Computational Analysis of Mesomerism in para-Substituted mer-NCN Pincer Platinum(II) Complexes,Including its Relationships with Hammett σp Substituent Parameters

Density Functional Theory studies of square-planar Pt^II pincer structures, (4-Z-NCN)PtCl ([4-Z-NCN]⁻=[4-Z-2,6-(Me₂NCH₂)₂C₆H₂-N,C,N]⁻, Z=H, NO₂, CF₃, CO₂H, CHO, Cl, Br, I, F, SMe, SiMe₃, tBu, OH, NH₂, NMe₂), enable characterisation of mesomerism for the pincer-Pt interaction. Relationships between Hammett σ_p substituent parameters of Z and DFT data obtained from NBO6 and AOMix computation are used to probe the interaction of the 5d_yz orbital of platinum with π-orbitals of the arene ring. Analogous computation for 2,6-(Me₂CH₂)₂C₆H₃Z (Z=H, CF₃, CHO, Cl, Br, I, F, SMe, SiMe₃, tBu, OH, NH₂) and (4-H-NCN)PtZ allows an estimation of the relative substituent effects of “(CH₂NMe₂)₂PtZ” on π-delocalisation in the pincer system.     

Tetramethyl guanidine-assisted synthesis and thermal crosslinking of multifunctional benzoxazine monomers based on natural phloretic acid

An efficient strategy to synthesize novel biobased multifunctional benzoxazine compounds was developed using the 1,1,3,3-tetramethyl guanidine (TMG)-triggered esterification of natural phloretic acid with organic halides as a key synthetic step. First, phloretic acid was combined with either aniline or furfurylamine to prepare the corresponding carboxylic acid-functional monobenzoxazine monomer. Next, the use of TMG enabled an efficient esterification of these compounds with di-, tri-, and tetra-functional benzyl bromide compounds at room temperature to afford a series of new multi-benzoxazine monomers tethered to an aromatic core. The effect of the functionality of the monomers on the curing process was analyzed, indicating that the reactivity during the thermally induced ring-opening increases with the number of furan and oxazine rings in the monomers. The resulting thermosets revealed good correlation between the number of oxazine rings in the structure of the monomer and the properties of the crosslinked materials. Furfurylamine-based polybenzoxazines showed improved thermal behavior compared to the aniline-based systems, due to the role of furan rings. All materials showed high T_g, good thermal stability, and promising flame retardancy properties.     

Copper Complexes with Diazoolefin Ligands and their Photochemical Conversion into Alkenylidene Complexes

Homometallic copper complexes with alkenylidene ligands are discussed as intermediates in catalysis but the isolation of such complexes has remained elusive. Herein, we report the structural characterization of copper complexes with bridging and terminal alkenylidene ligands. The compounds were obtained by irradiation of Cu^I complexes with N-heterocyclic diazoolefin ligands. The complex with a terminal alkenylidene ligand required isolation in a crystalline matrix, and its structural characterization was enabled by in crystallo photolysis at low temperature.     

A Water-Soluble Iridium Photocatalyst for Chemical Modification of Dehydroalanines in Peptides and Proteins

Dehydroalanine (Dha) residues are attractive noncanonical amino acids that occur naturally in ribosomally synthesised and post-translationally modified peptides (RiPPs). Dha residues are attractive targets for selective late-stage modification of these complex biomolecules. In this work, we show the selective photocatalytic modification of dehydroalanine residues in the antimicrobial peptide nisin and in the proteins small ubiquitin-like modifier (SUMO) and superfolder green fluorescent protein (sfGFP). For this purpose, a new water-soluble iridium(III) photoredox catalyst was used. The design and synthesis of this new photocatalyst, [Ir(dF(CF₃)ppy)₂(dNMe₃bpy)]Cl₃, is presented. In contrast to commonly used iridium photocatalysts, this complex is highly water soluble and allows peptides and proteins to be modified in water and aqueous solvents under physiologically relevant conditions, with short reaction times and with low reagent and catalyst loadings. This work suggests that photoredox catalysis using this newly designed catalyst is a promising strategy to modify dehydroalanine-containing natural products and thus could have great potential for novel bioconjugation strategies.     

Standing Waves on an Infinitely Deep Perfect Fluid Under Gravity

The existence of two-dimensional standing waves on the surface of an infinitely deep perfect fluid under gravity is established. When formulated as a second-order equation for a real-valued function w on the 2-torus and a positive parameter μ, the problem is fully nonlinear (the highest order x-derivative appears in the nonlinear term but not in the linearization at 0) and completely resonant (there are infinitely many linearly independent eigenmodes of the linearization at 0 for all rational values of the parameter μ). Moreover, for any prescribed order of accuracy there exists an explicit approximate solution of the nonlinear problem in the form of a trigonometric polynomial. Using a Nash-Moser method to seek solutions of the nonlinear problem as perturbations of the approximate solutions, the existence question can be reduced to one of estimating the inverses of linearized operators at non-zero points. After changing coordinates these operators become first order and non-local in space and second order in time. After further changes of variables the main parts become diagonal with constant coefficients and the remainder is regularizing, or quasi-one-dimensional in the sense of [22]. The operator can then be inverted for two reasons. First, the explicit formula for the approximate solution means that, restricted to the infinite-dimensional kernel of the linearization at zero, the inverse exists and can be estimated. Second, the small-divisor problems that arise on the complement of this kernel can be overcome by considering only particular parameter values selected according to their Diophantine properties. A parameter-dependent version of the Nash-Moser implicit function theorem now yields the existence of a set of unimodal standing waves on flows of infinite depth, corresponding to a set of values of the parameter μ>1 which is dense at 1. Unimodal means that the term of smallest order in the amplitude is cos x cos t, which is one of many eigenfunctions of the completely resonant linearized problem.     

ELECTROMECHANICAL WAVES IN CERAMICS——NUMERICAL SIMULATION

A simple one-dimensional model is used to simulate numerically the propagation oflinear and nonlinear waves in a deformable ceramic.The nummrical scheme used providesthe response in stress or strain and electric field within the sample and the voltage at aresistive external circuit connecting the two faces of the sample.Space-time diagrams of thepropagation are obtained for various mechanical loads.The voltage response obtainedagress well with experimental results in the linear regime.In the nonlinear one,thesteepening of the electromechanical wave yielding a shock wave is exhibited.     

Hydroindene-derived chiral synthons from carotol and their cytotoxicity

Ten enantiomerically pure hydroindene-derived compounds obtained by the transformation of (+)-carotol, the main constituent of carrot seed essential oil, were examined for their ability to inhibit the growth of myeloid leukaemia (HL-60) cancer cell lines. All compounds showed significant activity, which was comparable to the most active volatile organic compounds, such as trans–trans-farnesol, citral and nerolidol. Based on the bioactivity and molecular modelling, a 3D QSAR pharmacophore model was generated.