Room temperature-stable electride as a synthetic organic reagent: application to pinacol coupling reaction in aqueous media

Room temperature-stable inorganic electride [Ca(24)Al(28)O(68)](4+)4e(-) was employed for a pinacol coupling reaction in aqueous media. Ca-Al-O gel formed by the destruction of the crystal structure of an electride by water media played a key role in transferring the electron to electrophilic aldehydes. Aromatic aldehydes reacted smoothly with moderate to high yields.     

Density functional theory study on carbon dioxide absorption into aqueous solutions of 2-amino-2-methyl-1-propanol using a continuum solvation model

We used density functional theory (DFT) calculations with the latest continuum solvation model (SMD/IEF-PCM) to determine the mechanism of CO(2) absorption into aqueous solutions of 2-amino-2-methyl-1-propanol (AMP). Possible absorption process reactions were investigated by transition-state optimization and intrinsic reaction coordinate (IRC) calculations in the aqueous solution at the SMD/IEF-PCM/B3LYP/6-31G(d) and SMD/IEF-PCM/B3LYP/6-311++G(d,p) levels of theory to determine the absorption pathways. We show that the carbamate anion forms by a two-step reaction via a zwitterion intermediate, and this occurs faster than the formation of the bicarbonate anion. However, we also predict that the carbamate readily decomposes by a reverse reaction rather than by hydrolysis. As a result, the final product is dominated by the thermodynamically stable bicarbonate anion that forms from AMP, H(2)O, and CO(2) in a single-step termolecular reaction.     

Photomechanical bending of salicylideneaniline crystals

Platelike microcrystals of N-3,5-di-tert-butylsalicylidene-3-nitroaniline repeatedly bend and straighten upon alternate irradiation with UV and visible light. The mechanism of bending was elucidated by X-ray crystallographic analyses before and after photoirradiation.     

2'-O,4'-C-aminomethylene-bridged nucleic acid modification with enhancement of nuclease resistance promotes pyrimidine motif triplex nucleic acid formation at physiological pH

Due to the instability of pyrimidine motif triplex DNA at physiological pH, triplex stabilization at physiological pH is crucial in improving its potential in various triplex-formation-based strategies in vivo, such as gene expression regulation, genomic DNA mapping, and gene-targeted mutagenesis. To this end, we investigated the thermodynamic and kinetic effects of our previously reported chemical modification, 2'-O,4'-C-aminomethylene-bridged nucleic acid (2',4'-BNA(NC)) modification of triplex-forming oligonucleotide (TFO), on triplex formation at physiological pH. The thermodynamic analyses indicated that the 2',4'-BNA(NC) modification of TFO increased the binding constant of the triplex formation at physiological pH by more than 10-fold. The number and position of the 2',4'-BNA(NC) modification in TFO did not significantly affect the magnitude of the increase in the binding constant. The consideration of the observed thermodynamic parameters suggested that the increased rigidity and the increased degree of hydration of the 2',4'-BNA(NC)-modified TFO in the free state relative to the unmodified TFO may enable the significant increase in the binding constant. Kinetic data demonstrated that the observed increase in the binding constant by the 2',4'-BNA(NC) modification resulted mainly from the considerable decrease in the dissociation rate constant. The TFO stability in human serum showed that the 2',4'-BNA(NC) modification significantly increased the nuclease resistance of TFO. Our results support the idea that the 2',4'-BNA(NC) modification of TFO could be a key chemical modification to achieve higher binding affinity and higher nuclease resistance in the triplex formation under physiological conditions, and may lead to progress in various triplex-formation-based strategies in vivo.     

Selective recovery of gold(III) using cotton cellulose treated with concentrated sulfuric acid

Novel utilization of cotton cellulose was developed by chemically modifying with concentrated sulfuric acid to prepare a novel kind of adsorption gel for gold. The adsorption behaviors of the gel were investigated for various metals from acidic chloride media. The gel was found to be highly selective for Au(III) over other precious and base metals tested over the whole concentration range of hydrochloric acid. The maximum adsorption capacity for Au(III) was evaluated as 6.21 mmol/g at 303 K. The amount of adsorbed Au(III) was increased with increasing temperature. A kinetic study for the adsorption of Au(III) at various temperatures confirmed the endothermic adsorption process following pseudo-first order kinetics. The activation energy was evaluated as 78.8 kJ/mol. Interestingly, it was found that the adsorbed Au(III) was reduced to elemental form which was evidenced by the clearly visible elemental gold particles which was further confirmed by means of the X-ray diffraction spectrum and optical microscope image of the gel after the adsorption of Au(III). The mechanism of Au(III) adsorption on the cotton gel and its reduction to elemental gold was proved from the results of IR-spectra. The main mechanism could be explained in terms of the coordination of Au(III) to oxygen atom of C–O–C linkage of cross linked cotton gel and to the oxygen atoms of the hydroxyl groups at C₂ and C₃ atoms of pyranose ring of cotton cellulose followed by the reduction to metallic gold. The adsorbed gold in the cotton gel can easily be recovered by incineration.     

Ag(I) ion mediated formation of a C-A mispair by DNA polymerases

Silver turns up the A-C: In the presence of Ag(I) ions, a DNA polymerase incorporated deoxyadenosine (from dATP) at the site opposite cytosine in the template strand to afford the full-length product (see scheme), meaning that DNA polymerases prefer a C-Ag(I)-A base pair to the more thermodynamically stable C-Ag(I)-C base pair.     

Effects of Fluctuation and Segregation in the Rate Acceleration of ATRP Miniemulsion Polymerization

In the ATRP and SFRP miniemulsion polymerization, a particle size range may exist in which the polymerization rate is larger than that of the corresponding bulk polymerization. Here, MC simulations are applied to clarify the reason for the acceleration. It is shown that the statistical variation of the trapping agent concentration (fluctuation effect) dominates the acceleration for good living conditions, while the segregation effect is important when the bimolecular termination is significant. Even for the segregation‐dominated conditions, the polymerization rate cannot be predicted accurately without accounting for the fluctuation effect.

     

Reverse enantioselectivity in the lipase-catalyzed desymmetrization of prochiral 2-carbamoylmethyl-1,3-propanediol derivatives

Enantioselective acetylation of 2-carbamoylmethyl-1,3-propanediol derivatives was catalyzed effectively by lipase PS to give monoacetates with high enantioselectivity: The enantioselectivity depended on the 2-carbamoylmethyl groups. The reaction of N-monoalkylcarbamoylmethyl-1,3-propanediol afforded the monoacetate with the (S)-configuration, whereas N,N-dialkylcarbamoylmethyl-1,3-propanediol gave the monoacetate with the (R)-configuration.     

An abstract approach to Loewner chains

We present a new geometric construction of Loewner chains in one and several complex variables which holds on complete hyperbolic complex manifolds and prove that there is essentially a one-to-one correspondence between evolution families of order d and Loewner chains of the same order. As a consequence, we obtain a univalent solution (f _t : M → N) of any Loewner-Kufarev PDE. The problem of finding solutions given by univalent mappings (f _t : M → ? ⁿ ) is reduced to investigating whether the complex manifold ∪ _t≥0 f _t (M) is biholomorphic to a domain in ? ⁿ . We apply such results to the study of univalent mappings f: B ⁿ → ? ⁿ .     

Univalence criterion and quasiconformal extension of holomorphic mappings

In this paper we are concerned with solutions, in particular with the univalent solutions, of the Loewner differential equation associated with non-normalized subordination chains on the Euclidean unit ball B in ${\mathbb{C}^n}$ . We also give applications to univalence conditions and quasiconformal extensions to ${\mathbb{C}^n}$ of holomorphic mappings on B. Finally we consider the asymptotical case of these results. The results in this paper are complete generalizations to higher dimensions of well known results due to Becker. They improve and extend previous sufficient conditions for univalence and quasiconformal extension to ${\mathbb{C}^n}$ of holomorphic mappings on B.