Controlling a bunch of multiple filaments by means of a beam diameter

We demonstrate a three orders of magnitude increase and stability in the backscattered fluorescence signal from nitrogen molecules by terawatt femtosecond laser pulse induced air filaments using a new method. The method is based on squeezing the initial beam diameter using a telescope. The effect of laser shot-to-shot fluctuations was included in numerical simulations by a random distribution of the initial intensity in both squeezed and non-squeezed beams. Statistical processing of the simulation results shows that the average diameter of plasma channels as well as the total amount of free electrons generated in a bunch of multiple filaments in air is larger in the squeezed beam. Shot-to-shot stability of the simulated plasma density increases in the squeezed beam. The change of this plasma density with propagation distance is in good qualitative agreement with the change of the range-corrected nitrogen fluorescence signal with distance. PACS 42.65.Jx; 42.60.Jf; 42.68.Ay; 42.68.Wt     

Photodecomposition of several compounds commonly used as sunscreen agents

The photolysis reactions of three compounds commonly used as a sunscreen agents, Parsol 1789 (1-[4-(1,1-dimethylethyl)phenyl]-3-(4-methoxyphenyl)-1,3- propanedione), Oxybenzone ((2-hydroxy-4-methoxyphenyl)phenyl-methanone) and Padimate O (2-ethylhexyl-4-(dimethylamino)benzoate), were investigated to provide a chemical background to aid in the understanding of the photosensitization of the sunscreen agents. Photolysis was carried out in cyclohexane for 70–140 h using a mercury vapor lamp (450W) without excluding oxygen.

Irradation of Parsol 1789 in cyclohexane yielded tert-butylbenzene, p-tert-butylbenzoic acid and p-methoxybenzoic acid; products obtained from the combination of the sunscreen with the solvent included the cyclohexyl esters of p-methoxybenzoic acid, p-tert-butylbenzoic acid and methanoic acid; products obtained from the solvent included cyclohexanol, cyclohexanone and dicyclohexyl ether.

Irradiation of Oxybenzone in the cyclohexane for 100 h produced no detectable products by either gas or liquid chromatographic analysis. Oxybenzone was recovered unchanged and no products were observed from the photoinitiated reaction of oxygen with the solvent.

Irradiation of Padimate O in cyclohexane yielded the ethylhexyl esters of p-aminobenzoic acid, p-monomethylaminobenzoic acid and p-dimethylamino (o/m)-methylbenzoic acid, as well as products from the photoinitiated reaction of oxygen with the solvent.     

Fabrication and Determination of Refractive Index Profile of the Planar Waveguides by Wedge Technique

Several planar waveguides have been fabricated. The waveguides have been polished for determination of their refractiveindex profiles (RIP) by wedge method. The RIP determined by inserting the sample in a Mach-Zehnder interferometer andapplying fringe analysis methods.     

The speed of biased random walk on percolation clusters

 We consider biased random walk on supercritical percolation clusters in ℤ². We show that the random walk is transient and that there are two speed regimes: If the bias is large enough, the random walk has speed zero, while if the bias is small enough, the speed of the random walk is positive. Received: 20 November 2002 / Revised version: 17 January 2003 Published online: 15 April 2003 Research supported by Microsoft Research graduate fellowship. Research partially supported by the DFG under grant SPP 1033. Research partially supported by NSF grant #DMS-0104073 and by a Miller Professorship at UC Berkeley. Mathematics Subject Classification (2000): 60K37; 60K35; 60G50 Key words or phrases: Percolation – Random walk     

Headspace solvent microextraction of trihalomethane compounds into a single drop

Headspace solvent microextraction (HSME) into a single drop is developed for the determination of six trihalomethanes, CH2Cl2, CHCl3, C4H9Cl, CCl4, C2HCl3, and C2Cl4, in aqueous solution. A drop of benzyl alcohol containing bromoform, as an internal standard, is used for extraction. The analytes are extracted by suspending a 3-microL drop directly from the needle of a microsyringe. The needle passes through the septum of a vessel, and the needle tip appears above the surface of the solution. After the prescribed extraction time, the drop is drawn back into the syringe. The syringe is then removed, and its content is injected directly into a gas chromatography column for analysis. The main parameters affecting the HSME process, such as stirring speed, microdrop volume, sample solution temperature, microsyringe needle temperature, sample volume, solution pH, extracting solvent, and ionic strength of the solution, are studied. Also, the linear range and precision of the method are examined.     

Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites

The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal nodes. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni-MOF-74D, is evaluated vs. the nominally defect-free Ni-MOF-74 with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurtural (HMF) as a model reaction. The data indicates that Ni-MOF-74D features a set of 4-coordinate Ni–O₄ sites that exhibit unique vibrational signatures, redox potentials, binding motifs to HMF, and consequently superior electrocatalytic activity relative to the original Ni-MOF-74 MOF, being able to convert HMF to the desired 2,5-furandicarboxylic acid at 95% yield and 80% faradaic efficiency. Furthermore, having such rationally well-defined catalytic sites coupled with in situ Raman and infrared spectroelectrochemical measurements enabled the deduction of the reaction mechanism in which co-adsorbed *OH functions as a proton acceptor in the alcohol oxidation step and carries implications for catalyst design for heterogeneous electrosynthetic reactions en route to the electrification of the chemical industry.

The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control.