Analysis of Vicinal Water in Soft Contact Lenses Using a Combination of Infrared Absorption Spectroscopy and Multivariate Curve Resolution

In this paper, we propose a new spectroscopic method to explore the behavior of molecules near polymeric molecular networks of water-containing soft materials such as hydrogels. We demonstrate the analysis of hydrogen bonding states of water in the vicinity of hydrogels (soft contact lenses). In this method, we apply force to hydrated contact lenses to deform them and to modulate the ratio between the signals from bulk and vicinal regions. We then collect spectra at different forces. Finally, we extracted the spectra of the vicinal region using the multivariate curve resolution-alternating least square (MCR-ALS) method. We report the hydration states depending on the chemical structures of hydrogels constituting the contact lenses.     

Structure and properties of new olefin polymers

The relationship between molecular structures and physical properties of linear low density polyethylenes (LLDPEs) produced with single-site catalyst (SSC) was investigated. SSC polymerized LLDPE have excellent physical properties corresponding to its homogeneous molecular structure that had never been achieved by conventional Ziegler-Natta catalysts. It was found that some SSCs have the capability to produce LLDPEs with narrow molecular weight distribution but excellent melt properties. This result suggests that there exist long chain branches in these LLDPEs.     

Competitive Assay for Theophylline Based on an Abasic Site‐Containing DNA Duplex Aptamer and a Fluorescent Ligand

A fluorescence assay for theophylline, one of the common drugs for acute and chronic asthmatic conditions, has been developed based on an abasic site‐containing DNA duplex aptamer (AP aptamer) in combination with an abasic site‐binding fluorescent ligand, riboflavin. The assay is based on the competitive binding of theophylline and riboflavin at the abasic (AP) site of the AP aptamer. In the absence of theophylline, riboflavin binds to the receptor nucleotide opposite the AP site, which leads to fluorescence quenching of the riboflavin. Upon addition of theophylline, competitive binding occurs between theophylline and riboflavin, which results in an effective fluorescence restoration due to release of riboflavin from the AP site. From an examination of the optimization of the AP aptamers, the complex of riboflavin with a 23‐mer AP aptamer (5′‐TCT GCG TCC AGX GCA ACG CAC AC‐3′/5′‐GTG TGC GTT GCC CTG GAC GCA GA‐3′; X : the AP site (Spacer C3, a propylene residue)) possessing cytosine as a receptor nucleotide was found to show a selective and effective fluorescence response to theophylline; the limit of detection for theophylline was 1.1 μM . Furthermore, fluorescence detection of theophylline was successfully demonstrated with high selectivity in serum samples by using the optimized AP aptamer and riboflavin.     

Phase Separation in Methylsiloxane Sol-Gel Systems in a Small Confined Space

The organo-siloxane gel with co-continuous structure derived from methyltrimethoxysilane (MTMS) was synthesized in a confined space between parallel plates by inducing spinodal decomposition during sol-gel transition. The resultant gel morphology was 3-dimensionally observed by laser scanning confocal microscopy (LSCM). The sliced LSCM photographs revealed that the confined gels have inhomogeneity perpendicular to the plate, exhibiting a layered structure. The layered structure can be divided into three regions according to their morphology; interface, near-surface layer, bulk phase. The organo-siloxane depletion layer had formed in the vicinity of both hydrophobic and hydrophilic plates, and the bulk phase had formed slight away from the plates exhibited co-continuous structure. In addition, the confined gels exhibited no shrinkage during drying process that resulted in the larger domain size compared to the monolithic gel. The attractive interaction between the plates and the resultant organo-siloxane phase accounts for the inhibition of shrinkage of confined gels.     

Mode-mode coupling theory of itinerant electron antiferromagnetism in superconducting state

It has been considered since the first discovery of a high-T(c) cuprate that an antiferromagnetic (AF) state and a superconducting (SC) state are separated in it. However, it is very intriguing that the coexistence of the AF and SC states has recently been observed in HgBa(2)Ca(4)Cu(5)O(12+) (Hg-1245). Moreover, it is very novel that this coexistence of these two states appears if the SC-transition temperature T(c) is higher than the AF-transition temperature T(N). The mode-mode coupling theory can provide a clear elucidation of this novel phenomenon. A key point of this theory is that the AF susceptibility consists of the random-phase-approximation (RPA) term and the mode-mode coupling one. The RPA term works to make a positive contribution to the emergence of the antiferromagnetic critical point (AF-CP). In contrast, the mode-mode coupling term works to make a negative contribution to the emergence of the AF-CP. However, the growth of the SC-gap function in the d(x(2)-y(2))-wave SC state works to suppress the negative contribution of the mode-mode coupling term to the emergence of the AF-CP. Moreover, the effect of SC fluctuations near the SC-transition temperature T(c) suppresses the mode-mode coupling term of the AF susceptibility that works to hinder the AF ordering. For these two reasons, there is a possibility that the d(x(2)-y(2))-wave SC state is likely to promote the emergence of the AF-CP. Namely, the appearance of the above-mentioned novel coexistence of the AF and SC states observed in Hg-1245 can be explained qualitatively on the basis of this idea.     

InBr3-catalyzed reduction of ketones with a hydrosilane: deoxygenation of aromatic ketones and selective synthesis of secondary alcohols and symmetrical ethers from aliphatic ketones

An InBr₃-Et₃SiH reducing system was developed to selectively convert aliphatic ketones to a variety of secondary alcohols in moderate to good yields. An initial mixing of InBr₃ and PhSiH₃ was followed by the addition of aliphatic ketones and a solvent to afford the symmetrical ether derivatives.