranged from (1.0–4.2) × 10⁴ and 1.5–2.3, respectively. Bulk heterojunction photovoltaic cells with an ITO/PEDOT/PFO‐PTBT:PCBM/LiF/Al configuration were fabricated, and the devices using PFOPTBT (6.5:3.5) showed the best performance compared with those using PFO‐PTBT (9:1, 8.4:1.6). A maximum power conversion efficiency (PCE) of 0.50% (V_oc = 0.66 V, FF = 0.29) was achieved with PFO‐PTBT (6.5:3.5). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6175–6184, 2008     

Temperature-rise fractionation of poly(3-alkyl thiophenes)

In this article, we have investigated a temperature-rise fractionation procedure for poly(3-hexyl thophene) (P3HT) and poly(3-octyl thophene) (P3OT) that provides well-defined molecular weight (MW) fractions with improved molecular weight distributions (MWD) when compared with Soxhlet extraction. This process involves dispersing the material over C18-boned silica stationary phase in a jacketed column and using incremental rises in column temperature (T_col) to gradually improve solvent quality and selectively dissolve higher molecular weight samples with a narrow polydispersity (PDI). Fractionation of P3HT with ΔT_col = 5 °C in methylene chloride (MC) yielded 7 fractions ranging from M_p of 20 to 53 kg/mol with an average PDI of 1.80 compared with a mother sample of 3.10. Predominant recovery of P3HT was acquired for fractions with T_col > 20 °C (30 wt %). Subsequent separation of P3OT in methylene chloride, with a reduced ΔT_col of 3 °C per fraction, due to increased solubility from the longer alkyl chain, generated 8 fractions with a weight range of M_n = 22 to 57 kg/mol with an mean PDI of 1.23 with the mother sample having PDI = 2.34, demonstrating the tunability of this method. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2547–2555, 2009     

Elements of the Lagrangian Whitney trick

We investigate the possibility of a Lagrangian Whitney trick, a process to remove a pair of intersection points of a self-transverse Lagrangian immersion by a homotopy through Lagrangian immersions. There is a model for which a Lagrangian Whitney trick with compact support works assuming the model satisfies an area-capacity condition. Reduction of more general cases to the model, not necessarily fulfilling the area-capacity requirement, is possible if the given pair of double points admits a suitable symplectic disc and a certain Maslov-Viterbo index is 1. We look into an example to see the actualities of the Maslov-Viterbo index and the area-capacity conditions. The authors would like to thank the anonymous referee whose suggestions improved remarkably the exposition of the paper. This work was supported by the grant no.R01-2000-000-00004-0 from Korea Science & Engineering Foundation.     

Photothermal probe beam deflection measurement of thermal diffusivity of atmospheric air

We have used a modified photothermal probe beam deflection system with a back pumping configuration for the measurements of the temperature-dependent thermal diffusivity of atmospheric air. The results are consistent and reasonably well agree with the literature values. The measured thermal diffusivity values are the same for the same measuring temperature regardless of the beam offsets and the deflecting surface temperatures. For the gas with known temperature-dependent thermal diffusivity, this method can be used to deduce the temperature of a gas from the measured thermal diffusivity value.     

The best choice of subsample size (M,K) in 3 stage sampling

In this paper we extend the best choice of subsample size m in the 2-stage sampling,which suggested by Mohammad(1986), to the 3-stage sampling in cases of known and of unknown cost and variance ratio. We find the subsample size m,k which ensures more than the relative efficiency 90 %. Also we see that the choice of 3-stage subsample size depends on the design parameters using in 2-stage sampling.