Effect of interchain coupling on conducting polymer luminescence: excimers in derivatives of poly(phenylene vinylene)

Optical excitation of a chain in a polymer film may result in formation of an excimer, a superposition of on-chain excitons and charge-transfer excitons on the originally excited chain and a neighboring chain. The excimer emission is red-shifted compared to that of an on-chain exciton by an amount depending on the interchain coupling $t_\perp$. Setting up the excimer wavefunction and calculating the red shift, we determine average $t_\perp$ values, referred to a monomer, of 0.52 eV and 0.16 eV for poly(2,5-hexyloxy $p$-phenylene cyanovinylene), CN-PPV, and poly[2-methoxy, 5-(2'-ethyl-hexyloxy)-1, 4 p-phenylene vinylene], MEH-PPV, respectively, and use them to determine the effect of interchain distance on the emission.Comment: 10 pages, RevTeX, 1 PS figure, replaced version of cond-mat/9707095, accepted for publication in Phys. Rev. B, Rapid Communicatio

Gearing motion in cogwheel pairs of molecular rotors: weak-coupling limit

Variable-​temp. (VT) crystal structures, VT 1H spin-​lattice relaxation in static crystals, and DFT modeling of the rotational barriers of BCP rotators in cryst. arrays of a rod-​like mol. contg. two 1,​3-​bis(ethynyl)​bicyclo[1.1.1]​pentane (BCP) units demonstrate that a correlated gearing motion occurs in the limit of a weak coupling between two rotors in a pair

Surface Grafting of Poly(L-glutamates). 2. Helix Orientation

In this paper the average helix orientation of surface-grafted poly(γ-benzyl L-glutamate) (PBLG), poly(γ-methyl L-glutamate) (PMLG), and poly(γ-methyl L-glutamate)-co-(γ-n-stearyl L-glutamate) (PMLGSLG 70/30) was investigated by means of FT-IR transmission spectroscopy. The theoretical relation between the average tilt angle (θ) and the absorption peak areas of three different backbone amide bands could be calculated because their transition dipole moment directions with respect to the helix axis were known. From the normalized absorptions, the average tilt angles of grafted helices of PBLG, PMLG, and PMLGSLG 70/30 were determined. The somewhat larger average angle of PMLG helices of 35 ± 5° with respect to the substrate compared to the value of 32 ± 5° of PBLG was due to the higher grafting density of PMLG. Because of the smaller helix diameter as a result of the smaller size of the methyl side group, more PMLG helices grew on the same surface area. Sterical hindrance and unfavorable polar interactions between unidirectional aligned helices forced the PMLG helices in a more upright arrangement. The even more perpendicular orientation of PMLGSLG 70/30 (48 ± 6°) could be the result of incorporation of mainly γ-methyl L-glutamate N-carboxyanhydride (MLG-NCA) monomers during the initiation step. Incorporation of the much larger γ-n-stearyl L-glutamate N-carboxyanhydride (SLG-NCA) monomers afterward lead to enlarged angles with respect to the substrate. Due to swelling, a pronounced change in helix orientation of grafted PMLGSLG 70/30 in n-hexadecane was observed, resulting in an almost perpendicular helix orientation.

Ketogenic diet as a glycine lowering therapy in nonketotic hyperglycinemia and impact on brain glycine levels

BACKGROUND: Nonketotic hyperglycinemia (NKH) is a severe neurometabolic disorder characterized by increased glycine levels. Current glycine reduction therapy uses high doses of sodium benzoate. The ketogenic diet (KD) may represent an alternative method of glycine reduction. AIM: We aimed to assess clinical and biochemical effects of two glycine reduction strategies: high dose benzoate versus KD with low dose benzoate. METHODS: Six infants with NKH were first treated with high dose benzoate therapy to achieve target plasma glycine levels, and then switched to KD with low dose benzoate. They were evaluated as clinically indicated by physical examination, electroencephalogram, plasma and cerebral spinal fluid amino acid levels. Brain glycine levels were monitored by magnetic resonance spectroscopy (MRS). RESULTS: Average plasma glycine levels were significantly lower with KD compared to benzoate monotherapy by on average 28%. Two infants underwent comparative assessments of brain glycine levels via serial MRS. A 30% reduction of brain glycine levels was observed in the basal ganglia and a 50% reduction in the white matter, which remained elevated above normal, and was equivalent between the KD and high dose benzoate therapies. CSF analysis obtained while participants remained on the KD showed a decrease in glycine, serine and threonine levels, reflecting their gluconeogenetic usage. Clinically, half the patients had seizure reduction on KD, otherwise the clinical impact was variable. CONCLUSION: KD is an effective glycine reduction method in NKH, and may provide a more consistent reduction in plasma glycine levels than high-dose benzoate therapy. Both high-dose benzoate therapy and KD equally reduced but did not normalize brain glycine levels even in the setting of low-normal plasma glycine

Structure and photophysics of indigoids for singlet fission: Cibalackrot

We report an investigation of structure and photophysics of thin layers of cibalackrot, a sturdy dye derived from indigo by double annulation at the central double bond. Evaporated layers contain up to three phases, two crystalline and one amorphous. Relative amounts of all three have been determined by a combination of X-ray diffraction and FT-IR reflectance spectroscopy. Initially, excited singlet state rapidly produces a high yield of a transient intermediate whose spectral properties are compatible with charge-transfer nature. This intermediate more slowly converts to a significant yield of triplet, which, however, does not exceed 100% and may well be produced by intersystem crossing rather than singlet fission. The yields were determined by transient absorption spectroscopy and corrected for effects of partial sample alignment by a simple generally applicable procedure. Formation of excimers was also observed. In order to obtain guidance for improving molecular packing by a minor structural modification, calculations by a simplified frontier orbital method were used to find all local maxima of singlet fission rate as a function of geometry of a molecular pair. The method was tested at 48 maxima by comparison with the ab initio Frenkel-Davydov exciton model. Published under license by AIP Publishing

New strategies and designs in pancreatic cancer research: consensus guidelines report from a European expert panel

Although the treatment of pancreatic ductal adenocarcinoma (PDAC) remains a huge challenge, it is entering a new era with the development of new strategies and trial designs. Because there is an increasing number of novel therapeutic agents and potential combinations available to test in patients with PDAC, the identification of robust prognostic and predictive markers and of new targets and relevant pathways is a top priority as well as the design of adequate trials incorporating molecular-driven hypothesis. We presently report a consensus strategy for research in pancreatic cancer that was developed by a multidisciplinary panel of experts from different European institutions and collaborative groups involved in pancreatic cancer. The expert panel embraces the concept of exploratory early proof of concept studies, based on the prediction of response to novel agents and combinations, and randomised phase II studies permitting the selection of the best therapeutic approach to go forward into phase III, where the recommended primary end point remains overall survival. Trials should contain as many translational components as possible, relying on standardised tissue and blood processing and robust biobanking, and including dynamic imaging. Attention should not only be paid to the pancreatic cancer cells but also to microenvironmental factors and stem/stellate cell

Crystalline Arrays of Pairs of Molecular Rotors: Correlated Motion, Rotational Barriers, and Space-Inversion Symmetry Breaking Due to Conformational Mutations

The rod-like molecule bis 4-(4-pyridyl)ethynyl)bicyclo[2.2.2]oct-1-yl)buta-1,3-diyne, 1, contains two 1,4-bis(ethynyl)bicyclo[2.2.2]octane (ethynyl) chiral rotators linked by a diyne fragment and self assembles in a one-dimensional, monoclinic C2/c centrosymmetric structure where two equilibrium positions with large occupancy imbalance (88% versus 12%) are identified on a single rotor site Combining variable temperature (70-300 K) proton spin-lattice relaxation, H-1 T-1(-1), at two different H-1 Larmor frequencies (55 and 210 MHz) and DFT calculations of rotational barriers, we were able to assign two types of Brownian rotators with different activation energies, 1.85 and 6.1 kcal mol(-1), to the two H-1 spin-lattice relaxation processes on the single rotor site. On the basis of DFT calculations, the low-energy process has been assigned to adjacent rotors in a well-correlated synchronous motion, whereas the high-energy process is the manifestation of an abrupt change in their kinematics once two blades of adjacent rotors are seen to rub together. Although crystals of 1 should be second harmonic inactive, a large second-order optical response is recorded when the electric field oscillates in a direction parallel to the unique rotor axle director. We conclude that conformational mutations by torsional interconversion of the three blades of the BCO units break space-inversion symmetry in sequences of mutamers in dynamic equilibrium in the crystal in domains at a rnesoscopic scale comparable with the wavelength of light used A control experiment was performed with a crystalline film of a similar tetrayne molecule, 1,4-bis(3-((trimethylsilyl)ethynyl)bicyclo-[1.1.1]pent-1-yObuta-1,3-diyne, whose bic-ydopentane units can rotate but are achiral and produce no second-order optical response

Paternal attractiveness and the effects of differential allocation of parental investment

The differential allocation hypothesis (DAH) predicts that an individual should vary its reproductive investment according to the attractiveness of its mate. A recently revised version of the DAH makes explicit that investment can be positive, i.e. higher for the offspring of attractive males which should be of higher quality, or negative, i.e. higher for offspring of unattractive males, for example compensating for inheriting poor paternal genes. Moreover, investment can be made by the father and the mother. Here, we tested whether experimental manipulation of male attractiveness affected parental investment at different reproductive stages and thus influenced fitness-related traits in offspring. In two aviaries, all male zebra finches, Taeniopygia guttata, were given red leg rings to increase attractiveness and in two aviaries all males received green leg rings to decrease attractiveness. This controlled for assortative mating between treatments. Ring colour was merely an experimental manipulation of male attractiveness, not paternal quality, so we might expect additional investment to elevate offspring quality. Eggs were cross-fostered between and within treatments to allow differentiation of effects of investment in eggs and nestlings. Clutch and brood sizes were standardized. Both positive and negative investment were observed: Eggs from red-ringed fathers had higher yolk to albumen ratios than eggs from green-ringed fathers. Nestlings from eggs laid and incubated by parents in the red-ringed group had higher hatching masses than those in the green-ringed group. Both parents in the green-ringed group fed nestlings more frequently than red-ringed parents. Offspring performance was influenced by the treatment of both foster and biological parents, but combined effects of these different investment patterns on fitness-related traits were ambiguous. Male attractiveness appeared to affect patterns of reproductive investment but not consistently across all forms of reproductive investment suggesting that the costs and benefits of differential allocation vary among individuals and across contexts