Fluorous phase transfer catalysts: From onium salts to crown ethers

Fluorous quaternary ammonium and phosphonium salts, as well as fluorous macrocyclic ligands, such as crown and aza-crown ethers, have been gradually emerging as viable alternatives to classical phase transfer catalysts. The major results thus far obtained in this burgeoning field will be the focus of this review.     

A note on the classification of Fano manifolds of middle index

We rule out a doubtful case in the classification of Fano manifolds of middle indexMathematics Subject Classification (2000): 14J40, 14J45     

Symmetry in the geometry of metric contact pairs

We prove that the universal covering of a complete locally symmetric normal metric contact pair manifold with decomposable ? is a Calabi‐Eckmann manifold or the Riemannian product of a sphere and . We show that a complete, simply connected, normal metric contact pair manifold with decomposable ?, such that the foliation induced by the vertical subbundle is regular and reflections in the integral submanifolds of the vertical subbundle are isometries, is the product of globally ?‐symmetric spaces or the product of a globally ?‐symmetric space and . Moreover in the first case the manifold fibers over a locally symmetric space endowed with a symplectic pair.     

A segmentation procedure of the pervious area of the aorta artery from CT images without contrast medium

In this paper, we develop an algorithm for the segmentation of the pervious lumen of the aorta artery in computed tomography (CT) images without contrast medium, a challenging task due to the closeness gray levels of the different zones to segment. The novel approach of the proposed procedure mainly resides in enhancing the resolution of the image by the application of the algorithm deduced from the mathematical theory of sampling Kantorovich operators. After the application of suitable digital image processing techniques, the pervious zone of the artery can be distinguished from the occluded one. Numerical tests have been performed using 233 CT images, and suitable numerical errors have been computed and introduced ex novo to evaluate the performance of the proposed method. The above procedure is completely automatic in all its parts after the initial region of interest (ROI) selection. The main advantages of this approach relies in the potential possibility of performing diagnosis concerning vascular pathologies even for patients with severe kidney diseases or allergic problems, for which CT images with contrast medium cannot be achieved.     

On cubic-linear polynomial mappings

In the field of the Jacobian conjecture it is well-known after Dru?kowski that from a polynomial ‘cubic-homogeneous’ mapping we can build a higher-dimensional ‘cubic-linear’ mapping and the other way round, so that one of them is invertible if and only if the other one is. We make this point clearer through the concept of ‘pairing’ and apply it to the related conjugability problem: one of the two maps is conjugable if and only if the other one is; moreover, we find simple formulas expressing the inverse or the conjugations of one in terms of the inverse or conjugations of the other. Two nontrivial examples of conjugable cubic-linear mappings are provided as an application.     

A macrocyclic ligand as receptor and Zn(II)-complex receptor for anions in water: binding properties and crystal structures

Binding properties of 24,29-dimethyl-6,7,15,16-tetraoxotetracyclo[19.5.5.0(5,8).0(14,17)]-1,4,9,13,18,21,24,29-octaazaenatriaconta-Δ(5,8),Δ(14,17)-diene ligand L towards Zn(II) and anions, such as the halide series and inorganic oxoanions (phosphate (Pi), sulfate, pyrophosphate (PPi), and others), were investigated in aqueous solution; in addition, the Zn(II)/L system was tested as a metal-ion-based receptor for the halide series. Ligand L is a cryptand receptor incorporating two squaramide functions in an over-structured chain that connects two opposite nitrogen atoms of the Me(2)[12]aneN(4) polyaza macrocyclic base. It binds Zn(II) to form mononuclear species in which the metal ion, coordinated by the Me(2)[12]aneN(4) moiety, lodges inside the three-dimensional cavity. Zn(II)-containing species are able to bind chloride and fluoride at the physiologically important pH value of 7.4; the anion is coordinated to the metal center but the squaramide units play the key role in stabilizing the anion through a hydrogen-bonding network; two crystal structures reported here clearly show this aspect. Free L is able to bind fluoride, chloride, bromide, sulfate, Pi, and PPi in aqueous solution. The halides are bound at acidic pH, whereas the oxoanions are bound in a wide range of pH values ranging from acidic to basic. The cryptand cavity, abundant in hydrogen-bonding sites at all pH values, allows excellent selectivity towards Pi to be achieved mainly at physiological pH 7.4. By joining amine and squaramide moieties and using this preorganized topology, it was possible, with preservation of the solubility of the receptor, to achieve a very wide pH range in which oxoanions can be bound. The good selectivity towards Pi allows its discrimination in a manner not easily obtainable with nonmetallic systems in aqueous environment.     

Effects of the net charge on abundance and stability of supramolecular surfactant aggregates in gas phase

Self-assembling of amphiphilic molecules under electrospray ionization (ESI) conditions is characterized by quite unexpected phenomenology. The noticeable differences with respect to the condensed phase are attributable to the absence of the surfactant-solvent interactions, the presence of net charge in the aggregates, and the strong deviation from equilibrium conditions. Aiming to investigate the effects of the net charge on abundance and stability of supramolecular surfactant aggregates, positively and negatively charged aggregates of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium methane sulfonate (MetS), butane sulfonate (ButS) and octane sulfonate (OctS) have been studied by ESI mass spectrometry, energy resolved mass spectrometry and density functional theory calculations. The negatively charged aggregates are found to be less stable than their positive counterparts. The results are consistent with a self-assembling pattern dominated by electrostatic interactions involving the counterions and head groups of the investigated amphiphilic compounds while the alkyl chains point outwards, protecting the aggregates from unlimited growth processes.     

Bismuth-Based Halide Perovskites for Photocatalytic H2 Evolution Application

Metal halide perovskites (MHPs), in particular lead-based perovskites, have earned recognized fame in several fields for their outstanding optoelectronic properties, including direct generation of free charge carriers, optimal ambipolar charge carrier transport properties, high absorption coefficient, point-defect tolerance, and compositional versatility. Nowadays, this class of materials represents a real and promising alternative to silicon for photovoltaic technologies. This worthy success led to a growing interest in the exploration of MHPs in other hot research fields, such as solar-driven photocatalytic water splitting towards hydrogen production. Nevertheless, many of these perovskites show air and moisture instability problems that considerably hinder their practical application for photocatalytic water splitting. Moreover, if chemical instability is a problem that can be in part mitigated by the optimization of the chemical composition and crystal structure, the presence of lead represents a real problem for the practical application of MHPs in commercial devices due to environmental and healthcare issues. To successfully overcome these problems, lead-free metal halide perovskites (LFMHPs) have gained increasing interest thanks to their optoelectronic properties, comparable to lead-based materials, and their more eco-friendly nature. Among all the lead-free perovskite alternatives, this mini-review considers bismuth-based perovskites and perovskite derivatives with a specific focus on solar-driven photocatalysis application for H₂ evolution. Special attention is dedicated to the structure and composition of the different materials and to the advantage of heterojunction engineering and the relative impact on the photocatalytic process.     

New π‐stacked benzofulvene polymer showing thermoreversible polymerization: Studies in macromolecular and aggregate structures and polymerization mechanism

The macromolecular and aggregate structures of poly[ethyl 1‐methylene‐3‐(4‐methylphenyl)‐1H‐indene‐2‐carboxylate] (poly‐ BF1 ; a new polymer based on a functionalized benzofulvene moiety showing interesting properties, i.e., thermoreversible polymerization/depolymerization behavior, high solubility in the most common organic solvents, and susceptibility to molecular manipulation) have been investigated with NMR spectroscopy, absorption and emission spectrophotometry, and transmission electron microscopy (TEM). Moreover, the polymerization mechanism has been studied to obtain further information on the polymer structure. The collected evidence is consistent in indicating for poly‐ BF1 a vinyl (1,2) polymer structure stabilized by means of aromatic stacking interactions. Furthermore, TEM studies performed on metal replicas have shown that the polymer is liable to give nanostructured aggregates. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3289–3304, 2005     

Refinement of the crystal and molecular structure of 3,5-diamino-1,2,4-dithiazolium bromide. Comparative investigation on the thiouret hydrohalides

The crystal and molecular structure of 3,5-diamino-1,2,4-dithiazolium bromide has been refined from three-dimensional counter data (856 reflections) by least-squares methods, anisotropically for the nonhydrogen and isotropically for the hydrogen atoms, to a finalR=0.036:a=9.948(1),b=12.731(1),c=5.098(1) Å, B=98.70(1)° at 18°C,Z=4,P2₁/n. The S-S (2.075 Å) distance is intermediate between those of the thiouret hydrochloride and hydroiodide. The C-N(terminal) and C-N(bridging) distances are close to their average value (1.322 Å) within their standard deviations. Thev(NH₂) and (NH₂) frequencies of the thiouret hydrohalides are close to those of dithiobiuret while thev(NH) and (NH) bands are, as expected, absent. Thev(CN) andv(CS) bands are shifted to higher and lower frequencies, respectively, while a newv(SS) broad band is observed in the 430–410 cm^–1 region.