Portable X-Ray Fluorescence as a Rapid Technique for Surveying Elemental Distributions in Soil

Case studies from two sites demonstrate how concentration distributions of hazardous contaminants can be rapidly measured and visualized using portable XRF (X-ray fluorescence) coupled with geostatistical interpolation tools. In this study, lead is used as an exemplar due to its well-known detrimental effect on human health through long-term exposure. A portable Thermo Scientific NITON X-ray fluorescence (XRF) instrument was used for real-time in-situ concentration measurements, which were linked to GPS coordinates of the sampling locations. A 52 point mixed sampling density survey was performed at a site near Maynooth, Co. Kildare, and a second 58 survey undertaken at Dublin City University (DCU). At Maynooth, high concentrations of Pb (above 110 mg/kg) were found close to the site where a local canal meets a road. At the DCU site, results indicate high Pb concentrations (above 160 mg/kg) near a busy main road. Geostatistical techniques were used to generate concentration prediction and critical threshold contour surfaces for both sites. Linked with GPS coordinates for each sampling location, this technology enables the distribution of multiple elements to be mapped over wide areas in a relatively short time. Supplemental materials are available for this article. Go to the publisher's online edition of Spectroscopy Letters to view the supplemental file.     

Applications of quantum cascade lasers for sensitive trace gas measurements of CO, CH4, N2O and HCHO

We describe here a sensitive quantum cascade laser absorption spectrometer (QCLAS) employed for aircraft based measurements during the GABRIEL 2005 and HOOVER 2006 and 2007 campaigns. This 3-channel instrument measures CO, HCHO, CH₄ and N₂O using a 64-m path double corner cube White cell. Performance of the instrument was examined for the four species and precisions for CO, N₂O and CH₄ were measured in the field to be 0.5, 0.5 and 0.7% respectively (2σ). The 1σ detection limit for HCHO was ∼500 pptv for a 2 s average, while signal averaging of the HCHO over a 2 min time interval resulted in a 150 pptv detection limit with a duty cycle of 60%. PACS  82.80.Gk; 07.88.+y; 42.62.-b; 92.60.H-     

Ultrafast observation of a solvent dependent spin state equilibrium in CpCo(CO)

We report the observation of a solvent-dependent spin state equilibrium in the 16-electron photoproduct CpCo(CO). Time-resolved infrared spectroscopy has been used to observe the concurrent formation of two distinct solvated monocarbonyl photoproducts, both of which arise from the same triplet CpCo(CO) precursor. Experiments in different solvent environments, combined with electronic structure theory calculations, allow us to assign the two solvated photoproducts to singlet and triplet CpCo(CO)(solvent) complexes. These results add to our previous picture of triplet reactivity for 16-electron organometallic photoproducts, in which triplets were not believed to interact strongly with solvent molecules. In the case of this photoproduct, it appears that spin crossover does not present a significant barrier to reactivity, and relative thermodynamic stabilities determine the spin state of the CpCo(CO) photoproduct in solution on the picosecond time scale. While the existence of transition metal complexes with two thermally accessible spin states is well-known, this is, to our knowledge, the first observation of a transient photoproduct that exhibits an equilibrium between two stable spin states, and also the first observed case in which a solvent has been able to coordinate as a token ligand to two spin states of the same photoproduct.     

Mechanochemistry: opportunities for new and cleaner synthesis

The aim of this critical review is to provide a broad but digestible overview of mechanochemical synthesis, i.e. reactions conducted by grinding solid reactants together with no or minimal solvent. Although mechanochemistry has historically been a sideline approach to synthesis it may soon move into the mainstream because it is increasingly apparent that it can be practical, and even advantageous, and because of the opportunities it provides for developing more sustainable methods. Concentrating on recent advances, this article covers industrial aspects, inorganic materials, organic synthesis, cocrystallisation, pharmaceutical aspects, metal complexes (including metal-organic frameworks), supramolecular aspects and characterization methods. The historical development, mechanistic aspects, limitations and opportunities are also discussed (314 references).     

Surface-enhanced Raman scattering study of the kinetics of self-assembly of carboxylate-terminated n-alkanethiols on silver

Adsorption of 11-mercaptoundecanoic acid (MUA) on silver from methanol and aqueous solutions was monitored in situ by surface-enhanced Raman scattering (SRES) spectroscopy. While adsorption of MUA from methanol is a one-step formation of a thiol-bound monolayer, SERS spectra reveal that monolayer formation from aqueous solution involves interactions of both carboxylate and thiol groups of MUA with the silver surface. Several Raman scattering bands, including the ν(C-S), ν(s)(COO(-)), and ν(C-C), were used to investigate the evolution of the structure of adsorbed MUA on silver surfaces. The time-dependent profiles of these bands for assembly from aqueous solution indicate a multistep process, which is initiated by the binding of both carboxylate and thiol groups to silver, producing a mixture of gauche and trans conformations. In a subsequent step, the COO-Ag interactions are displaced by stronger S-Ag bonds, leading to ordering of the resulting monolayer with formation of a complete SAM with all-trans conformations. The results also showed that the adsorption process depended strongly on the solution pH and surface potential of the metal. These factors can significantly affect the participation and displacement of -COO(-) during self-assembly of MUA from aqueous solution.     

Unraveling the Mechanism of the Photodeprotection Reaction of 8‐Bromo‐ and 8‐Chloro‐7‐hydroxyquinoline Caged Acetates

Photoremovable protecting groups (PPGs) when conjugated to biological effectors forming “caged compounds” are a powerful means to regulate the action of physiologically active messengers in vivo through 1‐photon excitation (1PE) and 2‐photon excitation (2PE). Understanding the photodeprotection mechanism is important for their physiological use. We compared the quantum efficiencies and product outcomes in different solvent and pH conditions for the photolysis reactions of (8‐chloro‐7‐hydroxyquinolin‐2‐yl)methyl acetate (CHQ‐OAc) and (8‐bromo‐7‐hydroxyquinolin‐2‐yl)methyl acetate (BHQ‐OAc), representatives of the quinoline class of phototriggers for biological use, and conducted nanosecond time‐resolved spectroscopic studies using transient emission (ns‐EM), transient absorption (ns‐TA), transient resonance Raman (ns‐TR²), and time‐resolved resonance Raman (ns‐TR³) spectroscopies. The results indicate differences in the photochemical mechanisms and product outcomes, and reveal that the triplet excited state is most likely on the pathway to the product and that dehalogenation competes with release of acetate from BHQ‐OAc, but not CHQ‐OAc. A high fluorescence quantum yield and a more efficient excited‐state proton transfer (ESPT) in CHQ‐OAc compared to BHQ‐OAc explain the lower quantum efficiency of CHQ‐OAc relative to BHQ‐OAc.     

Galois representations,automorphic forms,and the Sato-Tate Conjecture

The present text consists of notes of several lectures on the proof of the Sato-Tate Conjecture given up through 2008. The goal of the lectures was to explain the statement and the main ideas of the proof. The notes are somewhat dated; shortly after they were written, the author, together with Bernet-Lamb, Geraghty, and Taylor, were able to prove the analogue of the Sato-Tate conjecture for all elliptic modular forms. In particular, Theorems 2.4 and 2.5 are not conditional, and the condition on the j-invariant in Theorem 1.1 is superfluous. Moreover, the methods of proof outlined in sections 3 and 4 have been generalized and extended in a number of ways, notably in a series of articles by Barnet-Lamb, Gee, Geraghty, and Taylor, by Thorne, and by Calegari and Geraghty.     

Branching Brownian Motion with Catalytic Branching at the Origin

We consider a branching Brownian motion in which binary fission takes place only when particles are at the origin at a rate β>0 on the local time scale. We obtain results regarding the asymptotic behaviour of the number of particles above λt at time t, for λ>0. As a corollary, we establish the almost sure asymptotic speed of the rightmost particle. We also prove a Strong Law of Large Numbers for this catalytic branching Brownian motion.