Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

A Stochastic Subgradient Method for Distributionally Robust Non-convex and Non-smooth Learning

Journal of Optimization Theory and Applications - We consider a distributionally robust formulation of stochastic optimization problems arising in statistical learning, where robustness is with...     

Revealing the Effect of Surface Composition on Multiwalled Carbon Nanotubes Supported Pt-Fe Alloy Electrocatalysts for Methanol Oxidation Performance

The designs of efficient and inexpensive Pt-based catalysts for methanol oxidation reaction (MOR) are essential to boost the commercialization of direct methanol fuel cells. Here, the highly catalytic performance PtFe alloys supported on multiwalled carbon nanotubes (MWCNTs) decorating nitrogen-doped carbon (NC) have been successfully prepared via co-engineering of the surface composition and electronic structure. The Pt₁Fe₃@NC/MWCNTs catalyst with moderate Fe³⁺ feeding content (0.86 mA/mg_Pt) exhibits 2.26-fold enhancement in MOR mass activity compared to pristine Pt/C catalyst (0.38 mA/mg_Pt). Furthermore, the CO oxidation initial potential of Pt₁Fe₃@NC/MWCNTs catalyst is lower relative to Pt/C catalyst (0.71 V and 0.80 V). Benefited from the optimal surface compositions, the anti-corrosion ability of MWCNT, strong electron interaction between PtFe alloys and MWCNTs and the N-doped carbon (NC) layer, the Pt₁Fe₃@NC/MWCNTs catalyst presents an improved MOR performance and anti-CO poisoning ability. This study would open up new perspective for designing efficient electrocatalysts for the DMFCs field.     

Excellent UV-absorbing cotton fabric with high durability and hydrophobicity based on surface-initiated ATRP of polymerizable organic UV-absorber

Cellulose - Ultraviolet (UV) protective cotton fabric is a convenient and reliable way to protect human body from sunlight. Herein, a polymerizable UV-absorber,...     

Special John-Nirenberg-Campanato spaces via congruent cubes

Let p ∈ [1, ∞), q ∈ [1, ∞), α∈ R, and s be a non-negative integer. Inspired by the space JNp introduced by John and Nirenberg(1961) and the space B introduced by Bourgain et al.(2015), we introduce a special John-Nirenberg-Campanato space JN^con_(p,q,s) over Rⁿ or a given cube of R;with finite side length via congruent subcubes, which are of some amalgam features. The limit space of such spaces as p →∞ is just the Campanato space which coincides with the space BMO(the space of functions with bounded mean oscillations)when α = 0. Moreover, a vanishing subspace of this new space is introduced, and its equivalent characterization is established as well, which is a counterpart of the known characterization for the classical space VMO(the space of functions with vanishing mean oscillations) over Rⁿ or a given cube of Rⁿ with finite side length.Furthermore, some VMO-H¹-BMO-type results for this new space are also obtained, which are based on the aforementioned vanishing subspaces and the Hardy-type space defined via congruent cubes in this article. The geometrical properties of both the Euclidean space via its dyadic system and congruent cubes play a key role in the proofs of all these results.     

Periodicity of Two-Dimensional Bonding of Main Group Elements

In the periodic table the position of each atom follows the ‘aufbau’ principle of the individual electron shells. The resulting intrinsic periodicity of atomic properties determines the overall behavior of atoms in two-dimensional (2D) bonding and structure formation. Insight into the type and strength of bonding is the key in the discovery of innovative 2D materials. The primary features of 2D bonding and the ensuing monolayer structures of the main-group II–VI elements result from the number of valence electrons and the change of atom size, which determine the type of hybridization. The results reveal the tight connection between strength of bonding and bond length in 2D networks. The predictive power of the periodic table reveals general rules of bonding, the bonding-structure relationship, and allows an assessment of published data of 2D materials.     

High-fidelity Recognition of Organotrifluoroborate Anions (R−BF3−) as Designer Guest Molecules

The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF₃⁻). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF₃⁻, by cyanostar macrocycles that are size-complementary to the inorganic BF₄⁻ progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K⁺ salts of R−BF₃⁻ anions.     

Interfacial instability of ferrofluid flow under the influence of a vacuum magnetic field

This study is to numerically test the interfacial instability of ferrofluid flow under the presence of a vacuum magnetic field. The ferrofluid parabolized stability equations(PSEs) are derived from the ferrofluid stability equations and the Rosensweig equations, and the characteristic values of the ferrofluid PSEs are given to describe the ellipticity of ferrofluid flow. Three numerical models representing specific cases considering with/without a vacuum magnetic field or viscosity are created to mathematically examine the interfacial instability by the computation of characteristic values. Numerical investigation shows strong dependence of the basic characteristic of ferrofluid Rayleigh-Taylor instability(RTI) on viscosity of ferrofluid and independence of the vacuum magnetic field.For the shock wave striking helium bubble, the magnetic field is not able to trigger the symmetry breaking of bubble but change the speed of the bubble movement. In the process of droplet formation from a submerged orifice, the collision between the droplet and the liquid surface causes symmetry breaking. Both the viscosity and the magnetic field exacerbate symmetry breaking. The computational results agree with the published experimental results.     

Chemistry of Pentafluorosulfanyl Derivatives and Related Analogs: From Synthesis to Applications

Pentafluorosulfanyl (SF₅)-containing compounds and corresponding analogs are a highly valuable class of fluorine-containing building blocks owing to their unique properties. The reason for that is the set of peculiar and tremendously beneficial characteristics they can impart on molecules once introduced onto them. Despite this, their application in distinct scientific fields remains modest, given the extremely harsh reaction conditions needed to access such compounds. The recent synthetic approaches via S−F, and C−SF₅ bond formation as well as the use of SF₅-containing building blocks embody a “stairway-to-heaven” loophole in the synthesis of otherwise-inaccessible chemical scaffolds only a few years ago. Herein, we report and evaluate the properties of the SF₅ group and analogs, by summarizing synthetic methodologies available to access them as well as following applications in material science and medicinal chemistry since 2015.     

Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.