Thermal and nonthermal physiochemical processes in nanoscale films of amorphous solid water

Amorphous solid water (ASW) is a disordered version of ice created by vapor deposition onto a cold substrate (typically less than 130 K). It has a higher free energy than the crystalline phase of ice, and when heated above its glass transition temperature, it transforms into a metastable supercooled liquid. This unusual form of water exists on earth only in laboratories, after preparation with highly specialized equipment. It is thus fair to ask why there is any interest in studying such an esoteric material. Much of the scientific interest results from the ability to use ASW as a model system for exploring the physical and reactive properties of liquid water and aqueous solutions. ASW is also thought to be the predominant form of water in the extremely cold temperatures of many interstellar and planetary environments. In addition, ASW is a convenient model system for studying the stability of amorphous and glassy materials as well as the properties of highly porous materials. A fundamental understanding of such properties is invaluable in a diverse range of applications, including cryobiology, food science, pharmaceuticals, astrophysics, and nuclear waste storage, among others. Over the past 15 years, we have used molecular beams and surface science techniques to probe the thermal and nonthermal properties of nanoscale films of ASW. In this Account, we present a survey of our research on the properties of ASW using this approach. We use molecular beams to precisely control the deposition conditions (flux, incident energy, and incident angle) and create compositionally tailored, nanoscale films of ASW at low temperatures. To study the transport properties (viscosity and diffusivity), we heat the amorphous films above their glass transition temperature, T(g), at which they transform into deeply supercooled liquids prior to crystallization. The advantage of this approach is that at temperatures near T(g), the viscosity is approximately 15 orders of magnitude larger than that of a normal liquid. As a result, the crystallization kinetics are dramatically slowed, increasing the time available for experiments. For example, near T(g), a water molecule moves less than the distance of a single molecule on a typical laboratory time scale (～1000 s). For this reason, nanoscale films help to probe the behavior and reactions of supercooled liquids at these low temperatures. ASW films can also be used for investigating the nonthermal reactions relevant to radiolysis.     

The characteristics of carbon nanotube‐reinforced poly(phenylene sulfide) nanocomposites

Multiwall carbon nanotube reinforced poly (phenylene sulfide) (PPS) nanocomposites were successfully fabricated through melt compounding. Structural, electrical, thermal, rheological, and mechanical properties of the nanocomposites were systematically studied as a function of carbon nanotube (CNT) fraction. Electrical conductivity of the polymer was dramatically enhanced at low loading level of the nanotubes; the electrical percolation threshold lay between 1 and 2 wt % of the CNTs. Rheological properties of the PPS nanocomposites also showed a sudden change with the CNT fraction; the percolation threshold was in the range of 0–0.5 wt % of CNTs. The difference in electrical and rheological percolation threshold was mainly due to the different requirements needed in the carbon nanotube network in different stages. The crystallization and melting behavior of CNT‐filled PPS nanocomposites were studied with differential scanning calorimetry; no new crystalline form of PPS was observed in the nanocomposites, but the crystallization rate was reduced. The thermal and mechanical properties of the nanocomposites were also investigated, and both of them showed significant increase with CNT fraction. For 5 wt % of CNT‐filled PPS composite, the onset of degradation temperature increased by about 13.5°C, the modulus increased by about 33%, and tensile strength increased by about 172%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Skin surface microflora of the saddle-back tamarin monkey,Saguinus fuscicollis

The resident skin surface microflora of 12 male and three femaleSaguinus fuscicollis was studied. The suprapubic-circumgenital gland surface and the perirectal area were most heavily colonized (10⁶–10⁸ colony forming units/cm²), but high numbers of organisms were also present on the abdomen, the sternal gland surface, and palms and plantar surfaces. Bacteria were also recovered from hair clippings as well as from shaven skin surface, although at much lower densities (10²–10⁴ colony forming units/cm²). Coagulase negative staphylococci, gram-negative bacteria,Streptococcus species and coryneform bacteria were most dominant.Staphylococcus aureus and species ofBacillus were also present. Fungi, yeast, and dermatophytes were infrequently recovered or completely absent. The microbial flora of these tamarins appears to be closely associated with the secretions of the circumgenital scent gland and would therefore be ideally situated to participate in the generation or modification of chemical signals.     

Detergency of used motor oil from cotton and polyester fabrics

A study was conducted to identity factors contributing to the difficult removal of used motor oil from textile materials by detergency. Infrared spectroscopy and gel permeation chromatography of used motor oil showed that the oil was a saturated aliphatic hydrocarbon with molecular weight around 950. X-ray analysis revealed that particulates present in the used motor oil contained S, Mg, Al, Si, K, Ca, Fe, Ni, Cu, and Zn. Used motor oil was distributed throughout the cotton fibers with similar concentration of oil in the lumen, secondary wall, and surface crenulation. Higher relative concentrations of used motor oil were observed in the secondary wall of the fiber than has been reported for human sebum. No oil was found in the interior of polyester fibers although high concentrations of oil were detected in the interfiber spaces and on the fiber surfaces of polyester fibers. Dispersant additives of motor oil are though to enhance penetration into the cotton structure and wicking over the polyester fibers, making the nonpolar used motor oil very difficult to remove by detergency.     

Structural Basis for The Recognition of Deaminated Nucleobases by An Archaeal DNA Polymerase

With increasing temperature, nucleobases in DNA become increasingly damaged by hydrolysis of exocyclic amines. The most prominent damage includes the conversion of cytosine to uracil and adenine to hypoxanthine. These damages are mutagenic and put the integrity of the genome at risk if not repaired appropriately. Several archaea live at elevated temperatures and thus, are exposed to a higher risk of deamination. Earlier studies have shown that DNA polymerases of archaea have the property of sensing deaminated nucleobases in the DNA template and thereby stalling the DNA synthesis during DNA replication providing another layer of DNA damage recognition and repair. However, the structural basis of uracil and hypoxanthine sensing by archaeal B-family DNA polymerases is sparse. Here we report on three new crystal structures of the archaeal B-family DNA polymerase from Thermococcus kodakarensis (KOD) DNA polymerase in complex with primer and template strands that have extended single stranded DNA template 5’-overhangs. These overhangs contain either the canonical nucleobases as well as uracil or hypoxanthine, respectively, and provide unprecedented structural insights into their recognition by archaeal B-family DNA polymerases.     

Effects of Adenine Methylation on the Structure and Thermodynamic Stability of a DNA Minidumbbell

DNA methylation is a prevalent regulatory modification in prokaryotes and eukaryotes. N¹-methyladenine (m¹A) and N⁶-methyladenine (m⁶A) have been found to be capable of altering DNA structures via disturbing Watson–Crick base pairing. However, little has been known about their influences on non-B DNA structures, which are associated with genetic instabilities. In this work, we investigated the effects of m¹A and m⁶A on both the structure and thermodynamic stability of a newly reported DNA minidumbbell formed by two TTTA tetranucleotide repeats. As revealed by the results of nuclear magnetic resonance spectroscopic studies, both m¹A and m⁶A favored the formation of a T·m¹A and T·m⁶A Hoogsteen base pair, respectively. More intriguingly, the m¹A and m⁶A modifications brought about stabilization and destabilization effects on the DNA minidumbbell, respectively. This work provides new biophysical insights into the effects of adenine methylation on the structure and thermodynamic stability of DNA.     

Local-scale analysis of carbon mitigation strategies: Tompkins County,New York,USA

The costs and potential for several carbon mitigation options were analyzed for Tompkins County, NY, within several categories: terrestrial carbon sequestration, local power generation, transportation, and energy end-use efficiency. The total county emissions are about 340 Gg C/year, with current biomass sequestration rates of about 121 Gg C/year. The potential for mitigation with the options examined, assuming full market penetration, amounts to at least 234 Gg C/year (69%), with 100 Gg C/year (29%) at no net cost to the consumer. Effective carbon mitigation strategies for this county based on costs per mg carbon and maximum potential include reforestation of abandoned agricultural lands for terrestrial carbon sequestration, biomass production for residential heating and co-firing in coal power plants, changes in personal behavior related to transportation (e.g., carpooling or using public transportation), installation of numerous residential energy-efficient products and development of local wind power. The principal barriers to the implementation of these approaches are discussed and policies for overcoming these barriers are analyzed.     

A pilot study of the efficacy of residuum lodges for managing sediment delivery to impoundment reservoirs

Residuum lodges comprise small dams constructed on feeder streams immediately before they enter a reservoir, behind which ponds form, where sediment is deposited. Despite their construction on many impoundment reservoirs (IRE) and catchwaters, little research has previously investigated their efficacy at removing sediments from feeder streams. The current pilot study has, therefore, been carried out at an IRE supplying Halifax, West Yorkshire, UK, where a residuum lodge was recently cleaned out. Sediment concentrations reaching the reservoir were reduced by up to 42% although no certain impacts were noted on the other water quality variables that were measured. Moreover, it was found that the clearance operation did not result in the release of excessive quantities of sediment into the reservoir. It was estimated that the cleared residuum lodge would take 12 years to refill. A survey of other residuum lodges in the Yorkshire region showed there to be considerable differences in their remaining capacities.     

Particle-induced network formation in linear PDMS filled with silica

We study the formation of permanent elastomers from linear PDMS chains by solution blending with up to 25 wt% fumed silica. The physical networks are characterized by time-domain multiple-quantum NMR. Based upon dynamic parameters measured for the linear precursor polymer, we develop a reliable strategy for component separation in this complex heterogeneous system, providing information on the amount of monomers involved in network-like material, in elastically inactive yet entangled linear chains, and isotropically mobile chain ends, as well as on the effective network chain length as measured via the average residual dipolar coupling constant. The use of untreated silica leads to permanent networks, for which the NMR results correlate well with macroscopic determinations of the relaxed Young modulus and the degree of swelling. Surface-modified silicas do not lead to percolated network structures, but still lead to the formation of 20–40% network-like material, with effective network chain lengths that depend on the surface functionalization and thus on the nanoparticle dispersion. Characteristic changes in the mobile chain end fraction with temperature, in particular its decrease with increasing degree of filling are interpreted as a consequence of altered contour-length fluctuations. An aging experiment conducted on a sample prepared by melt blending reveals the microscopic changes in the network structure occurring over many months.