Agile Detection of Chemical Warfare Agents by Machine Vision: a Supramolecular Approach

The supramolecular detection by image analysis of a simulant chemical warfare agent on a solid device containing a selective molecular sensor based on a BODIPY scaffold is reported. The recognition properties were investigated in solution, demonstrating high affinity (log K 6.60) and sensitivity (LOD 10 ppt). A test strip also confirmed the sensing properties in gas phase. Image analysis of the solid device allows quantitative information about the simulant to be obtained, recovering the sensor almost 5 times and thus confirming the goal of the supramolecular approach.     

Charge transfer complexes of some N-methylated thiohydantoins with molecular iodine

Using a series of N-methylated thiohydantoins as substrates, the donor properties of the sulfur atom are measured by determining the stability constants (K) of their adducts with molecular iodine. The K's have been determined by recording the UV-visible spectra of several CH₂Cl₂ solutions with different amounts of the reagents. The experimental data fit the 1:1 adduct model for all the compounds. The K values, compared with those previously found for the unsubstituted hydantoins and with those obtained for 5-methyl-2-thiohydantoin, show that the hydrogen-bonding interaction between the NH hydrogen and the S-bonded iodine plays an important role in determining the stability of the adduct. The K values obtained for several pentaatomic rings, all containing the thioureido group  HN C() NH , are discussed on the basis of the influence of the substituents at C-4 and C-5 on the donor properties of the sulfur atom.     

Topochemical Synthesis of Two‐Dimensional Transition‐Metal Phosphides Using Phosphorene Templates

Transition‐metal phosphides (TMPs) have emerged as a fascinating class of narrow‐gap semiconductors and electrocatalysts. However, they are intrinsic nonlayered materials that cannot be delaminated into two‐dimensional (2D) sheets. Here, we demonstrate a general bottom‐up topochemical strategy to synthesize a series of 2D TMPs (e.g. Co₂P, Ni₁₂P₅, and Co_xFe_2?xP) by using phosphorene sheets as the phosphorus precursors and 2D templates. Notably, 2D Co₂P is a p‐type semiconductor, with a hole mobility of 20.8 cm² V^?1 s^?1 at 300 K in field‐effect transistors. It also behaves as a promising electrocatalyst for the oxygen evolution reaction (OER), thanks to the charge‐transport modulation and improved surface exposure. In particular, iron‐doped Co₂P (i.e. Co_1.5Fe_0.5P) delivers a low overpotential of only 278 mV at a current density of 10 mA cm^?2 that outperforms the commercial Ir/C benchmark (304 mV).     

Excitonic condensation in a symmetric electron-hole bilayer

Using diffusion Monte Carlo simulations we have investigated the ground state of a symmetric electron-hole bilayer and determined its phase diagram at T = 0. We find clear evidence of an excitonic condensate, whose stability however is affected by an in-layer electronic correlation. This stabilizes the electron-hole plasma at large values of the density or interlayer distance, and the Wigner crystal at low density and large distance. We have also estimated pair correlation functions and low-order density matrices to give a microscopic characterization of correlations as well as to try and estimate the condensate fraction.     

Excitation of stable transverse wavepackets with quadratic and cubic susceptibilities

We have identified a family of (2+1)D spatial solitary waves which can stably propagate in bulk media in the presence of coexisting diffraction, self-focusing Kerr and quadratic nonlinearities. In a conspicuous range of excitation conditions close to the stationary solutions, the emerging wavepackets are immune to the detrimental occurrence of filamentation and collapse, typical of pure Kerr media. The presence of a second-order contribution to the cubic nonlinear response is, therefore, able to prevent optical damage in applications relying on self-guidance. We show that the cross-phase modulation plays an important effect on stability. Our estimate shows that the effects of the cubic susceptibility cannot be neglected below a certain beam size in realistic crystals (e.g. KTP or similar).     

The limit state of indefinite plates on elastoplastic continuum

Summary The limit analysis of indefinite plates resting on a continuous elastoplastic medium and subjected to a load distributed over a partial surface with a circular boundary yields the fundamental equation governing the problem. Minimum conditions are set and the solution that supplies the collapse load of the plate-soil system is found by variational calculus.

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Sommario Si analizza lo stato limite delle piastre indefinite, appoggiate su un mezzo elastoplastico continuo e sottoposte a carico ripartito su una superficie parziale a contorno circolare, pervenendo all'equazione fondamentale che regge il problemaImponendo quindi delle condizioni minimizzanti, si trova, tramite il calcolo variazionale, la soluzione che fornisce il carico di collasso del sistema piastra-suolo.

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This research was supported by the CNR (National Research Council).     

Adducts of 2-aminothiophenol with acetylenic nitriles or esters and their conversion into benzothiazoles and/or 1,4-benzothiazines

The reaction between 2-aminothiophenol 1 and acetylenic nitriles or esters 2a-d leads to the vinyl thio-ethers 3a-d. The conversion of 3 into benzothiazoles 8 and/or 1,4-benzothiazines 9 , in boiling dimethyl sulfoxide, has been achieved. A possible pathway involving benzothiazolines 5 as key intermediates is suggested.     

Soluzioni periodiche di una classe di equazioni differenziali del terz’ ordine quasi lineari

Sommario. Si studia il problema della esistenza di soluzioni armoniche per una classe di equazioni differenziali periodiche del terz’ ordine di tipo quasi lineare, e si stabilisce un criterio di esistenza che estende precedenti risultati. Ricerca eseguita nell’ambito del Gruppo di Ricerca n. 11 del Comitato per la Matematica del C. N. R.     

Thiazolidin-4-one formation. Mechanistic and synthetic aspects of the reaction of imines and mercaptoacetic acid under microwave and conventional heating

Microwave irradiation of a mixture of benzylidene-anilines and mercaptoacetic acid in benzene gives 1,3-thiazolidin-4-ones in very high yield (65-90%), whereas the same reaction performed through using the conventional method, at reflux temperature, requires a much longer time and gives a much lower yield (25-69%). This difference seems to be due to some intermediates and by-products formed during the conventional reaction. On the basis of 1H NMR studies, two different mechanisms, acting in benzene and in DMF, respectively, have been hypothesized for the thiazolidin-4-one system formation.     

A general synthesis of water soluble upper rim calix[n]arene guanidinium derivatives which bind to plasmid DNA

The reaction of O-alkylated p-aminocalix[n]arenes (n=4, 6, 8) with N,N′-di(tert-butoxycarbonyl)thiourea in the presence of HgCl₂ and subsequent removal of the protective groups with hydrochloric acid led to the new water soluble calix[n]guanidinium derivatives (p-guanidiniumcalix[n]arenes) 20-23. With the exception of tetraoctyl-p-guanidiniumcalix[4]arene 21, which forms a macroscopic gelatinous aggregate even at very low concentration, all the synthesised guanidinium calixarenes show good solubility in water and sharp NMR signals. Moreover, these compounds are not cytotoxic and bind to plasmid DNA.