Effect of dispersion on the diffusion zone in two-phase laminar flows in microchannels

Aim of the present work is to investigate the reaction–diffusion process of a two species system under laminar flow in a T-shaped microchannel. A zone formed at the interface between the aqueous solutions of these two species is affected by advection and diffusion. Through theoretical analyses and experimental results, the effect of dispersion has been shown to influence this diffusion zone. We have defined a parameter called effective diffusivity, to account for the dispersion effects and observed it to be a function of the channel Peclet number. In the limiting case of low Peclet number, this parameter is constant and turns out to be equal to the molecular diffusivity. We have also related effective diffusivity and the dispersion coefficient through scaling estimates.     

Extraction and Characterization of Cellulose Nanowhiskers from Balsa Wood

Summary: In this study cellulose nanowhiskers were obtained from balsa wood. For this purpose, fibers of balsa wood were exposed to hydrolysis reactions for lignin and hemicellulose digestion and acquisition of nano-scale cellulose. Transmission electron microscopy (TEM) results demonstrated that the obtained cellulose nanocrystals had average length and thickness of 176 (±68 nm) and 7.5 (±2.9 nm), respectively. Infrared spectroscopy (FTIR) and wide angle x-ray diffraction (WAXD) showed that the process for extracting the nanowhiskers digested nearly all the lignin and hemicellulose from the balsa fiber and still preserved the aspect ratio and crystallinity satisfactory enough for future application as nanofillers in polymer nanocomposites. The thermogravimetric analysis (TGA) showed that the onset temperature of thermal degradation of the cellulose nanocrystals (226 °C) was higher than the onset temperature of the balsa fiber (215 °C), allowing its use in molding processes with polymers melts.     

Aziridination of alkenes using N-iodo-N-potassio-p-toluenesulphonamide as a nitrene precursor

N-Iodo-N-potassio-p-toluenesulphonamide was found to be a convenient nitrene precursor for the aziridination of alkenes in the presence of copper catalysts.     

N‐Heterocyclic Carbene,High Oxidation State Molybdenum Alkylidene Complexes: Functional‐Group‐Tolerant Cationic Metathesis Catalysts

We synthesized the first N‐heterocyclic carbene (NHC) complexes of Schrock’s molybdenum imido alkylidene bis(triflate) complexes. Unlike existing bis(triflate) complexes, the novel 16‐electron complexes represent metathesis active, functional‐group‐tolerant catalysts. Single‐crystal X‐ray structures of two representatives of this novel class of Schrock catalysts are presented and reactivity is discussed in view of their structural peculiarities. In the presence of monomer (substrate), these catalysts form cationic species and can be employed in ring‐closing metathesis (RCM), ring‐opening metathesis polymerization (ROMP), as well as in the cyclopolymerization of α,ω‐diynes. Monomers containing functional groups, which are not tolerated by the existing variations of Schrock’s catalyst, e.g., sec‐amine, hydroxy, and carboxylic acid moieties, can be used. These catalysts therefore hold great promise in both organic and polymer chemistry, where they allow for the use of protic monomers.     

Alkyne‐Mediated Approach to the Synthesis of (4R,5R)‐5‐Hydroxy‐4‐decanolide and (−)‐Muricatacin

The asymmetric synthesis of two naturally occurring 5‐hydroxy‐γ‐butyrolactones, (4R,5R)‐5‐hydroxy‐4‐decanolide ( 1a ) and (?)‐muricatacin ( 2 ), is described using a general alkyne‐mediated strategy. The key steps involved are Sonogashira coupling for the desired carbon‐chain extension followed by Sharpless asymmetric dihydroxylation to construct the hydroxy‐lactone framework.     

Heterometallic Triply‐Bridging Bis‐Borylene Complexes

Triply‐bridging bis‐{hydrido(borylene)} and bis‐borylene species of groups 6, 8 and 9 transition metals are reported. Mild thermolysis of [Fe₂(CO)₉] with an in situ produced intermediate, generated from the low‐temperature reaction of [Cp*WCl₄] (Cp*=η⁵‐C₅Me₅) and [LiBH₄?THF] afforded triply‐bridging bis‐{hydrido(borylene)}, [(μ₃‐BH)₂H₂{Cp*W(CO)₂}₂{Fe(CO)₂}] ( 1 ) and bis‐borylene, [(μ₃‐BH)₂{Cp*W(CO)₂}₂{Fe(CO)₃}] ( 2 ). The chemical bonding analyses of 1 show that the B?H interactions in bis‐{hydrido (borylene)} species is stronger as compared to the M?H ones. Frontier molecular orbital analysis shows a significantly larger energy gap between the HOMO‐LUMO for 2 as compared to 1 . In an attempt to synthesize the ruthenium analogue of 1 , a similar reaction has been performed with [Ru₃(CO)₁₂]. Although we failed to get the bis‐{hydrido(borylene)} species, the reaction afforded triply‐bridging bis‐borylene species [(μ₃‐BH)₂{WCp*(CO)₂}₂{Ru(CO)₃}] ( 2′ ), an analogue of 2 . In search for the isolation of bridging bis‐borylene species of Rh, we have treated [Co₂(CO)₈] with nido‐[(RhCp*)₂(B₃H₇)], which afforded triply‐bridging bis‐borylene species [(μ₃‐BH)₂(RhCp*)₂Co₂(CO)₄(μ‐CO)] ( 3 ). All the compounds have been characterized by means of single‐crystal X‐ray diffraction study; ¹H, ¹¹B, ¹³C NMR spectroscopy; IR spectroscopy and mass spectrometry.