Laser ablation in liquids : Applications in the synthesis of nanocrystals

This review is essentially an update of one entitled “πBonding and The Lone Pair Effect in Multiple Bonds Between Heavier Main Group Elements” which was published more than 10 years ago in this journal.1 The coverage of that survey was focused on the synthesis, structure, and bonding of stable compounds2 of heavier main group elements that correspond to the skeletal drawings reproduced in Tables 1 and 2. A row of numbers is listed at the bottom of each column in these tables. This refers to the number of stable complexes from each class that are currently known. The numbers in parentheses refer to the number of stable species that were known at the time of the previous review. Clearly, many of the compound classes listed have undergone considerable expansion although some remain stubbornly rare. The most significant developments for each class will be discussed in detail under the respective sections. As will be seen, there are also a limited number of multiple bonded heavier main group species that do not fit neatly in the classifications in Tables 1 and 2. However, to keep the review to a manageable length, the limits and exclusions, which parallel those used earlier, are summarized as follows: (i) discussion is mainly confined to compounds where experimental data on stable, isolated species have been obtained, (ii) stable compounds having multiple bonding between heavier main group elements and transition metals are not generally discussed, (iii) compounds in which a multiple bonded heavier main group element is incorporated within a ring are generally not covered, and (iv) hypervalent main group compounds that may incorporate faux multiple bonding are generally excluded. Such compounds are distinguished from those in Tables 1 and 2 in that they apparently require the use of more than four valence bonding orbitals at one or more of the bonded atoms. The remainder of this review is organized in a similar manner to that of the previous one wherein the compounds to be discussed are classified according to those summarized in Tables 1 and 2. The key unifying feature of almost all molecules discussed in this review is that they are generally stabilized by the use of bulky substituents which block associative or various decomposition pathways.3 Since the previous review was published in 1999, several review articles that cover parts of the subject matter have appeared.4

π-Bonding and the Lone Pair Effect in Multiple Bonds Involving Heavier Main Group Elements: Developments in the New Millennium

Perfluorinated acids (PFAs) are an emerging class of environmental contaminants present in various environmental and biological matrices. Two major PFA subclasses are the perfluorinated sulfonic acids (PFSAs) and carboxylic acids (PFCAs). The physicochemical properties and partitioning behavior for the linear PFA members are poorly understood and widely debated. Even less is known about the numerous branched congeners with varying perfluoroalkyl chain lengths, leading to confounding issues around attempts to constrain the properties of PFAs. Current computational methods are not adequate for reliable multimedia modeling efforts and risk assessments. These compounds are widely present in surface, ground, marine, and drinking waters at concentrations that vary from pg L(-1) to microg L(-1). Concentration gradients of up to several orders of magnitude are observed in all types of aquatic systems and reflect proximity to known industrial sources concentrated near populated regions. Some wastewaters contain PFAs at mg L(-1) to low g L(-1) levels, or up to 10 orders of magnitude higher than present in more pristine receiving waters. With the exception of trifluoroacetic acid, which is thought to have both significant natural and anthropogenic sources, all PFSAs and PFCAs are believed to arise from human activities. Filtration and sorption technologies offer the most promising existing removal methods for PFAs in aqueous waste streams, although sonochemical approaches hold promise. Additional studies need to be conducted to better define opportunities from evaporative, extractive, thermal, advanced oxidative, direct and catalyzed photochemical, reductive, and biodegradation methods. Most PFA treatment methods exhibit slow kinetic profiles, hindering their direct application in conventional low hydraulic residence time systems.

Perfluoroalkyl sulfonic and carboxylic acids: a critical review of physicochemical properties, levels and patterns in waters and wastewaters, and treatment methods.

Multiphoton‐absorbing organic materials for microfabrication, emerging optical applications and non‐destructive three‐dimensional imaging

Wettability of porous polydimethylsiloxane surface: morphology study

CW CO 2 laser-photosensitized (SF 6 ) oxidation of hexafluoropropene, chlorotrifluoroethene, l,l-dichlorodifluoroethene, 1,2-dichlorodifluoroethene and hexafluoro-1,3-butadiene with molecular oxygen at total pressure 13-26.5 kPa leads with all but the last to the formation of carbonyl halides. The distribution of these products suggests that the oxidation occurs via a cleavage of intermediary dioxetanes. The reactivities of the olefins towards oxygen at mean effective temperature 710 K are nearly equal.

Laser-Driven Oxidation of Some Haloolefins.

Wall-less conditions of continuous wave CO2 laser photosensitized (SF6) oxidation of tetrafluoroethene with molecular O2(3Σ) reveal quite different features for this reaction compared with oxidation conducted in hot wall reactors. The laser-driven oxidation is accompanied by chemiluminescence and is suggested to proceed via an intermediate dioxetane to yield solely carbonyl fluoride. At higher pressures reaction occurs as an explosion with a lower pressure limit significantly different from that for hot-tube reactions and affords COF2, CF4, SOF2, and CO.

Continuous Wave Carbon Dioxide Laser‐Driven Oxidation of Tetrafluoroethene with Molecular Oxygen.

There is a continuing interest in the use of polymer films as insulating components of sensors; a number of such films have been prepared by polymer sputtering or vacuum deposition processes involving gas phase pyrolysis/photolysis and by plasma decomposition of monomers. An attractive and rather new technique for the deposition of novel polymer films is IR laser ablation of polymers containing polar groups. We have recently studied this process with poly(vinyl chloride) (PVC), poly(vinyl acetate) (PVAc) and poly(vinyl chloride-co-vinyl acetate) P(VC/VAc) to establish its specific features and differences to conventional pyrolysis.

Laser Ablative Deposition of Polymer Films: A Promise for Sensor Fabrication

Organosilicon Compounds. Part 134. Electronic Interactions Displayed in the Spectra of Substituted Alkoxytrimethylsilanes.

Laser powered homogeneous co-pyrolysis of tetramethylcyclotetrasiloxane and 1,1-dimethyl-1-silacyclobutane affords products in a ratio consistent with the transient existence of hydroxy(methyl)silylene and its addition to transient dimethylsilene. The suggestion that hydroxy(methyl)silylene is very reactive towards dimethylsilene but not towards butadiene is supported by a semiempirical AM1 calculation.

Laser Powered Homogeneous Decomposition of Tetramethylcyclotetrasiloxane. A Source for Hydroxy(methyl)silylene.

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