Optical spectroscopy of a polyfluorene copolymer at high pressure: intra- and intermolecular interactions

We present optical spectroscopy studies of the conjugated polymer poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) at high pressure. The photoluminescence spectrum of F8BT in a dilute solid-state solution in polystyrene redshifts by 320 meV over 7.4 GPa, while that of a F8BT thin film redshifts 460 meV over a comparable pressure range. We attribute the redshift in solution to intrachain pressure effects, principally conformational planarization. The additional contribution from interchain pi-electron interactions accounts for the larger redshift of thin films.     

Spacetime emergence of the robertson-walker universe from a matrix model

Using a novel, string theory-inspired formalism based on a Hamiltonian constraint, we obtain a conformal mechanical system for the spatially flat four-dimensional Robertson-Walker Universe. Depending on parameter choices, this system describes either a relativistic particle in the Robertson-Walker background or metric fluctuations of the Robertson-Walker geometry. Moreover, we derive a tree-level M theory matrix model in this time-dependent background. Imposing the Hamiltonian constraint forces the spacetime geometry to be fuzzy near the big bang, while the classical Robertson-Walker geometry emerges as the Universe expands. From our approach, we also derive the temperature of the Universe interpolating between the radiation and matter dominated eras.     

Diels-Alder approach for the construction of halogenated, o-nitro biaryl templates and application to the total synthesis of the anti-HIV agent siamenol

A rapid Diels-Alder approach to halogenated biaryl templates is described. These biaryl templates are available in two steps from the corresponding aromatic aldehydes. The scope of subsequent Suzuki couplings on the biaryl chlorides is explored. Good tolerance for both electron-donating and electron-withdrawing groups in the coupling process can be achieved. Further functionalization of the biaryl templates is described. Hydrogenation of the nitro moiety with concomitant removal of the benzyl ether yields the o-anilino, o-phenolic polyaryls. Selective reduction of the nitro group can be accomplished. Alternatively, the benzyl ether can be selectively removed under Lewis acidic conditions. The utilization of the Diels-Alder adducts for the synthesis of a series of chlorinated carbazoles via the Cadogan cyclization is also demonstrated. Finally, application of this technology to the total synthesis of siamenol, an anti-HIV agent, is reported.     

Surface chemistry and rheology of polysulfobetaine-coated silica

We have measured the viscosity of suspensions of colloidal silica particles (d = 300 nm) and the properties of silica surfaces in solutions of a polymer consisting of zwitterionic monomer groups, poly(sulfobetaine methacrylate), polySBMA. This polymer has potential use in modifying surface properties because the polymer is net uncharged and therefore does not generate double-layer forces. The solubility of the polymer can be controlled and varies from poor to good by the addition of sodium chloride salt. Ellipsometry was used to demonstrate that polySBMA adsorbs to silica and exhibits an increase in surface excess at lower salt concentration, which is consistent with a smaller area per molecule at low salt concentration. Neutron reflectivity measurements show that the adsorbed polymer has a thickness of about 3.7 nm and is highly hydrated. The polymer can be used to exercise considerable control over suspension rheology. When silica particles are not completely covered in polymer, the suspension produces a highly viscous gel. Atomic force microscopy was used to show this is caused by bridging of polymer between the particles. At higher surface coverage, the polymer can produce either a high or very low viscosity slurry depending on the sodium chloride concentration. At high salt concentration, the suspension is stable, and the viscosity is lower. This is probably because the entrainment of many small ions renders the polymer film highly hydrophilic, producing repulsive surface forces and lubricating the flow of particles. At low salt concentrations, the polymer is barely soluble and more densely adsorbed. This produces less stable and more viscous solutions, which we attribute to attractive interactions between the adsorbed polymer layers.     

A reactive Ru-binaphtholate building block with self-tuning hapticity

A versatile Ru-BINO building block is reported, which offers a straightforward entry point into the chemistry of atropisomeric binaphtholate complexes of ruthenium. Reaction of RuCl(2)(PPh(3))(3)6a with Tl(2)((S)-BINO) affords Ru((S)-BINO)(PPh(3))(2)7 as a mixture of isomers: in 7', the BINO ligand is bound via η(3)-CCO,η(1)-O' donors, and in symmetrical 7″, via η(3)-CCO,η(3)-O'C'C' interactions. The bis(enolate) BINO bonding mode in the latter, not previously observed for any metal, underscores the remarkable geometric and electronic flexibility of the binaphtholate moiety. The BINO ligand proves able to stabilize complexes containing as few as two, and as many as four, additional ligands in 7 and its derivatives, enabling a synthetic versatility that contrasts with that of the superficially similar o-catecholate complex Ru(o-cat)(PPh(3))(3). As with the important achiral Ru precursor 6a, complex 7 undergoes facile transformation into a range of products under mild conditions, including acetonitrile, pyridine, and vinylidene derivatives. Single-crystal X-ray structures are reported for three of these complexes: Ru(η(3),η(3)-(S)-BINO)(PPh(3))(2)7″, Ru(η(3),η(1)-(S)-BINO)(PPh(3))(2)(MeCN) 9, and Ru(η(3),η(1)-(S)-BINO)(PPh(3))(py)(2)11. (13)C{(1)H} NMR signatures are proposed for new and known BINO coordination modes (η(1)-O,η(1)-O'; η(1)-C1,η(1)-O'; η(3)-CCO,η(3)-O'C'C'; η(3)-CCO,η(1)-O'; η(6)-C(6),η(1)-O'), as a potential aid to further developments in late-metal BINO chemistry.     

A sensitive method for determination of allergenic fragrance terpene hydroperoxides using liquid chromatography coupled with tandem mass spectrometry

Different compositions of monoterpenes are utilized for their pleasant scent in cosmetics and perfumes. However, the most commonly used fragrance terpenes easily oxidize upon contact with air, forming strongly skin‐sensitizing hydroperoxides. Due to their thermolability and low UV absorbance, detection methods for hydroperoxides are scarce. For the first time, a simple and sensitive method using LC/ESI‐MS/MS was developed to quantitatively determine hydroperoxides from the common fragrance compounds linalool, linalyl acetate, and limonene. The method was applied to autoxidized petitgrain oil and sweet orange oil. A separation was accomplished using a C₃ column. The method LOD for the investigated hydroperoxides in the essential oils was below 0.3 μg/mL, corresponding to 0.3 ppm. For prevention purposes and according to EU regulations, concentrations in cosmetics exceeding 100 ppm in “rinse‐off” and 10 ppm in “stay‐on” products of linalool and limonene must be labeled. However, the products may still contain allergens, such as hydroperoxides, formed by oxidative degradation of their parent terpenes. The sensitivity and selectivity of the presented LC/MS/MS method enables detection of hydroperoxides from the fragrance terpenes linalool, linalyl acetate, and limonene. However, for routine measurements, the method requires further validation.     

Total Synthesis of (18S)‐ and (18R)‐Homolargazole by Rhodium‐Catalyzed Hydrocarboxylation

Homolargazole derivatives, in which the macrocycle of natural largazole is extended by one methylene group, were prepared by the recently developed rhodium‐catalyzed hydrocarboxylation reaction onto allenes. This strategy gives access to both the (18S)‐ and (18R)‐stereoisomers in high stereoselectivity under ligand control.     

Synthesis and crystal structure of the new high-pressure phase CdB2O4

The use of high-pressure/high-temperature conditions (7.5 GPa and 1100 degrees C; Walker-type multianvil apparatus) led to the synthesis of a new cadmium borate CdB2O4, starting from stoichiometric mixtures of the oxides. The crystal structure was determined on the basis of single crystal X-ray diffraction data, to reveal the hexagonal space group P6(3) with a=885.2(2), c=716.72(8) pm, Z=8, R1=0.0178, and wR2=0.0388 (all data). CdB2O4 is built up from interconnected layers of BO4-tetrahedra and exhibits for the first time the basic structure of a family of compounds, represented by BaGa2O4, KAlSiO4, KGeAlO4, KCoPO4, CaP2N4 and the recently discovered SrP2N4. The lack of superstructure ordering in CdB2O4 was confirmed by electron diffraction. Additionally, a B--O--B angle of 180 degrees was found in this borate for the first time.