User Training at SSRL: Crystallography,X-ray Absorption Spectroscopy,Small-Angle X-ray Scattering,and X-ray Scattering Techniques

The Stanford Synchrotron Radiation Lightsource (SSRL) is a national scientific user facility at the SLAC National Accelerator Laboratory that provides high-brightness X-ray beams, innovative experimental facilities, and expert scientific support as a resource to study our world at the atomic and molecular level. Operating within this context and being closely associated with a major research university (Stanford), SSRL is strongly committed to providing unique educational experiences, and serves as a vital training ground for future generations of scientists and engineers. As part of this program, SSRL oversees a series of schools and workshops each year which deliver theoretical, experimental, and hands-on training by leading experts in their respective fields. Several of the courses held this year, attended by graduate students, postdoctoral fellows, educators and junior/senior investigators, are described in this report.     

Effects of functional groups on surface pressure-area isotherms of hydrophilic silicone polymers

Organic/inorganic hybrid silicone polymers are increasingly used in cosmetics, inks and paints, and fabric care applications owing to their special Si-O bond characteristics. Because of the presence of organic as well as inorganic groups, they show the properties of both, and the presence of hydrophobic as well as hydrophilic character makes them behave like a hybrid polymer. Though they are widely used, the utilization of hydrophilically modified silicones on a large scale has mainly been empirical due to lack of fundamental knowledge about variation in their properties with systematic change in their structure. The choice of moieties for hydrophilic modification of silicones in most of the earlier works has been nonionic based on ethylene oxide and propylene oxide groups, however, very little is known about their ionic counterparts. The current work focuses on understanding the behavior of functionally grafted silicone polymers with respect to the variation in the hydrophilic part of the grafting chain. Hydrophilically grafted silicone polymers form monolayers at the air-water interface, which are stabilized by interactions of functional groups with water. The present work examined the effects of functional group modifications on the conformational behavior of chains at the interface. It was observed that the shape of the chain depends on the available area at the interface (or surface pressure), and there are conformational changes with an increase in the number of molecules per unit area. While a poly(dimethylsiloxanes) (PDMS) chain may undergo stretched to helix transition as predicted earlier, this may not be the case for hydrophilically grafted chains. On the basis of the shape of the surface pressure-area isotherm and correlation with the scaling theory, a gradation in hydrophilicity of functional groups and hence modified silicone chains at the air-water interface is predicted.     

Electroluminescence from hybrid organic–inorganic LEDs based on thermally evaporated CdS thin films

Hybrid organic–inorganic light emitting devices combine the color purity and durability of inorganic light emitting diodes (LEDs) with high efficiency, flexibility and low processing cost of organic LEDs (OLEDs). A significant challenge is to incorporate inorganic nanocrystals inside the OLED structure. In the present work, thin films of CdS were successfully incorporated inside standard OLED structure using vacuum thermal evaporation technique. For the characterization of these films, they were deposited on plain glass plates at room temperature and studied using structural (XRD and TEM), morphological (SEM and AFM) and optical (UV and PL) techniques. The films were found to be composed of nanocrystals of CdS in which the size of the crystals increased with the increase in film thickness. The hybrid organic–inorganic LEDs showed improved luminance and efficiency as compared to the organic LED without CdS layers.     

Enhancement of light extraction efficiency of organic light emitting diodes using nanostructured indium tin oxide

Improved outcoupling efficiency of organic light emitting diodes (OLEDs) is demonstrated by incorporating a nanostructured indium tin oxide (NSITO) film between a conducting anode and a glass substrate. NSITO film was fabricated using rf-sputtering at oblique angle (85°). Significant reduction in refractive index and improved transmission of NSITO film was observed. OLEDs were then fabricated onto NSITO film to extract the ITO-glass waveguided modes. Extraction efficiency was enhanced by 80% without introducing any detrimental effects to operating voltage, current density, and angular invariance of emission spectra of OLEDs.     

Facile synthesis,growth mechanism,and optical properties of CdSe nanoparticles in self-assembled micellar media and their efficient conjugation with proteins

This article demonstrates the influence of various surfactants of different polarities—anionic, sodium dodecyl sulfate, cationic, hexadecyltrimethylammonium bromide and non-ionic, and polyoxyethylene iso-octyl phenyl ether (TX-100)—on the formation of CdSe nanoparticles in aqueous solutions. The surfactant-stabilizing effect has been monitored using transmission electron microscopy. Spectral properties of CdSe nanoparticles have been investigated; the structure of the long-wave edge of the fundamental absorption band of CdSe nanoparticles has been analyzed. It has been shown that the variation of the synthesizing conditions (stabilizer’s nature and concentration, CdSe concentration, etc.) allows the tailoring of the CdSe nanoparticle size in the range of 8–17 nm. Lifshitz–Slyrzov–Wagner kinetic analysis has also been performed using the size variation according to ripening temperature and time period. The differences in the stabilization ability of tested substances are discussed with respect to their structure and possible mechanism of the surface interaction with the nanoparticles. The flexible surface chemistry of the CdSe-micelles causes them to be water soluble and allows their further conjugation with protein molecules through electrostatic attraction. The interaction between functionalized CdSe nanoparticles with protein molecules have been investigated using fluorescence spectroscopy.     

Study of uranium contamination of ground water in Punjab state in India using X-ray fluorescence technique

The elemental concentration of uranium in the samples collected from the ground water and the canal water in the Bathinda district of Punjab state, India, have been investigated using X-ray fluorescence technique. The residues obtained after drying the water samples were analysed using the energy dispersive X-ray fluorescence spectrometer consisting of Mo-anode X-ray tube equipped with selective absorbers as an excitation source and an Si(Li) detector. The uranium concentration values in significant fraction of the shallow ground water samples from the hand pumps is found to be above the permissible level of 15?ppb recommended by World Health Organisation for the drinking water, and its values in the canal water samples are below 5?ppb. To investigate the flyash from the coal-fired thermal power plants as a possible source of ground water contamination, the water samples collected from the surroundings of the power plants and the flyash samples were also analyzed. The results rule out flyash as a source of uranium contamination. Agrochemical processes occurring in the calcareous soils in the region are the favoured potential source of uranium contamination of the ground water.     

Applicability study on existing dosimetry systems to high-power Bremsstrahlung irradiation

Applicability of the existing dosimetry systems to high-power Bremsstrahlung irradiation was investigated through a dose intercomparison study, where several dosimeters were irradiated in the dose range 4–12 kGy in identical polyethylene phantoms in a Bremsstrahlung beam obtained from a 5-MeV electron accelerator. Included in the study were alanine dosimeters molded by three different binders, three types of liquid dosimeters—ceric-cerous, dichromate and ethanol-chlorobenzen (ECB), and glutamine powder. The dosimeter responses for Bremsstrahlung radiation were analyzed at the issuing laboratories, and the dose values determined using calibration based on cobalt-60 gamma-ray irradiation. Dose values for all the three dose levels for all dosimetry systems were in good agreement—better than 3%. The results of the study demonstrate that these existing dosimetry systems have a potential for application to high-power Bremsstrahlung irradiation.     

Thiabowls: synthesis, molecular structure and the solid state architecture of tetrathia-[4]-peristylane

Synthesis of tetrathia-[4]-peristylane, the first thiabowl, from the dimer of cyclooctatetraene has been accomplished. The X-ray crystal structure of the tetrathiabowl indicates significant departure from the expected C_4v symmetry and in the solid state it exhibits a multi-columnar arrangement and a novel ‘self-inclusion’ phenomenon, directed by a network of SS and CHS interactions.     

Synthesis of Polylactide under Inert Atmosphere and Vacuum

The ring-opening polymerization (ROP) of L- lactide was carried out in bulk using various initiators along with triphenylphosphine (PPh₃) as co-initiator. Equimolar addition of triphenylphosphine increased the molecular masses of polylactide (PLA). The polymerization was carried out at 403.15 K up to 155 hr. Different experiments were carried out over a wide range of monomer to initiator (M_o/I_o) ratios. It was found that maximum molecular weight of polylactide was observed when M_o/I_o ratio was 2500–2700. Polymerization reactions were carried out under two different environments in the reaction vessel, an inert cover and a partial vacuum. The average molecular weight of polylactide was determined by using size exclusion chromatography. The increase of polymerization time increased the weight average molecular weight but after prolonged reaction time, the molecular weight decreased gradually.     

In situ cryocrystallization of diphenyl ether: C-H...pi mediated polymorphic forms

Polymorphism in diphenyl ether has been identified during in situ crystallization via single-crystal X-ray diffraction. Only weak inter- and intramolecular C-H...pi interactions control the packing of the molecules in both crystal forms monoclinic centrosymmetric (P21/n) in form I and orthorhombic noncentrosymmetric (P212121) in form II.