First example of continuous-flow reaction conditions for biomimetic reductive amination of fluorine-containing carbonyl compounds

This study presents the first example of continuous-flow reaction conditions for biomimetic reductive amination of fluorinated carbonyl compounds using silica-adsorbed DBU as catalyst for on-column process. This new on-column process features operationally convenient conditions, higher chemical yields and purity of products as compared with traditional in-flask reactions. Furthermore the removal of base-catalyst is not an issue in this process at all, as the catalyst (DBU) remains on the column in the “reaction zone”, the feature which makes the overall process substantially more efficient and inexpensive, in particular, for large-scale synthesis of the target α-perfluoroalkyl amines.     

Self-disproportionation of enantiomers of isopropyl 3,3,3-(trifluoro)lactate via sublimation: Sublimation rates vs. enantiomeric composition

The presented results convincingly demonstrate that self-disproportionation of enantiomers via sublimation is substantially more complex phenomenon then was previously believed. We demonstrate that the racemic form of isopropyl 3,3,3-trifluoro-2-hydroxypropanoate (1) sublimed faster regardless of the starting enantiomeric composition of the enantiomerically enriched mixtures studied in the range from 20.8, 36.8, 58.7 to 79.4% ee. This preferential sublimation of the racemic form allowed for, the most possibly simple, preparation of optically pure samples of compound 1. In this work we also suggest some general experimental procedures, which may be easily used to facilitate the interpretation of the data collected in different laboratories.     

A mechanically controlled indicator displacement assay

Push a host: Mechanical compression was applied to a host monolayer at an interface, which facilitated an indicator displacement assay. The fluorescence resonance energy transfer (FRET) between the host and indicator was switched on by this compression. Addition of D-glucose caused the indicator to be displaced, effectively quenching the FRET process.     

Metal-Containing Initiator Systems. 30. Vinyl Polymerization Initiated with Bis(ethyl acetoacetato)copper(II) and Maleimide

Some electron-accepting compounds such as maleimide (MIm), maleic anhydride (MAn), and tetracyanoquinodimethane were found to show pronounced accelerating effects on vinyl polymerization initiated with metal chelates. The polymerization of methyl methacrylate (MMA) initiated with bis(ethyl acetoacetato)-copper(II) (Cu(eacac)₂) and MIm was studied kinetically in benzene. The overall activation energy of the polymerization was calculated to be 11.5 kcal/mol. This value was much lower than that (17.6 kcal/mol) for the polymerization of MMA with Cu(eacac)₂ alone. The polymerization rate (R_p) was expressed as R_p =k[MIm]^1/2 [Cu(eacac)₂]^1/2 [MMA] The first-order dependence of R_p on the monomer concentration indicated that the monomer had no participation in the initiation step, in contrast with polymerization in the absence of MIm (where a monomer concentration dependence of 1.4th order was observed). Electronic spectroscopic study revealed that a complex between MIm and Cu(eacac)₂ had been formed. The ligand radical, an acetylcarboethoxymethyl radical, was trapped by 2-methyl-2-nitrosopropane in the reactions of Cu(eacac)₂ with MIm and with MAn in benzene. From these results the mechanism of the initiation of polymerization is discussed.     

Co-Ni obliquely evaporated tape and its magnetic and recording characteristics

This paper describes technology for a Co-Ni evaporated tape, a metal evaporated, or ME tape fabricated by a vacuum evaporation method, focusing on magnetic properties, microstructure, recording characteristics and noise prosperties. The high reproduced signal output, low noise and high resolution of ME tape obtained by using a ring head are attributed to oblique anisotropy and a particle-like structure. A breakthrough in improving the durability of ME tape has been achieved by technological improvements in tribology.     

Catalytic and biochemical features of a monoclonal antibody heavy chain, JN1-2, raised against a synthetic peptide with a hemagglutinin molecule of influenza virus

It has long been an important issue to produce a catalytic antibody that possesses the ability to lose the infectivity of a bacteria or virus. The monoclonal antibody JN1-2 was generated using a synthetic peptide (TGLRNGITNKVNSVIEKAA) conjugated with human IgG. The peptide sequence includes the conserved region of the hemagglutinin molecule (HA(1) and HA(2) domains), which locates on the envelope of the influenza virus and plays an important role in influenza A virus infection. The monoclonal antibody specifically reacted with the HA2 domain, not only of H2 but also of an H1 strain of the H1N1 subtype (H1 strain). The heavy chain (JN1-2-H) isolated from the parent antibody showed catalytic activity cleaving the above antigenic peptide with very high turnover (kcat = 26 min(-1)), and it could slowly degrade the recombinant HA(2) domain by the catalytic function. Interestingly, the heavy chain exhibited the ability to reduce the infectivity of type A H1N1 but not type B, indicating specificity to type A. This characteristic monoclonal catalytic antibody heavy chain could suppress the infection of the influenza virus in vitro assays.     

Amyloid-β peptide structure in aqueous solution varies with fragment size

Various fragment sizes of the amyloid-β (Aβ) peptide have been utilized to mimic the properties of the full-length Aβ peptide in solution. Among these smaller fragments, Aβ16 and Aβ28 have been investigated extensively. In this work, we report the structural and thermodynamic properties of the Aβ16, Aβ28, and Aβ42 peptides in an aqueous solution environment. We performed replica exchange molecular dynamics simulations along with thermodynamic calculations for investigating the conformational free energies, secondary and tertiary structures of the Aβ16, Aβ28, and Aβ42 peptides. The results show that the thermodynamic properties vary from each other for these peptides. Furthermore, the secondary structures in the Asp1-Lys16 and Asp1-Lys28 regions of Aβ42 cannot be completely captured by the Aβ16 and Aβ28 fragments. For example, the β-sheet structures in the N-terminal region of Aβ16 and Aβ28 are either not present or the abundance is significantly decreased in Aβ42. The α-helix and β-sheet abundances in Aβ28 and Aβ42 show trends--to some extent--with the potential of mean forces but no such trend could be obtained for Aβ16. Interestingly, Arg5 forms salt bridges with large abundances in all three peptides. The formation of a salt bridge between Asp23-Lys28 is more preferred over the Glu22-Lys28 salt bridge in Aβ28 but this trend is vice versa for Aβ42. This study shows that the Asp1-Lys16 and Asp1-Lys28 regions of the full length Aβ42 peptide cannot be completely mimicked by studying the Aβ16 and Aβ28 peptides.     

Quantum condensates classified in superconductivity with topology in the Minkowski space-time

A substantial problem in the macroscopic theory of pure superconductivity has been left forgotten for a long time since London and London in 1935. An impression survived that the Meissner effect is more substantial than the zero-resistivity. But, the London equation [I], the Newtonian equation of motion, was abandoned, whereas the London equation [II], derived from the Maxwell equations, was postulated. The London equation [II] included the logical gap [ α ] in real time, whereas the London equation [I] has been ignored without even noting the logical gap [ β ] in space. Microscopically, after the publication of F. London's book and the discovery of the isotope effect in 1950, the success of the Bardeen--Cooper--Schrieffer (BCS) theory in 1957 was likely to have finally given the definitive explanation on superconductivity by proving only the London equation [II] that claimed the coherent condensation of Cooper pairs in the momentum space. Since then, these arguments have been regarded to be a standard among various preceding theories. Meanwhile, the London equation [I] has faded away and has been long-forgotten. But we must not abandon the London equation [I], and, rather, retrieve it. We later recognized also that the DC-component of a persistent current can never be determined by using the Fourier transform analysis, because of its singularity at ω?=?0 and q ?=?0 with huge differences of space-time domain. Quite recently, in 2003, we first recognized a proper and harmonious view to simultaneously account for (i) the zero-resistivity in an open system with (i-c) the resultant persistent current in a closed system, and (ii) the perfect diamagnetism at T???0?K in the space-time aspects in terms of the gauge field theory. Here, we further clarify where and how we have lost and found a properly perspective view of the superconductivity. Here, we eliminate two logical gaps [ α ] and [ β ] by using the gauge field theory for further clarifying a position of the previous and present works. We especially classify superconductors with topology which eventually leads us such as (ii-2D) magnetic flux quantization in a ring. By projecting the 3-dimensional BCS-theory with the concept of ‘coherence’ among an enormous number of Bosons like Cooper pairs onto the (1?+?3)-dimensional Minkowski space-time [β?=?(v/c)?=?0], we clarify responses of the ground state Ψ _macro at T???0?K in a set of the basic equations, for (i) the zero-resistivity, [E _K ???qφ( R )]?=?0 at ω?=?0 and (ii) the perfect diamagnetism [?K ???qA ( R )]?=?0 at q ?=?0 as an inevitable consequence at the gauge fields in the proper theory of superconductivity.     

2D Nanoarchitectonics: Soft Interfacial Media as Playgrounds for Microobjects,Molecular Machines,and Living Cells

Soft and flexible two-dimensional (2D) systems, such as liquid interfaces, would have much more potentials in dynamic regulation on nano–macro connected functions. In this Minireview article, we focus especially on dynamic motional functions at liquid dynamic interfaces as 2D material systems. Several recent examples are selected to be explained for overviewing features and importance of dynamic soft interfaces in a wide range of action systems. The exemplified research systems are mainly classified into three categories: (i) control of microobjects with motional regulations; (ii) control of molecular machines with functions of target discrimination and optical outputs; (iii) control of living cells including molecular machine functions at cell membranes and cell/biomolecular behaviors at liquid interface. Sciences on soft 2D media with motional freedom and their nanoarchitectonics constructions will have increased importance in future technology in addition to popular rigid solid 2D materials.