Salvatore Pincherle

Commemorazione letta davanti alla Classe di Scienze fisiche, matematiche e naturali della Reale Accademia Nazionale dei Lincei nell'adunanza del 5 dicembre 1937-XVI.     

Solid-phase microextraction and gas chromatography–mass spectrometry for rapid characterisation of semi-hard cheeses

A headspace solid-phase microextraction (HS-SPME) method in combination with gas chromatography–mass spectrometry (GC–MS) has been used for extraction and identification of components of the volatile fraction of Provola dei Nebrodi, a typical semi-hard Sicilian cheese. Cheese samples from different producers and at different ripening stages have been examined. The effects of various conditions (e.g. sample volume, sample headspace volume, sample heating temperature, extraction time, etc.) on extraction efficiency were studied in order to optimise the technique. The technique used made it possible to identify 61 components: fatty acids from C₂ to C₁₄ and their esters, aldehydes, alcohols, methyl ketones, -lactones, aromatic compounds, hydrocarbons and terpenes. The main components were butanoic, hexanoic and octanoic acids. The linear free fatty acids (FFA) from C₂ to C₁₀ were quantified by using the standard addition method. Calibration curves constructed for the FFA spiked into cheese were highly linear with a correlation coefficient R²>0.998. Significant statistical differences (P0.05) were evident for the even-carbon-number fatty acids during ripening.     

A hybrid living/organic electrochemical transistor based on the Physarum polycephalum cell endowed with both sensing and memristive properties

A hybrid bio-organic electrochemical transistor was developed by interfacing an organic semiconductor, poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate), with the Physarum polycephalum cell. The system shows unprecedented performances since it could be operated both as a transistor, in a three-terminal configuration, and as a memristive device in a two terminal configuration mode. This is quite a remarkable achievement since, in the transistor mode, it can be used as a very sensitive bio-sensor directly monitoring biochemical processes occurring in the cell, while, as a memristive device, it represents one of the very first examples of a bio-hybrid system demonstrating such a property. Our system combines memory and sensing in the same system, possibly interfacing unconventional computing. The system was studied by a full electrical characterization using a series of different gate electrodes, namely made of Ag, Au and Pt, which typically show different operation modes in organic electrochemical transistors. Our experiment demonstrates that a remarkable sensing capability could potentially be implemented. We envisage that this system could be classified as a Bio-Organic Sensing/Memristive Device (BOSMD), where the dual functionality allows merging of the sensing and memory properties, paving the way to new and unexplored opportunities in bioelectronics.     

An extension of Babbage’s criterion for primality

Let n > 1 and k > 1 be positive integers. We show that if $$\left( {\begin{array}{*{20}c} {n + m} \\ n \\ \end{array} } \right) \equiv 1 (\bmod k)$$ for each integer m with 0 ≤ m ≤ n ? 1, then k is a prime and n is a power of this prime. In particular, this assertion under the hypothesis that n = k implies that n is a prime. This was proved by Babbage, and thus our result may be considered as a generalization of this criterion for primality.     

Approximating the maximum 3-edge-colorable subgraph problem

We offer the following structural result: every triangle-free graph G of maximum degree 3 has 3 matchings which collectively cover at least of its edges, where γ_o(G) denotes the odd girth of G. In particular, every triangle-free graph G of maximum degree 3 has 3 matchings which cover at least 13/15 of its edges. The Petersen graph, where we can 3-edge-color at most 13 of its 15 edges, shows this to be tight. We can also cover at least 6/7 of the edges of any simple graph of maximum degree 3 by means of 3 matchings; again a tight bound.For a fixed value of a parameter k≥1, the Maximum k-Edge-Colorable Subgraph Problem asks to k-edge-color the most of the edges of a simple graph received in input. The problem is known to be APX-hard for all k≥2. However, approximation algorithms with approximation ratios tending to 1 as k goes to infinity are also known. At present, the best known performance ratios for the cases k=2 and k=3 were 5/6 and 4/5, respectively. Since the proofs of our structural result are algorithmic, we obtain an improved approximation algorithm for the case k=3, achieving approximation ratio of 6/7. Better bounds, and allowing also for parallel edges, are obtained for graphs of higher odd girth (e.g., a bound of 13/15 when the input multigraph is restricted to be triangle-free, and of 19/21 when C₅’s are also banned).     

Topological Features of Massive Bosons on Two-Dimensional Einstein Space–Time

In this paper, we tackle the problem of constructing explicit examples of topological cocycles of Roberts’ net cohomology, as defined abstractly by Brunetti and Ruzzi. We consider the simple case of massive bosonic quantum field theory on the two-dimensional Einstein cylinder. After deriving some crucial results of the algebraic framework of quantization, we address the problem of the construction of the topological cocycles. All constructed cocycles lead to unitarily equivalent representations of the fundamental group of the circle (seen as a diffeomorphic image of all possible Cauchy surfaces). The construction is carried out using only Cauchy data and related net of local algebras on the circle.     

Counteranion dependent protonation and aggregation of tetrakis(4-sulfonatophenyl)porphyrin in organic solvents

The tetrabutylammonium salt of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) is soluble in dichloromethane, and the general properties of this compound have been investigated as function of various added acids HX (X = Cl, Br, I, CF(3)COO, CF(3)SO(3), TFPB) through UV-vis absorption spectroscopy, steady state fluorescence emission, and resonance light-scattering (RLS) techniques. Upon addition of HX, the initial monomeric free base TPPS is readily converted in an aggregated species, whose spectroscopic features are independent of the nature of the counteranion X. All the spectroscopic evidence suggest a J-type arrangement of chromophores in this aggregate, involving strong hydrogen bonds, electrostatic, and dispersive interactions. In the specific case of chloride and bromide, in the presence of a TBAX excess, the addition of the corresponding acid leads to a monomeric ion-pair between the TBA cations and the diacid TPPS, whose central core is strongly interacting with the halide. On further increasing the acid concentration in these latter solutions, fully protonated species are formed that eventually start to aggregate.     

Platinum(II) complexes bearing 1,1'-bis(diphenylphosphino)ferrocene as building blocks for functionalized redox active porphyrins

Reactions of the cationic complex ions [PtMe(Me2SO)(PP)]+ (PP = dppf (1,1'-bis(diphenylphosphino)ferrocene) and dppe (1,2-bis(diphenylphosphino)ethane)) with 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin (TpyP) led to the formation of the symmetrical tetraplatinated porphyrin complexes, [PtMe(PP)]4TpyP.X4 (PP = dppf, X = CF3SO3-, 3, and PP = dppe, X = BF4-, 5) containing the organometallic fragment [PtMe(PP)]. The precursor sulfoxide platinum complexes [PtMe(Me2SO)(dppf)]CF3SO3, 2 and [PtMe(Me2SO)(dppe)]BF4, 4, were prepared by halide abstraction from [PtMeCl(dppf)], 1, and by controlled protonolysis of [PtMe2(dppe)] respectively, in the presence of a small amount of dimethyl sulfoxide. All these starting platinum(II) compounds, as well as the porphyrin derivatives 3 and 5, were fully characterized through elemental analysis, 1H NMR mono- and bidimensional, 31P[1H], 31P-1H HMBC, UV/Vis absorption and photophysical measurements. The X-ray crystal structure of complex 1 has been determined. In order to ascertain the electronic influence of ferrocene, the spectroscopic and redox properties of 3 were compared with those of TPyP and of the analogous 5. Cyclic voltammetry (CV), differential pulse voltammetry (DPV), 1H and 31P NMR data, and UV/Vis data, all suggest a certain degree of communication between the central porphyrin and the peripheral hetero-bimetallic fragments. In contrast, no detectable interaction among these peripheral groups seem to come into play. Unlikely from the porphyrin derivative 5, formation of well defined fluorescent mesoscopic ring structures was easily achieved by simple evaporation from diluted dichloromethane solutions of 3.