Polyhedral metallaheteroborane chemistry. Synthesis, spectroscopy, structure and dynamics of eleven-vertex {RhNB(9)} and {PtCB(9)} metallaheteroboranes

Reaction between [RhCl(PPh(3))(3)] and the [nido-6-NB(9)H(11)](-) anion in CH(2)Cl(2) yields orange eleven-vertex [8,8-(PPh(3))(2)-nido-8,7-RhNB(9)H(11)]. Reaction of the [nido-6-CB(9)H(12)](-) anion with [cis-PtCl(2)(PMe(2)Ph)(2)] in methanol affords yellow eleven-vertex [9-(OMe)-8,8-(PMe(2)Ph)(2)-nido-8,7-PtCB(9)H(10)], which is also formed from the reaction of MeOH with [8,8-(PPh(3))(2)-nido-8,7-PtCB(9)H(10)]. Both compounds have been characterised by single-crystal X-ray diffraction analysis and examined by NMR spectroscopy and have structures based on eleven-vertex nido-type geometries, with the metal centre and the heteroatoms in the adjacent (8)- and (7)-positions on the pentagonal open face. The metal-to-heteroborane bonding sphere of is fluxional, with a DeltaG(double dagger) value of 48.4 kJ mol(-1). DFT calculations on the model compounds [8,8-(PH(3))(2)-nido-8,7-RhNB(9)H(11)] and [8,8-(PH(3))(2)-nido-8,7-RhSB(9)H(10)] have been carried out to define the fluxional process and the intermediates involved.     

Azatricarbaborane 7-t-Bu-arachno-7,1,5,12-NC3B8H12 and Parent Tricarbaboranes nido-[5,6,9-C3B7H10]- and -5,6,9-C3B7H11

The neutral azatricarbaborane 7-t-Bu-arachno-7,1,5,12-NC(3)B(8)H(12), isolated as a side product (yield 2%) from the new synthesis of 7-t-BuNH2-nido-7,8,9-C(3)B(8)H(10) (yield 70%), can be easily converted to the first parent representatives of the 10-vertex nido family of tricarbaboranes, [5,6,9-C(3)B(7)H(10)]- and 5,6,9-C(3)B(7)H(11).     

Differential pulse voltammetric determination of selected nitrophenols on novel type of porous silver working electrode prepared by powder metallurgy

Nitrophenols are important environmental pollutants and their monitoring is important because of their genotoxic and ecotoxic properties. Easy electrochemical reduction of nitro groups can be used for their voltammetric determination using mercury based electrodes. However, requirements of green analytical chemistry prompted us to investigate a novel type of silver porous electrode (AgPE) prepared by powder metallurgy compatible with both “green” and “white” analytical chemistry requirements. In this paper, AgPE was for the first time successfully used for differential pulse voltammetric determination of micromolar concentrations of 2-nitrophenol (NP), 2,4-dinitrophenol (DNP), and 2,4,6-trinitrophenol (TNP) in aqueous media. The main advantage of the novel method is the possibility to use small sample volume (down to 25 μL) and to work in the presence of oxygen when using supporting electrolyte of pH 3. This advantage partially compensates the fact that the obtained sensitivity and limit of detection are not better than with the previously investigated electrodes.     

Tailoring of polymers by combination of ionic and radical controlled polymerizations

Poly(methyl methacrylate)s with terminal bromine atom, prepared by bromination of anionically polymerized MMA, were used as ATRP macroinitiators giving di- and triblock copolymers with MMA, styrene and butyl acrylate blocks. Multifunctional ATRP macroinitiators were synthesized by introducing bromomethyl or 2-bromoacyloxy groups onto the main chain of polystyrene or poly(4-methyl styrene) and used for ATRP grafting of tert-butyl acrylate leading to densely grafted copolymers with more or less uniform grafts.     

The Phototoxic Potential of the Flavonoids,Taxifolin and Quercetin

Quercetin, one of the most abundant polyphenols in the plant kingdom has been shown to be photodegraded on exposure to UV light. Despite the fact, it is a component of several dermatological preparations. Its phototoxic potential has not been evaluated to date. The aim of this study was to assess whether photo‐induced degradation of quercetin is linked to phototoxic effects on living cells. Its dihydro derivative, taxifolin, was included in the study. For evaluation, the 3T3 Neutral Red Uptake Phototoxicity Test according to OECD TG 432 was used. To better approximate human skin, HaCaT keratinocytes, normal human epidermal keratinocytes and dermal fibroblasts were used, apart from the Balb/c 3T3 cell line. Quercetin showed a dose‐dependent photodegradation in aqueous and organic environments and a phototoxic effect on all used cells. Quercetin pretreatment and following UVA exposure resulted in increased reactive oxygen species production and intracellular glutathione level depletion in human dermal fibroblasts. Taxifolin was found completely nonphototoxic and photostable. As only in vitro methodology was used, further studies using 3D skin models and/or human volunteers are needed to confirm whether exposure to sunlight, tanning sunbeds and/or phototherapy in people using cosmetics containing quercetin is a health risk.     

Unusual interaction of alkynes with nine-vertex arachno-monocarbaboranes 4-CB8H14 and [4-CB8H13]-

Alkynes R(1)R(2)C(2) react with the neutral monocarbaborane arachno-4-CB(8)H(14) (1) at elevated temperatures (115-120 degrees C) under the formation of the derivatives of the ten-vertex dicarbaborane nido-5,6-C(2)B(8)H(12) (2) of general formula 9-Me-5,6-R1,R2-nido-5,6-C(2)B(8)H(9) (where R1,R2 = H,H 2a; Me,Me 2b; Et,Et 2c, H,Ph 2d, and Ph,Ph 2e) in moderate yields (26-52%). Side reaction with PhC(2)H also yields 1-Ph-6-Me-closo-1,2-C(2)B(8)H(8) (3d). In contrast, the reaction between [arachno-4-CB(8)H(13)](-) anion ((-)) and PhC(2)H produces a mixture of the closo anions [1-CB7H8]- (4-) and [1-CB6H7]- (5-) (yields 32 and 24%, respectively). Individual compounds were isolated and purified by liquid chromatography and characterized by NMR spectroscopy ((11)B, (1)H and (13)C) combined with two-dimensional [(11)B-(11)B]-COSY and (1)H-{(11)B(selective)}NMR techniques.