SEC–MALLS analysis of ethylenediamine-pretreated native celluloses in LiCl/<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylacetamide: softwood kraft pulp and highly crystalline bacterial,tunicate, and algal celluloses

Softwood and hardwood bleached kraft pulps (SBKP and HBKP, respectively) and highly crystalline native celluloses such as algal, tunicate, bacterial and cotton lint celluloses were dissolved in 8 % (w/v) LiCl/N,N-dimethylacetamide (DMAc) after ethylenediamine (EDA) pretreatment. Complete dissolution of SBKP and other highly crystalline native celluloses in 8 % LiCl/DMAc was achieved after solvent exchange from EDA to DMAc through methanol. Neutral sugar composition analysis showed no significant differences between the original and EDA-treated pulps. A combination of size-exclusion chromatography and multi-angle laser light scattering (SEC–MALLS) was used to analyze the cellulose solutions after dilution to 1 % (w/v) LiCl/DMAc. The 0.05 % (w/v) solutions of highly crystalline cellulose in 1 % (w/v) LiCl/DMAc contained entangled molecules, and therefore 0.025 % (w/v) cellulose solutions in 1 % (w/v) LiCl/DMAc were used in the SEC–MALLS analysis to obtain reliable conformation plots (or double-logarithmic plots of molecular mass vs. root-mean-square radius). All the cellulose samples except SBKP gave conformation plots with slope values of 0.56–0.57, showing that these cellulose molecules had random-coil conformations. In contrast, SBKP gave a slope value of 0.35, indicating that some branched structures were present in the high-molecular-mass fraction. Double-logarithmic plots of the reduced viscosities of the cellulose solutions in 1 % (w/v) LiCl/DMAc versus the molecular mass were linear, except for SBKP, also suggesting the presence of anomalous cellulose structures in SBKP.     

Ablation thresholds and morphological changes of poly-l-lactic acid for pulse durations in the femtosecond-to-picosecond regime

Biodegradable polymers such as poly-l -lactic acid (PLLA) are essential tools for a wide range of medical applications because of their mechanical robustness and bio-affinity. Laser processing is commonly used to construct various structures from biodegradable polymers. However, in general, polymers deteriorate rapidly owing to laser-induced heating effects. In this study, we investigate the optimum irradiation conditions for PLLA processing, using an ultrafast laser and finely controlling the pulse duration over the femtosecond-to-picosecond range. We report on the morphological characteristics of the craters generated by single-shot and multiple-shot laser irradiation under pulse duration control. Our results show that crater morphology and damage threshold in the single-shot regime depend on pulse duration and that the degree of crater unevenness is insensitive to pulse duration in the multishot regime.     

Additive effects of amines on asymmetric hydrogenation of quinoxalines catalyzed by chiral iridium complexes

The additive effects of amines were realized in the asymmetric hydrogenation of 2-phenylquinoxaline, and its derivatives, catalyzed by chiral cationic dinuclear triply halide-bridged iridium complexes [{Ir(H)[diphosphine]}(2) (μ-X)(3) ]X (diphosphine=(S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl [(S)-BINAP], (S)-5,5'-bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole [(S)-SEGPHOS], (S)-5,5'-bis(diphenylphosphino)-2,2,2',2'-tetrafluoro-4,4'-bi-1,3-benzodioxole [(S)-DIFLUORPHOS]; X=Cl, Br, I) to produce the corresponding 2-aryl-1,2,3,4-tetrahydroquinoxalines. The additive effects of amines were investigated by solution dynamics studies of iridium complexes in the presence of N-methyl-p-anisidine (MPA), which was determined to be the best amine additive for achievement of a high enantioselectivity of (S)-2-phenyl-1,2,3,4-tetrahydroquinoxaline, and by labeling experiments, which revealed a plausible mechanism comprised of two cycles. One catalytic cycle was less active and less enantioselective; it involved the substrate-coordinated mononuclear complex [IrHCl(2) (2-phenylquinoxaline){(S)-BINAP}], which afforded half-reduced product 3-phenyl-1,2-dihydroquinoxaline. A poorly enantioselective disproportionation of this half-reduced product afforded (S)-2-phenyl-1,2,3,4-tetrahydroquinoxaline. The other cycle involved a more active hydride-amide catalyst, derived from amine-coordinated mononuclear complex [IrCl(2) H(MPA){(S)-BINAP}], which functioned to reduce 2-phenylquinoxaline to (S)-2-phenyl-1,2,3,4-tetrahydroquinoxaline with high enantioselectivity. Based on the proposed mechanism, an Ir(I) -JOSIPHOS (JOSIPHOS=(R)-1-[(S(p) )-2-(dicyclohexylphosphino)ferrocenylethyl]diphenylphosphine) catalyst in the presence of amine additive resulted in the highest enantioselectivity for the asymmetric hydrogenation of 2-phenylquinoxaline. Interestingly, the reaction rate and enantioselectivity were gradually increased during the reaction by a positive-feedback effect from the product amines.     

Visualization of microvessels by angiography using inverse‐Compton scattering X‐rays in animal models

The fundamental performance of microangiography has been evaluated using the S‐band linac‐based inverse‐Compton scattering X‐ray (iCSX) method to determine how many photons would be required to apply iCSX to human microangiography. ICSX is characterized by its quasi‐monochromatic nature and small focus size which are fundamental requirements for microangiography. However, the current iCSX source does not have sufficient flux for microangiography in clinical settings. It was determined whether S‐band compact linac‐based iCSX can visualize small vessels of excised animal organs, and the amount of X‐ray photons required for real time microangiography in clinical settings was estimated. The iCSX coupled with a high‐gain avalanche rushing amorphous photoconductor camera could visualize a resolution chart with only a single iCSX pulse of ～3 ps duration; the resolution was estimated to be ～500 µm. The iCSX coupled with an X‐ray cooled charge‐coupled device image sensor camera visualized seventh‐order vascular branches (80 µm in diameter) of a rabbit ear by accumulating the images for 5 and 30 min, corresponding to irradiation of 3000 and 18000 iCSX pulses, respectively. The S‐band linac‐based iCSX visualized microvessels by accumulating the images. An iCSX source with a photon number of 3.6 × 10³–5.4 × 10⁴ times greater than that used in this study may enable visualizing microvessels of human fingertips even in clinical settings.     

Spreading properties of a three-component reaction-diffusion model for the population of farmers and hunter-gatherers

In this paper, we investigate the spreading properties of solutions of farmer and hunter-gatherer model which is a three-component reaction-diffusion system. Ecologically, the model describes the geographical spreading of an initially localized population of farmers into a region occupied by hunter-gatherers. This model was proposed by Aoki, Shida and Shigesada in 1996. By numerical simulations and some formal linearization arguments, they concluded that there are four different types of spreading behaviors depending on the parameter values. Despite such intriguing observations, no mathematically rigorous studies have been made to justify their claims. The main difficulty comes from the fact that the comparison principle does not hold for the entire system. In this paper, we give theoretical justification to all of the four types of spreading behaviors observed by Aoki et al. Furthermore, we show that a logarithmic phase drift of the front position occurs as in the scalar KPP equation. We also investigate the case where the motility of the hunter-gatherers is larger than that of the farmers, which is not discussed in the paper of Aoki et al.     

Kurzkettenverzweigung von Polyvinylalkohol. 1. Mitt. Synthese von Modell-Polymeren

Ohne Zusammenfassung     

Tunable Synchronicity of Molecular Valence Tautomerism with Macroscopic Solid-Liquid Transition by Molecular Lattice Engineering

The combination of a cobalt-dioxolene core that exhibits valence tautomerism (VT) with pyridine-3,5-dicarboxylic acid functionalized with chains bearing two, four, or six oxyethylene units led to new complexes ConEGEspy (n = 2, 4, and 6). These complexes commonly form violet crystals of the low-spin (ls)-[Co^III(nEGEspy)₂(3,6-DTBSQ)(3,6-DTBCat)] (ls-[Co^III], 3,6-DTBSQ = 3,6-di-tert-butyl semiquinonato, 3,6-DTBCat = 3,6-di-tert-butyl catecholato). Interestingly, violet crystals of Co2EGEspy in the ls-[Co^III] transitioned into a green liquid, accompanied by an almost complete VT shift (94 %) to the high-spin (hs)-[Co^II(nEGEspy)₂(3,6-DTBSQ)₂] (hs-[Co^II]) upon melting. In contrast, violet crystals of Co4EGEspy and Co6EGEspy in the ls-[Co^III] exhibited partial VT (33 %) and only a 9.3 % VT shift after melting, respectively. These data demonstrate the tunability of the synchronicity of the molecular VT and macroscopic solid-liquid transitions by optimizing the tethered chains, thus establishing a new strategy for coupling bistable molecules with the macroscopic world.     

Effect of Edge Functionalization on the Bottom-Up Synthesis of Nano-Graphenes

We demonstrate the effect of edge functionalization on the on-surface Ullmann coupling of nano-carbon materials. Unlike 10,10′-Dibromo-9,9′-bianthryl (DBBA), which is widely known to form anthracene polymers and armchair-edge graphene nanoribbons on Au(111), newly-developed precursor named 5-bromo-11(10-bromoanthracene-9-yl)anthra[2,3-b : 7,6-b′]dithiophene (BABAT) with isomers, which has similar structure as DBBA with one anthracene substituted with anthradithiophene, was found to make intramolecular C−C bonding instead of long anthracene polymers after annealing at 200 °C on Au(111). The mechanism was investigated using first-principle density functional theory, which revealed that on-surface polymerization is not kinetically preferred in case of BABAT. The reaction rate of intramolecular C−C bonding of BABAT is ∼206 times faster than that of DBBA. The intramolecular C−C bonding in DBBA biradicals, on the other hand, do not take place because of faster reverse reaction. By referring to electron density of BABAT biradicals, it was concluded that thiophene functionalization modifies distribution of electron density in BABAT radicals and facilitates electrophilic addition, leading to intramolecular C−C bonding after 200 °C annealing. These results indicate that the design of radical moiety is particularly important in the on-surface Ullmann-type coupling.