Gold(I) and Gold(0) Complexes of Phosphinine-Based Macrocycles

A "CO-like matrix", showing coordination analogous to that of carbonyl groups, is provided by silacalix[4]phosphinine macrocycles. Reaction with Au(I) leads to the first gold(I) complexes of macrocycles, which can be reduced with sodium or potassium to the paramagnetic gold(0) complexes (an example is shown), as evidenced by cyclic voltammetry and EPR spectroscopy.     

Relationship between (2 + 1) and (3 + 1)-Friedmann–Robertson–Walker cosmologies; linear,non-linear,and polytropic state equations

It is shown that Friedmann–Robertson–Walker (FRW) cosmological models coupled to a single scalar field and to a perfect fluid fitting a wide class of matter perfect fluid state equations, determined in (3+1) dimensional gravity can be related to their (2+1) cosmological counterparts, and vice-versa, by using simple algebraic rules relating gravitational constants, state parameters, perfect fluid and scalar field characteristics. It should be pointed out that the demonstration of these relations for the scalar fields and potentials does not require the fulfilment of any state equation for the scalar field energy density and pressure. As far as to the perfect fluid is concerned, one has to demand the fulfilment of state equations of the form p+ = f(). If the considered cosmologies contain the inflation field alone, then any (3+1) scalar field cosmology possesses a (2+1) counterpart, and vice-versa. Various families of solutions are derived, and we exhibited their correspondence; for instance, solutions for pure matter perfect fluids and single scalar field fulfilling linear state equations, solutions for scalar fields coupled to matter perfect fluids, a general class of solutions for scalar fields subjected to a state equation of the form p + = are reported, in particular Barrow–Saich, and Barrow–Burd–Lancaster–Madsen solutions are exhibited explicitly, and finally perfect fluid solutions for polytropic state equations are given.     

Curvature in causal BD-type inflationary cosmology

We study a closed model of the universe filled with viscous fluid and quintessence matter components in a Brans-Dicke type cosmological model. The dynamical equations imply that the universe may look like an accelerated flat Friedmann-Robertson-Walker universe at low redshift. We consider here dissipative processes which follow a causal thermodynamics. The theory is applied to viscous fluid inflation, where accepted values for the total entropy in the observable universe are obtained.     

LETTER: BTZ Black Hole from (3+1) Gravity

We propose an approach for constructing spatial slices of (3+1) spacetimes with cosmological constant but without a matter content, which yields (2+1) vacuum with solutions. The reduction mechanism from (3+1) to (2+1) gravity is supported on a criterion in which the Weyl tensor components are required to vanish together with a dimensional reduction via an appropriate foliation. By using an adequate reduction mechanism from the Plebaski–Carter[A] solution in (3+1) gravity, the (2+1) BTZ solution can be obtained.     

Formation of a phosphorus-phosphorus bond by successive one-electron reductions of a two-phosphinines-containing macrocycle: crystal structures, EPR, and DFT investigations.

Chemical and electrochemical reductions of the macrocycle 1 lead to the formation of a radical monoanion anion [1](*)(-) whose structure has been studied by EPR in liquid and frozen solutions. In accord with experimental (31)P hyperfine tensors, DFT calculations indicate that, in this species, the unpaired electron is mainly localized in a bonding sigma P-P orbital. Clearly, a one-electron bond (2.763 A) was formed between two phosphorus atoms which, in the neutral molecule, were 3.256 A apart (crystal structure). A subsequent reduction of this radical anion gives rise to the dianion [1](2)(-) which could be crystallized by using, in the presence of cryptand, Na naphthalenide as a reductant agent. As shown by the crystal structure, in [1](2)(-), the two phosphinine moieties adopt a phosphacyclohexadienyl structure and are linked by a P-P bond whose length (2.305(2) A) is only slightly longer than a usual P-P bond. When the phosphinine moieties are not incorporated in a macrocycle, no formation of any one-electron P-P bond is observed: thus, one-electron reduction of 3 with Na naphthalenide leads to the EPR spectrum of the ion pair [3](*)(-) Na(+); however, at high concentration, these ion pairs dimerize, and, as shown by the crystal structure of [(3)(2)](2)(-)[(Na(THF)(2))(2)](2+) a P-P bond is formed (2.286(2) A) between two phosphinine rings which adopt a boat-type conformation, the whole edifice being stabilized by two carbon-sodium-phosphorus bridges.     

Preparation and Properties of Nanostructured Rubber Composites with Montmorillonite

Montmorillonite exfoliated nanoclay was prepared by treating montmorillonite with an alkyalmmonium salt. It has been characterized by FT-IR spectroscopy and thermal analysis (TGA-DTA). The nanoclay composites, in which the rubber matrix was introduced by mixing solutions of the elastomer with the organically modified clay was then compounded with carbon black filler at 2.5, 5, 10, 15 phr loading level of nanoclay. The sulfur cured rubber samples were tested against a reference compound not filled with the nanoclay. Rheometrical and scorch measurements have shown that the nanoclay increases the curing speed and reduces the scorch safety. A very high reinforcement and stiffening effect due to the nanoclay was observed especially at 5 and 10 phr nanoclay filling level and especially at low extension modulus which can be increased up to 40% its original level than in the reference compound. An anisotropic behavior has been recorded in the stress-strain curve: for instance the 50% modulus was found >20% higher when measured parallel to the alignment of the exfoliated nanoclay lamellae in comparison to the modulus perpendicular to the lamellae orientation. The compounds with nanoclay show no adverse effects in tensile strength and in tear resistance, in De Mattia crack initiation and in abrasion resistance. Nanoclay reduces also the hysteresis and heat build up of the rubber compounds.     

Fullerene C60 Trichloromethylation Through CCl4 Plasmalysis or Sonolysis

The trichloromethylation of C₆₀ fullerene was achieved either under plasmalysis conditions, i.e. by arcing a solution of C₆₀ in CCl₄ between two graphite electrodes, or by sonolysis of C₆₀ in CCl₄. The resulting products were studied by UV–VIS and FT-IR spectroscopy as well as by thermogravimetric analysis in comparison to the trichloromethyl adducts formed by radiolysis or photolysis of C₆₀ in CCl₄. A reference study on the plasmalysis of pure CCl₄ has revealed the formation of carbon soot and hexachlorobenzene. The formation of the latter compound was suppressed when C₆₀ was present in CCl₄.     

On modeling the dissolution of sedimentary rocks in acidic environments. An overview of selected mathematical methods with presentation of a case study

Different environmental processes utilize calcium carbonate and sedimentary rocks, for instance sedimentary rocks are used for water purification as filters and utilized also for acid remediation of process waters before being discarded. Additionally sedimentary rocks are used in another very important environmental process, wet Flue Gas Desulfurization. In this process, limestone and carbonates in general play one important role because of their dissolution and provision of the necessary amount of calcium ions used for the precipitation of gypsum. The objective of this study is to present in a first place an overview of a reduced number of specific theoretical and empirical mathematical models applied to the dissolution of carbonates in acidic environments with provision of additional developments and details, secondly a case study was presented where a suitable time of exposure and surface diffusivity obtained analytically by different methods well describe the experimental results. There were justifications for this choice. The experimental data and the related mathematical modeling were performed considering transient conditions. In the present work diverse raw materials were tested in order to reveal their suitability for wet Flue Gas Desulfurization. The research was focused on products from $\text{ CO }_{2}$ CO 2 fixation processes materials as well as other types of limestone samples. In this way it was found that also waste materials from different environmental processes, like $\text{ CO }_{2}$ CO 2 fixation can be used for Flue Gas Desulfurization.     

Radiation-Induced Polymerization of Vinylidene Chloride in Bulk and Included in Thiourea Crystals

Vinylidene chloride (VDC) or 1,1-dichloroethylene was polymerized with γ radiation in bulk or as inclusion complex in thiourea crystals (inclusion polymerization). The resulting poly(vinylidenechloride) (PVDC) samples obtained from the two different polymerization techniques were characterized by FT-IR and electronic absorption spectroscopies, by ozonolysis and by thermal analysis (TGA, DTG and DTA). It was found that two selective secondary reactions occur in the two PVDC samples, respectively obtained from bulk polymerization or from inclusion polymerization. In the former case, the main reaction is only a crosslinking reaction, while in the latter case, with the PVDC included into the thiourea channels, the crosslinking reaction is fully inhibited and instead a dehydrohalogenation reaction takes place producing the polyene structures. The presence of polyene structures in the PVDC synthesized by the inclusion polymerization was demonstrated by electronic absorption spectroscopy and by ozonolysis experiments. The presence of polyene segments in the PVDC causes a reduction in the thermal stability of the polymer, lowers its melting point and reduces its crystallinity.     

Synthesis and Study of the Thermal and Chiro-Optical Properties of Polyacetylenes with Bulky Side Groups: Poly(1-ethynyl-4-biphenyl), Poly(1-ethynyl-4- phenoxybenzene) and Poly(1-ethynyl-4-pentylbenzene)

The monosubstituted acetylenes 1-ethynyl-4-biphenyl, 1-ethynyl-4-phenoxybenzene and 1-ethynyl-4-pentylbenzene were polymerized to the corresponding polyacetylenes with bulky side substituents: PEBIP, PEPHENO and PEPB, respectively, using a Rh(I) complex as polymerization catalyst. The FT-IR and UV-VIS spectra of PEBIP, PEPHENO and PEPB were studied using the corresponding spectra of polyphenylacetylene (PPA), polytolylacetylene (PETOL) and poly(1-ethynyl-naphthalene) PEN as reference. Based on the spectral analysis, high cis-trasoid structures were assigned to PEBIP, PEPHENO and PEPB. The specific optical rotation of PEBIP, PEPHENO and PEPB was measured in the chiral solvent α (-)pinene and, only for PEPB, also in α (+)pinene. It was found that even at low concentration PEBIP, PEPHENO and PEPB cause changes in the specific optical rotation of the chiral medium where they have been dissolved. This phenomenon has not been observed when toluene or atactic polystyrene are dissolved in the same chiral solvent in similar concentration. This suggests that the polyacetylenes with bulky side groups are able to rearrange in a helical configuration (prevalently right-handed or vice-versa, depending on the type of chiral medium used) once hosted in a chiral medium giving a contribution to the chirality of the solvent where they have been dissolved. The thermal stability of PEBIP, PEPHENO and PEPB was studied under N₂ flow by thermal analysis (TGA, DTG and DTA) in comparison to reference monosubstituted polyacetylenes PPA, PETOL and PEN. The results show that the thermal stability of monosubstituted polyacetylenes is greatly improved by the presence of bulky substitutents as theoretically expected, and similarly, also the char-forming tendency increases with the bulkiness of the side groups.