Theoretical Modeling of the Surface-Guided Self-Assembly of Functional Molecules

Directing the self-assembly of organic building blocks with 2D templates has been a promising method to create molecular superstructures having unique physicochemical properties. In this work the on-surface self-assembly of simple ditopic functional molecules confined inside periodic nanotemplates was modeled by means of the lattice Monte Carlo simulation method. Two types of confinement, that is honeycomb porous networks and parallel grooves of controlled diameter and width were used in the calculations. Additionally, the effect of (pro)chirality of the adsorbing molecules on the outcome of the templated self-assembly was examined. To that end, enantiopure and racemic assemblies were studied and the resulting structures were identified and classified. The obtained findings demonstrated that suitable tuning of the structural parameters of the templates enables directing the self-assembly towards linear and cyclic aggregates with controlled size. Moreover, chiral resolution of the molecular conformers using honeycomb networks with adjusted pore size was found possible. Our theoretical predictions can be helpful in designing structured surfaces to direct self-assembly and polymerization of organic functional building blocks.     

Degradation of Amino-(3-methoxyphenyl)methanephosphonic Acid by Alternaria sp

Alternaria sp. isolated from the surface of carrot ( Daucus carota ) seeds appeared to be able to degrade amino-(4-methoxyphenyl)-methanephosphonic acid using it as a sole source of carbon, nitrogen, and phosphorus for growth.     

Azulene‐Based Macrocyclic Receptors for Recognition and Sensing of Phosphate Anions

Herein we report the synthesis and detailed studies of the anion‐binding properties of two 20‐membered macrocyclic tetramide receptors: one symmetrical, containing two identical azulene‐based bisamide units, the other a hybrid, containing a dipicolinic bisamide unit and an azulene‐based bisamide unit. Analysis of the crystal structures of the macrocyclic receptors revealed their preference for adopting similar well‐preorganized bent‐sheet conformations, both as free receptors and in their complexes with anions. Studies of the optical properties of both receptors revealed abilities to selectively sense phosphate anions (H₂PO₄^?, HP₂O₇^3?), allowing for naked‐eye detection of the presence of these guests in DMSO. Binding studies in solution confirmed that the receptors bind strongly to a series of anions even in highly demanding media, such as mixtures of DMSO with water or with methanol. Comparison of the anion affinity of linear analogues with that of the macrocyclic receptors evidenced the importance of macrocyclic topology. Quantitative analysis revealed that the macrocyclic receptors are selective for H₂PO₄^? over other anions. The affinity to H₂PO₄^? seen for the symmetrical receptor, containing two azulene‐based subunits, is much higher than for the hybrid macrocycle containing both the azulene‐based and pyridine‐derived subunits. This highlights that the azulene‐based building block serves efficiently as both a binding site and a structure‐preorganizing motif.     

Synthesis and characterisation of coating polyurethane cationomers containing fluorine built-in hard urethane segments

Polyurethane cationomers were synthesised in the reaction of 4,4’-methylenebis(phenyl isocyanate) with polyoxyethylene glycol (M?= 2,000) or poly(tetrafluoroethyleneoxide-co-difluoromethylene oxide) α,ω-diisocyanate and N-methyl diethanolamine. Amine segments were built-in to the urethane-isocyanate prepolymer in the reaction with 1-bromobutane or formic acid, and then they were converted to alkylammonium cations. The obtained isocyanate prepolymers were then extended in the aqueous medium that yielded stable aqueous dispersions which were applied on the surfaces of test poly(tetrafluoroethylene) plates. After evaporation of water, the dispersions formed thin polymer coatings. ¹H, ¹³C NMR and IR spectral methods were employed to confirm chemical structures of synthesised cationomers. Based on ¹H NMR and IR spectra, the factors κ and α were calculated, which represented the polarity level of the obtained cationomers. The DSC, wide angle X-ray scattering and atom force microscopy methods were employed for the microstructural assessment of the obtained materials. Changes were discussed in the surface free energy and its components, as calculated independently according to the method suggested by van Oss–Good, in relation to chemical and physical structures of cationomers as well as morphology of coating surfaces obtained from those cationomers. Fluorine incorporated into cationomers (about 30%) contributed to lower surface free energy values, down to about 15 mJ/m². That was caused by gradual weakening of long-range interactions within which the highest share is taken by dispersion interactions.     

Homogeneity and the disjoint arcs property

Some previous results of the author towards a classification of homogeneous metric continua are improved. The disjoint arcs property is fully revealed in this context. In particular, closed -manifolds, , are characterized as those homogeneous continua which do not have the disjoint arcs property.

     

Symmetries of Cauchy-Riemann spaces

We simplify and generalize Cartan's results on Cauchy-Riemann spaces admitting continuous groups of automorphisms. We describe all such spaces in terms of local coordinates.     

Preparation and semiconducting properties of Th3As4

The resistivity, thermoelectric power and Hall constant in the temperature range of 78–830 K were determined for polycrystalline Th₃As₄ samples obtained by annealing thin thorium slabs in arsenic vapour. The samples examined were n-type semiconductors with a carrier concentration ranging from 1.0 × 10¹⁸cm^?3 to 2.8 × 10¹⁸ cm^?3 for which the effective mass was found to be equal to 0.55–0.76m₀. The Hall mobility, about 450cm²V^?1s^?1 at room temperature, obeys a $\text{T}{}^{\mathrm{<mtext>?3</mtext><mtext>2</mtext>}}$ law at high temperatures. On the basis of the electrical measurements the forbidden gap of Th₃As₄ was found to be equal to 0.43 eV.     

Probing interfacial organization in surface monolayers using tethered pyrene. 1. Structural mediation of electron and proton access to adsorbates

We have synthesized and characterized a family of self-assembled monolayers containing pyrene derivatives on gold and indium-doped tin oxide (ITO) substrates. The covalently bound pyrene functionalities serve as either spectroscopic or electrochemical probes of their immediate environment, and we explore their electrochemical response in this paper. When these compounds are the only constituents bound to the interfaces, the molecules enjoy significant structural freedom. The addition of aliphatic adsorbates to the interfaces serves to place the pyrene derivatives in a more restricted environment. Cyclic voltammetry shows that the organization of a monolayer with pyrene derivatives, and the position of the terminal pyrene within such monolayer, depend sensitively on the length of the pyrene tether and the presence or absence of aliphatic interfacial species, as well as the identity of the substrate.     

Locking entanglement with a single qubit

We study the loss of entanglement of a bipartite state subjected to discarding or measurement of one qubit. Examining behavior of different entanglement measures, we find that entanglement of formation, entanglement cost, logarithmic negativity, and one-way distillable entanglement are lockable measures in that they can decrease arbitrarily after measuring one qubit. We prove that any convex and asymptotically noncontinuous measure is lockable. As a consequence, all the convex-roof measures can be locked. The relative entropy of entanglement is shown to be a nonlockable measure.