MOLECULAR PACKING IN TRIACYL-sn-GLYCEROLS: INFLUENCES OF ACYL CHAIN LENGTH AND UNSATURATION

The molecular packing in triacylglycerols having different acyl chains has been examined by differential scanning calorimetry, powder X-ray diffraction and vibrational spectroscopy (infrared and Raman) techniques. In the triacylglycerols examined, the acyl chain length, unsaturation or the position of substitution on the glycerol were changed systematically to observe their influence on the molecular packing in different polymorphic forms. Variation in the 3-acyl chain length of 1,2-dipalmitoyl-3-acyl-sn-glycerols (PPX) influenced the molecular packing along the long axis in the stable polymorphic forms. Three different modes of packing were observed. If X ≤ 4, the compounds packed in a bilayer structure similar to diacylglycerols, or if X ≥ 10 and ≤ 16 the compounds packed in a bilayer structure but similar to mono acid triacylglycerols. However for intermediate 3-acyl chain lengths, as in PP6 and PP8 the stable packing can occured only through chain segregation resulting in a trilayer structure. In the triacylglycerols containing unsaturated acyl chains, 1,2-dioleoyl-3-acyl-sn-glycerols (00X) and 1,3-dioleoyl-Z-acyl-sn-glycerols (0X0) the stable polymorphic forms packed in a trilayer structure where the odd acyl chains segregated and formed a middle layer. In a metastable hexagonal packing (α-phase) the long range ordering is minimal. Because of this lack of specific chain-chain interaction the 3-short acyl chain compounds of PPX packed in a unimolecular length structure (except PP2) whereas the 3-long acyl chain compounds packed in a bilayer structure. In orthorhombic perpendicular and triclinic parallel packing where the specific chain-chain interaction is increased, the end plane methyl packing and the glycerol conformation played important roles in the formation of bi-, tri- and hexalayer structures. The driving force in the formation of these different structures is to minimize the crystal defects created by the odd acyl chains and to enhance the specific chain-chain interactions. The presence of an odd acyl chain influenced the lateral chain packing as well, e.g., the stability of the orthorhombic perpendicular packing is enhanced by the presence of an odd acyl chain and even in some cases it is favored over the triclinic parallel packing. The odd acyl chain at the 1- or 3position of -sn-glycerol stabilized the orthorhombic perpendicular packing. This indicates the glycerol conformation is probably perpendicular to the layer plane and thus is different from the monoacid triacylglycerols.     

Synthesis of twist-twist pi-conjugated di-sec-alkylstilbenes and stilbene polymers

Twist-twist pi-conjugated (TTPC) pi systems promise unique properties with their 90 degrees twist angles. Di-sec-alkyl substituted stilbenes, 5, were prepared by low-valent titanium coupling of phenyl ketones, 4. Long alkyl chains stopped the coupling reaction. Stilbenes 5 were shown to be approximately 90% TTPC. Inserting TTPC units into poly(p-phenylene) polymers created highly fluorescent, soluble, TTPC pi systems with weak electronic segmentation for organic light emitting diode (OLED) studies.     

An Ethenoadenine FAD Analog Accelerates UV Dimer Repair by DNA Photolyase

Reduced anionic flavin adenine dinucleotide (FADH^?) is the critical cofactor in DNA photolyase (PL) for the repair of cyclobutane pyrimidine dimers (CPD) in UV‐damaged DNA. The initial step involves photoinduced electron transfer from *FADH^? to the CPD. The adenine (Ade) moiety is nearly stacked with the flavin ring, an unusual conformation compared to other FAD‐dependent proteins. The role of this proximity has not been unequivocally elucidated. Some studies suggest that Ade is a radical intermediate, but others conclude that Ade modulates the electron transfer rate constant (k_ET) through superexchange. No study has succeeded in removing or modifying this Ade to test these hypotheses. Here, FAD analogs containing either an ethano‐ or etheno‐bridged Ade between the AN1 and AN6 atoms (e‐FAD and ε‐FAD, respectively) were used to reconstitute apo‐PL, giving e‐PL and ε‐PL respectively. The reconstitution yield of e‐PL was very poor, suggesting that the hydrophobicity of the ethano group prevented its uptake, while ε‐PL showed 50% reconstitution yield. The substrate binding constants for ε‐PL and rPL were identical. ε‐PL showed a 15% higher steady‐state repair yield compared to FAD‐reconstituted photolyase (rPL). The acceleration of repair in ε‐PL is discussed in terms of an ε‐Ade radical intermediate vs superexchange mechanism.     

Ion-implantation-induced structural modifications in Y1Ba2Cu3O7−δ superconductor

Ion-implantation-induced structural modifications in Y₁Ba₂Cu₃O_7−δ superconductor are examined by a grazing angle X- ray diffraction technique. By employing a range of grazing angles from 0.3° to 10° it is shown that 100 KeV Ar⁺ inplantation of the superconductor leads to amorphization as well as modification of grain size and orientation at dose values lower than 10¹⁶ ions/ cm². At the dose of 5 × 10¹⁶ ions/ cm² the X-ray diffraction intensity is a factor of 6 less as compared to the original pellet, though the lines themselves are sharp. This shows coexistence of perovskite grains and amorphous matrix.     

Effect of non-specificity in shape, size, and dielectric properties on electromagnetic extinction and optical field enhancement from spherical nanolayered metal-dielectric particles

Metal-dielectric composite nanospheres can amplify the scattering, emission, and absorption signature of molecules in their vicinity. Their ability to redistribute electromagnetic fields and produce pockets of greatly amplified fields is the dominant cause in achieving enhancement effects, for example, for surface-enhanced Raman spectroscopy. Extensive use of the field amplification has been made in devising ultrasensitive tag (label)?Cbased spectroscopic techniques. For example, we have recently proposed nano-layered alternating metal-dielectric particles (nano-LAMP)??a symmetric implementation of which is a nanoparticle consisting of alternating metal and dielectric shells. Exceptional spatial and spectral control on amplification can be achieved by designing the size and location of metal and dielectric layers in this geometry. Theoretical understanding exists and an engineering optimization approach can be adapted to design a palette of probes exploiting this control and tunability. However, current fabrication techniques are limited in their ability to achieve the required specificity in the spherical configurations. Hence, we investigate here the effects of variability, introduced by fabrication approaches into the structure of nano-LAMPs, on their spectroscopic signature. In particular, theoretical results are presented for the effects on enhancement due to variability in size, shape, and dielectric environment in the cases of gold?Csilica, silver?Csilica, and copper?Csilica nano-LAMPs. The results obtained show that the shape and dielectric properties of the metal shell play a crucial role in experimentally realizing the specificity of the magnitude of the enhancement and determine the key parameters to control and test in experimental validations.     

Energy dependence of multiplicity in proton-nucleus collisions and models of multiparticle production

This is a continuation of our earlier investigation (Gurtuet al 1974Phys. Lett. 50 B 391) on multiparticle production in proton-nucleus collisions based on an exposure of emulsion stack to 200 GeV/c beam at the NAL. It is found that the ratioR _em = 〈n _s〉/〈n _ch〉, where 〈n _ch〉 is the charged particle multiplicity in pp-collisions, increases slowly from about 1 at 10 GeV/c to 1·6 at 68 GeV/c and attains a constant value of 1·71 ± 0·04 in the region 200 to 8000 GeV/c. Furthermore,R _em = 1·71 implies an effectiveA-dependence ofR _A =A ^0.18,i.e., a very weak dependence. Predictions ofR _em on various models are discussed and compared with the emulsion data. Data seem to favour models of hadron-nucleon collisions in which production of particles takes place through adouble step mechanism,e.g., diffractive excitation, hydrodynamical and energy flux cascade as opposed to models which envisage instantaneous production.     

Electronic transition dipole moment directions of reduced anionic flavin in stretched poly(vinyl alcohol) films

The IR and UV/vis linear dichroic spectra of reduced anionic flavin mononucleotide (FMNH-) partially oriented in poly(vinyl alcohol) (PVA) films have been measured to determine the direction of the major electronic transition dipole moments. The IR linear dichroism (LD) was measured in the 1750-1350 cm(-1) region to provide the overall molecular orientation of the FMNH- in the stretched films. Time-dependent density functional theory using the B3LYP functional was used to calculate the normal modes and the transition dipole moments of reduced lumiflavin. The calculated normal modes assisted in IR band assignments and in the determination of the IR transition dipole moment directions which were required for the determination of the orientation parameters for FMNH- in PVA films. The UV/vis LD spectrum was measured over the 200-700 nm region and was resolved into contributions from three pi-->pi* transitions. The directions of the transitions are 90 degrees+/-4 degrees at 440 nm, 79 degrees+/-4 degrees at 350 nm, and 93 degrees+/-4 degrees at 290 nm with counterclockwise rotations with respect to the N5-N10 axis. Comparison of the calculated and experimentally determined transition dipole moments allowed for refined assignment of the transition dipole moment directions. To our knowledge, this is the first experimental evidence that the 350-450 nm absorption arises from two unique transitions. Remarkably, the two lowest energy transition dipole moments for FMNH- are nearly parallel to those obtained in prior studies for both oxidized and semiquinone flavin.