Combination atmospheric pressure solids analysis probe and desorption electrospray ionization mass spectrometry ion source.

The atmospheric solids probe analysis (ASAP) probe was investigated as a means for conducting desorption electrospray ionization (DESI) using a commercially available ion source. Solid and liquid samples as well as a raw urine sample were placed on individual melting point tubes and were inserted into either a heated gas stream for ASAP analysis or a charged solvent spray for DESI-like experiments. Samples ranged in polarity, volatility, mass, (100-17,000 Da), and concentration (neat to submicromolar). Mass spectra of multiple samples were obtained within a single acquisition on a short time scale (<30 s per sample). The configuration of the ion source also allowed rapid switching (approximately 1 min) between ASAP, electrospray ionization (ESI), and DESI.

Fragmentation mechanisms of oxidized peptides elucidated by SID, RRKM modeling, and molecular dynamics.

The gas-phase fragmentation reactions of singly charged angiotensin II (AngII, DR(+)VYIHPF) and the ozonolysis products AngII+O (DR(+)VY*IHPF), AngII+3O (DR(+)VYIH*PF), and AngII+4O (DR(+)VY*IH*PF) were studied using SID FT-ICR mass spectrometry, RRKM modeling, and molecular dynamics. Oxidation of Tyr (AngII+O) leads to a low-energy charge-remote selective fragmentation channel resulting in the b(4)+O fragment ion. Modification of His (AngII+3O and AngII+4O) leads to a series of new selective dissociation channels. For AngII+3O and AngII+4O, the formation of [MH+3O](+)-45 and [MH+3O](+)-71 are driven by charge-remote processes while it is suggested that b(5) and [MH+3O](+)-88 fragments are a result of charge-directed reactions. Energy-resolved SID experiments and RRKM modeling provide threshold energies and activation entropies for the lowest energy fragmentation channel for each of the parent ions. Fragmentation of the ozonolysis products was found to be controlled by entropic effects. Mechanisms are proposed for each of the new dissociation pathways based on the energies and entropies of activation and parent ion conformations sampled using molecular dynamics.

Reactive uptake of trimethylamine into ammonium nitrate particles.

The reaction of trimethylamine (TMA) vapor with a polydisperse distribution of ammonium nitrate particles (20-500 nm dia.) was studied in a flow tube reactor with particle analysis by laser desorption (1064 nm) 70 eV electron ionization (EI) in an ion trap time-of-flight (IT-TOF) aerosol mass spectrometer. When the TMA vapor concentration was very high, essentially complete exchange of TMA for ammonia in the particles was achieved. When the TMA vapor concentration was lower ( approximately 500 ppb for a reaction time of 23 s), partial exchange was observed, and the initial reactive uptake coefficient was estimated to be on the order of 2 x 10(-3) at 20% RH. This value suggests that measurable exchange is possible in the atmosphere when particles are exposed to an amine concentration on the order of 1 ppb for a few hours. The effects of particle size, water content, and amine molecular structure on uptake remain to be elucidated.

Selective detection of gas-phase TNT by integrated optical waveguide spectrometry using molecularly imprinted sol-gel sensing films.

A chemical sensor was developed to detect the explosive 2,4,6-trinitrotoluene (TNT) utilizing planar integrated optical waveguide (IOW) attenuated total reflection spectrometry. Submicron thick films of organically modified sol-gel polymers were deposited on the waveguide surface as the sensing layer. Sol-gels were molecularly imprinted for TNT using covalently bound template molecules linked to the matrix through 1 or 2 carbamate linkages. Upon chemical cleavage of the template and displacement of the TNT-like pendant groups from the matrix, shape-selective binding sites were created that possess a primary amine group. The amine was used to deprotonate bound TNT yielding an anionic form that absorbs visible light. Binding of TNT and subsequent conversion to the anion results in the attenuation of light propagating through the waveguide, thus creating a spectrophotometric device. Sensitivity can be achieved by taking advantage of the substantial pathlength provided by the use of single mode IOWs. The limit-of-detection to gas-phase TNT was found to be five parts-per-billion (ppbV) in ambient air at a flow rate of 40 mL min(-1) given a 60 s sampling time. The sensor is highly selective for TNT due to the selectivity of binding site recognition of TNT and the subsequent generation of the TNT anion. Response to TNT is not reversible which results in an integrating sensor device which, in theory, can improve the ability to detect small amounts of the explosive if the exposure time is sufficient in length.

Peptide ozonolysis: product structures and relative reactivities for oxidation of tyrosine and histidine residues.

Angiotensin II (DRVYIHPF) and two analogs, (DRVYIAPA and DRVAIHPA), were used as model systems to study the ozonolysis of peptides containing tyrosine and histidine residues. The ESI mass spectrum of angiotensin II following exposure to ozone showed the formation of adducts containing one, three, and four oxygen atoms. CID and SID spectra of these adducts were consistent with formation of Tyr + O and His + 3O as expected from previous work with amino acids. However, several fragment ions observed in the CID and SID spectra suggested formation of a rather unexpected adduct, Tyr + 3O, and a small amount of the Phe + O adduct. These findings were confirmed by examining two angiotensin analogs. Exposure of DRVYIAPA to ozone resulted in the addition of either one or three oxygen atoms on Tyr, while DRVAIHPA showed only the addition of three oxygen atoms--all on His. Other noteworthy minor oxidation products were observed from these analogs including Tyr + 34 Da, His + 5 Da, His + 34 Da, and His + 82 Da. The reaction rates of the peptides with ozone were found to be similar: second-order rate coefficients are 274 +/- 3, 379 +/- 6, and 439 +/- 34 M(-1) s(-1) for DRVYIAPA, DRVAIHPA, and angiotensin II, respectively. The relative rates indicate (1) an isolated His residue has a slightly greater ozone reactivity than an isolated Tyr residue, and (2) the reaction rates of isolated residues are not additive when both residues are present in the same molecule.

Sensor for fluorene based on the incorporation of an environmentally sensitive fluorophore proximal to a molecularly imprinted binding site.

A fluorescence-based chemical sensor for fluorene was created by molecularly imprinting a sol-gel comprising the bridged silsesquioxane, bis(trimethoxysilylethyl)benzene. The template was covalently bound to the sol-gel matrix using a fluorene analogue functionalized silane. After chemical removal of template via cleavage of a carbamate linkage, an amine group was left that provided an attachment site for the environmentally sensitive fluorescent probe 7-nitrobenz-2-oxa-1,3-diazole (NBD). Fluorene binding was detected by a change in NBD fluorescence intensity induced by a difference in the local polarity around the probe when the recognition site is filled. Such an approach eliminated response to nonspecific binding to the matrix. Sensing films deposited on glass slides were shown to have response times of <60 s and detection limits below 10 parts-per-trillion. Binding experiments demonstrated that the materials had good selectivity for fluorene over close structural analogues including naphthalene, fluoranthene, and anthracene. However, the sensing design is limited by a lack of reversibility following fluorene binding.

Preferential extraction of hydrocarbons from fire debris samples by solid phase microextraction.

Headspace analysis by extraction/GC-MS is a common method of detecting volatile hydrocarbon accelerants in fire debris samples. Solid-phase microextraction was tested to determine if there is selective extraction of chemically distinct compounds. It was found that both the polydimethylsiloxane (PDMS) and Carboxen/PDMS solid phase microextraction fibers show preferential extraction of aliphatic or aromatic compounds from the headspace depending on fiber type and temperature. The Carboxen/PDMS fiber type showed particular (although not exclusive) selectivity for extraction of aromatic hydrocarbons. Other experimental considerations of SPME are noted.

The project nurse and pressure-relieving equipment.

This article describes the work of a project management nurse in improving accessibility and appropriate use of pressure-relieving equipment in an integrated (acute and community) trust. It examines key issues for future service development in the management and appropriate use of pressure-relieving equipment. The importance of education in maintaining the accuracy and process of recording pressure damage at ward level is also highlighted. One recommendation is that employing a pressure equipment assistant might improve the control and management of pressure equipment availability.