Biomimetic Peptide Catalytic Bond-Forming Utilizing a Mild Brønsted Acid

Since the global peptide drug market demand has been predicted to increase, highly efficient and inexpensive mass scale peptides are required. However, the production process raises questions about the cost of energy input, scale-up production, raw materials, and solvents treatment. This paper introduces 2 methods for the 2–4 mer oligopeptides bond formation for batch reaction utilizing 50–100 mol% of a mild Brønsted acid under the mild condition. One of the methods has been capably adapted to flow synthesis at room temperature using organic solvents with boiling points below 100 °C. The method applies the tert-butoxycarbonyl amino methoxy group, forming the desired dipeptide without solvent at mild temperatures. Furthermore, the conversion of the carboxylic acid leaving the group to phenyl ester promotes peptide bond formation, and the reaction were applied to di, tri, and tetrapeptide bond formation in excellent yield without notable racemization at ambient temperature (up to >99 % yield and 99 : 1 dr). Finally, this study proposes this new production method to overcome the limited scale-up production by reaction device scale: liquid phase biomimetic catalytic peptide flow synthesis utilizing a mild Brønsted acid.     

Macroscopic Polarization Change of Mononuclear Valence Tautomeric Cobalt Complexes Through the Use of Enantiopure Ligand

The crystallization of a complex having electron transfer properties in a polar space group can induce the polarization switching of a crystal in a specific direction, which is attractive for the development of sensors, memory devices, and capacitors. Unfortunately, the probability of crystallization in a polar space group is usually low. Noticing that enantiopure compounds crystallize in Sohncke space groups, this paper reports a strategy for the molecular design of non-ferroelectric polarization switching crystals based on the use of intramolecular electron transfer and chirality. In addition, this paper describes the synthesis of a mononuclear valence tautomeric (VT) cobalt complex bearing an enantiopure ligand. The introduction of enantiomer enables the crystallization of the complex in the polar space group (P2₁). The polarization of the crystals along the b-axis direction is not canceled out and the VT transition is accompanied by a change in the macroscopic polarization of the polar crystal. Polarization switching via electron transfer is realized at around room temperature.     

Long-Range Lateral Correlation between Self-Assembled Domains of Fluorocarbon-Hydrocarbon Tetrablocks by Quantitative GISAXS

The structure and lateral correlation of fluorocarbon-hydrocarbon tetrablock di(F10Hm) domains at the air/water interface have been determined by quantitative analysis of grazing incidence small-angle X-ray scattering (GISAXS) data. The measured GISAXS signals can be well represented by the full calculation of the form and structure factors. The form factor suggests that di(F10Hm) domains take a hemiellipsoid shape. Both major and minor axes of the hemiellipsoids monotonically increased in response to the elongation of the hydrocarbon blocks, which can be explained by the concominant increase in van der Waals interaction. The structure factor calculated from the GISAXS signals suggests that the domains take an orthorhombic lattice. Remarkably, the lateral correlation can reach over a distance that is more than 14 times longer than the distance to the nearest neighbors. Our data suggest that quantitative GISAXS enables the optimal design of mesoscopic self-assemblies at the air/water interface by fine-tuning of the structures of molecular building blocks.     

A CO Adsorption Site Change Induced by Copper Substitution in a Ruthenium Catalyst for Enhanced CO Oxidation Activity

Ru is an important catalyst in many types of reactions. Specifically, Ru is well known as the best monometallic catalyst for oxidation of carbon monoxide (CO) and has been practically used in residential fuel cell systems. However, Ru is a minor metal, and the supply risk often causes violent fluctuations in the price of Ru. Performance‐improved and cost‐reduced solid‐solution alloy nanoparticles of the Cu‐Ru system for CO oxidation are now presented. Over the whole composition range, all of the Cu_xRu_1?x nanoparticles exhibit significantly enhanced CO oxidation activities, even at 70 at % of inexpensive Cu, compared to Ru nanoparticles. Only 5 at % replacement of Ru with Cu provided much better CO oxidation activity, and the maximum activity was achieved by 20 at % replacement of Ru by Cu. The origin of the high catalytic performance was found as CO site change by Cu substitution, which was investigated using in situ Fourier transform infrared spectra and theoretical calculations.     

Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

On height isotopy classes of embeddings in the plane of a Morse function of a circle

Let \(\mathrm{SM}_{2n}(S^1,\mathbb {R})\) be a set of stable Morse functions of an oriented circle such that the number of singular points is \(2n\in \mathbb {N}\) and the order of singular values satisfies the particular condition. For an orthogonal projection \(\pi :\mathbb {R}^2\rightarrow \mathbb {R}\), let \({\tilde{f}}_0\) and \({\tilde{f}}_1:S^1\rightarrow \mathbb {R}^2\) be embedding lifts of f. If there is an ambient isotopy \(\tilde{\varphi }_t:\mathbb {R}^2\rightarrow \mathbb {R}^2\) \((t\in [0,1])\) such that \({\pi \circ \tilde{\varphi }}_t(y_1,y_2)=y_1\) and \(\tilde{\varphi }_1\circ {\tilde{f}}_0={\tilde{f}}_1\), we say that \({\tilde{f}}_0\) and \({\tilde{f}}_1\) are height isotopic. We define a function \(I:\mathrm{SM}_{2n}(S^1,\mathbb {R})\rightarrow \mathbb {N}\) as follows: I(f) is the number of height isotopy classes of embeddings such that each rotation number is one. In this paper, we determine the maximal value of the function I equals the n-th Baxter number and the minimal value equals \(2^{n-1}\).     

Gauss maps of the Ricci-mean curvature flow

In this paper, we investigate the Gauss maps of a Ricci-mean curvature flow. A Ricci-mean curvature flow is a coupled equation of a mean curvature flow and a Ricci flow on the ambient manifold. Ruh and Vilms (Trans Am Math Soc 149: 569–573, 1970) proved that the Gauss map of a minimal submanifold in a Euclidean space is a harmonic map, and Wang (Math Res Lett 10(2–3):287–299, 2003) extended this result to a mean curvature flow in a Euclidean space by proving its Gauss maps satisfy the harmonic map heat flow equation. In this paper, we deduce the evolution equation for the Gauss maps of a Ricci-mean curvature flow, and as a direct corollary we prove that the Gauss maps of a Ricci-mean curvature flow satisfy the vertically harmonic map heat flow equation when the codimension of submanifolds is 1.     

Computational Analysis Reveals a Critical Point Mutation in the N-Terminal Region of the Signaling Lymphocytic Activation Molecule Responsible for the Cross-Species Infection with Canine Distemper Virus

Infection of hosts by morbilliviruses is facilitated by the interaction between viral hemagglutinin (H-protein) and the signaling lymphocytic activation molecule (SLAM). Recently, the functional importance of the n-terminal region of human SLAM as a measles virus receptor was demonstrated. However, the functional roles of this region in the infection process by other morbilliviruses and host range determination remain unknown, partly because this region is highly flexible, which has hampered accurate structure determination of this region by X-ray crystallography. In this study, we analyzed the interaction between the H-protein from canine distemper virus (CDV-H) and SLAMs by a computational chemistry approach. Molecular dynamics simulations and fragment molecular orbital analysis demonstrated that the unique His28 in the N-terminal region of SLAM from Macaca is a key determinant that enables the formation of a stable interaction with CDV-H, providing a basis for CDV infection in Macaca. The computational chemistry approach presented should enable the determination of molecular interactions involving regions of proteins that are difficult to predict from crystal structures because of their high flexibility.