Cationic rhodium mono-phosphine fragments partnered with carborane monoanions [closo-CB11H6X6]- (X = H, Br). Synthesis, structures and reactivity with alkenes

Addition of the new phosphonium carborane salts [HPR(3)][closo-CB(11)H(6)X(6)] (R = (i)Pr, Cy, Cyp; X = H 1a-c, X = Br 2a-c; Cy = C(6)H(11), Cyp = C(5)H(9)) to [Rh(nbd)(mu-OMe)](2) under a H(2) atmosphere gives the complexes Rh(PR(3))H(2)(closo-CB(11)H(12)) 3 (R = (i)Pr 3a, Cy 3b, Cyp 3c) and Rh(PR(3))H(2)(closo-CB(11)H(6)Br(6)) 4 (R = (i)Pr 4a, Cy 4b, Cyp 4c). These complexes have been characterised spectroscopically, and for 4b by single crystal X-ray crystallography. These data show that the {Rh(PR(3))H(2)}(+) fragment is interacting with the lower hemisphere of the [closo-CB(11)H(6)X(6)](-) anion on the NMR timescale, through three Rh-H-B or Rh-Br interactions for complexes 3 and 4 respectively. The metal fragment is fluxional over the lower surface of the cage anion, and mechanisms for this process are discussed. Complexes 3a-c are only stable under an atmosphere of H(2). Removing this, or placing under a vacuum, results in H(2) loss and the formation of the dimer species Rh(2)(PR(3))(2)(closo-CB(11)H(12))(2) 5a (R = (i)Pr), 5b (R = Cy), 5c (R = Cyp). These dimers have been characterised spectroscopically and for 5b by X-ray diffraction. The solid state structure shows a dimer with two closely associated carborane monoanions surrounding a [Rh(2)(PCy(3))(2)](2+) core. One carborane interacts with the metal core through three Rh-H-B bonds, while the other interacts through two Rh-H-B bonds and a direct Rh-B link. The electronic structure of this molecule is best described as having a dative Rh(I) --> Rh(III), d(8)--> d(6), interaction and a formal electron count of 16 and 18 electrons for the two rhodium centres respectively. Addition of H(2) to complexes 5a-c regenerate 3a-c. Addition of alkene (ethene or 1-hexene) to 5a-c or 3a-c results in dehydrogenative borylation, with 1, 2, and 3-B-vinyl substituted cages observed by ESI-MS: [closo-(RHC[double bond, length as m-dash]CH)(x)CB(11)H(12-x)](-)x = 1-3, R = H, C(4)H(9). Addition of H(2) to this mixture converts the B-vinyl groups to B-ethyl; while sequential addition of 4 cycles of ethene (excess) and H(2) to CH(2)Cl(2) solutions of 5a-c results in multiple substitution of the cage (as measured by ESI-MS), with an approximately Gaussian distribution between 3 and 9 substitutions. Compositionally pure material was not obtained. Complexes 4a-c do not lose H(2). Addition of tert-butylethene (tbe) to 4a gives the new complex Rh(P(i)Pr(3))(eta(2)-H(2)C=CH(t)Bu)(closo-CB(11)H(6)Br(6)) 6, characterised spectroscopically and by X-ray diffraction, which show coordination of the alkene ligand and bidentate coordination of the [closo-CB(11)H(6)Br(6)](-) anion. By contrast, addition of tbe to 4b or 4c results in transfer dehydrogenation to give the rhodium complexes Rh{PCy(2)(eta(2)-C(6)H(9))}(closo-CB(11)H(6)Br(6)) 7 and Rh{PCyp(2)(eta(2)-C(5)H(7))}(closo-CB(11)H(6)Br(6)) 9, which contain phosphine-alkene ligands. Complex has been characterised crystallographically.     

Mechanisms behind the faceting of catanionic vesicles by polycations: chain crystallization and segregation

Vesicles composed of an anionic and a cationic surfactant, with a net negative charge, associate strongly with a hydrophobically modified polycation (LM200) and with an unmodified polycation with higher charge density (JR400), forming viscoelastic gel-like structures. Calorimetric results show that in these gels, LM200 induces a rise of the chain melting temperature (Tm) of the vesicles, whereas JR400 has the opposite effect. For both polymer-vesicle systems, the shear viscosity exhibits an inflection point at Tm, and for the LM200 system the measured relaxation times are significantly higher below Tm. The neat vesicles and the polycation-bound vesicles have a polygonal-like faceted shape when the surfactant chains in the bilayer are crystallized, as probed by cryo-transmission electron microscopy. Above Tm, the neat and the LM200-bound vesicles regain a spheroidal shape, whereas those in the JR400 system remain with a deformed faceted shape even above Tm. These shape changes are interpreted in terms of different mechanisms for the polymer-vesicle interaction, which seem to be highly dependent on polymer architecture, namely charge density and hydrophobic modification. A crystallization-segregation mechanism is proposed for the LM200-vesicle system, while, for the JR400-vesicle one, charge polarization-lateral segregation effects induced by the polycation in the catanionic bilayer are envisaged.     

Liquid mixtures of xenon with fluorinated species: xenon + sulfur hexafluoride

The vapor-liquid equilibrium of binary mixtures of xenon + SF6 has been measured at nine temperatures from 235.34 to 295.79 K and pressures up to 6.5 MPa. The mixture critical line is found to be continuous between the critical points of the pure components, and hence, the system can be classified as type I phase behavior in the scheme of van Konynenburg and Scott. The excess Gibbs free energies have been calculated, and the experimental results have been interpreted using the statistical associating fluid theory for potentials of variable range (SAFT-VR). Additionally, the SAFT-VR equation has been used to model other systems involving SF6 and alkanes, illustrating the predictability of the approach and further demonstrating the transferability of parameters between binary mixtures involving alkanes and xenon.     

Selective cross-couplings. Sequential Stille-Liebeskind/Srogl reactions of 3-chloro-4-arylthiocyclobutene-1,2-dione

The synthesis and initial reactivity studies of 2 are described. It was found that it participates in Stille couplings exclusively at the C-Cl site with a number of organostannanes (58-71% yield) in the absence of Cu(I). Then, these new derivatives were functionalized at the C-S site with boronic acids by switching to the Liebeskind-Srogl reaction conditions (in the presence of a Cu(I) carboxylate) to yield the bifunctionalized cyclobutenediones (44-90% yield).     

One-pot synthesis of 7H-dibenzo[b,d]azepin-7-one by heterogeneous flash vacuum pyrolysis with MCM-41 catalysts

Homogeneous and heterogeneous flash vacuum pyrolysis (fvp) reactions of 2-(1H-1,2,3-benzotriazol-1-yl)phenylethanone (1) are reported. Heterogeneous reactions were carried out with Al-MCM-41 catalysts, mesoporous molecular sieves of the type M41S. In both cases, 7H-dibenzo[b,d]azepin-7-one (4) was the major product; however, in the catalytic reactions, yields and selectivity were very high. A mechanism for this reaction is also discussed.     

Chemical physics: The standing of a mature discipline

Background

The use of immobilized enzymes for catalyzing various biotransformations is now a widely used approach. In recent years, cross-linked enzyme aggregates (CLEAs) have emerged as a novel and versatile biocatalyst design. The present work deals with the preparation of a CLEA from a commercial preparation, Pectinex? Ultra SP-L, which contains pectinase, xylanase and cellulase activities. The CLEA obtained could be used for any of the enzyme activities. The CLEA was characterized in terms of kinetic parameters, thermal stability and reusability in the context of all the three enzyme activities.

Results

Complete precipitation of the three enzyme activities was obtained with n-propanol. When resulting precipitates were subjected to cross-linking with 5 mM glutaraldehyde, the three activities initially present (pectinase, xylanase and cellulase) were completely retained after cross-linking. The V_max/K_m values were increased from 11, 75 and 16 to 14, 80 and 19 in case of pectinase, xylanase and cellulase activities respectively. The thermal stability was studied at 50°C, 60°C and 70°C for pectinase, xylanase and cellulase respectively. Half-lives were improved from 17, 22 and 32 minutes to 180, 82 and 91 minutes for pectinase, xylanase and cellulase respectively. All three of the enzymes in CLEA could be reused three times without any loss of activity.

Conclusion

A single multipurpose biocatalyst has been designed which can be used for carrying out three different and independent reactions; 1) hydrolysis of pectin, 2) hydrolysis of xylan and 3) hydrolysis of cellulose. The preparation is more stable at higher temperatures as compared to the free enzymes.     

Evidence for out-of-equilibrium crystal nucleation in suspensions of oppositely charged colloids

We report a numerical study of the rate of crystal nucleation in a binary suspension of oppositely charged colloids. Two different crystal structures compete in the thermodynamic conditions under study. We find that the crystal phase that nucleates is metastable and, more surprisingly, its nucleation free-energy barrier is not the lowest one. This implies that, during nucleation, there is insufficient time for subcritical nuclei to relax to their lowest free-energy structure. Such behavior is in direct contradiction with the common assumption that the phase that crystallizes most readily is the one with the lowest free-energy barrier for nucleation. The phenomenon that we describe should be relevant for crystallization experiments where competing solid structures are not connected by an easy transformation.     

Acoustic and thermal field investigation of low-cost dwellings, a case study in Brazil

The present paper presents acoustic and thermal performance evaluations carried out in low-cost houses located at the Vila Tecnológica de Curitiba (Technological Village of Curitiba), in Curitiba, Brazil. Two dwellings were evaluated, which were built according to different building systems: (1) the building system Batistella, built with pre-fabricated modules and elements, composed of reforestation wood and (2) the building system Constroyer, composed of expanded polystyrene (EPS) plates, framed in a welded iron mesh, with structural plastering. For the thermal performance evaluation, it was verified that the materials used in the envelope were quite significant for controlling heat gains and losses through the building elements as well as for regulating heat storage. In this case, the system with highest thermal inertia presented better results. Results showed that both building systems had poor acoustic performance, characterized by a low weighted apparent sound reduction index of the façade dB. The German DIN 4109 Norm recommends a minimum of dB. The weighted apparent sound reduction index measured for internal walls was dB and dB, for the building systems Battistela and Constroyer, respectively. The minimum required by German regulation VDI 4100 is dB, for internal walls.     

Uncovering seasonal patterns of 56 pesticides in surface coastal waters of the Ria Formosa lagoon (Portugal), using a GC-MS method

This study describes the simultaneous quantification of 56 pesticides in surface coastal water, supported by the development and validation of a gas chromatography (GC)–ion trap (IT) mass spectrometry (MS) method. Samples (500 mL) were pre-concentrated 2500 times by solid phase extraction (OASISTMHLB). The compounds were identified and quantified, within 35 minutes, by GC tandem mass spectrometry (GC-MS/MS) and GC-MS, respectively. The methodology proved to be highly specific for all target pesticides, with an average linearity of 0.99. Detection limits and recovery rates ranged from 0.4 to 1.3 ng L^?1 and 71% to 120%, respectively. The performance of the method was checked using water samples collected from nine sampling sites along the Ria Formosa Lagoon Natural Park (south of Portugal, n = 54) in each season (2010). The total annual concentrations of all pesticides in each category (fungicides, herbicides and insecticides) were 1.4, 0.6 and 9.0 µg L^?1, respectively. Moreover, 89% of the pesticides tested for were detected, 84% could be quantified and 25% had concentrations above the European recommended levels (2013/39/EU). The highest total loads of pesticides were found in the spring, which is in agreement with their seasonal application. Physicochemical parameters such as, nitrites, nitrates, ammonia and phosphates, also indicate poor water quality, supporting the fact that the Ria Formosa lagoon actually needs an effective monitoring programme for effective preservation of its natural reserve status.