Atmospheric Spectroscopy and Photochemistry at Environmental Water Interfaces.

The air-water interface is ubiquitous in nature, as manifested in the form of the surfaces of oceans, lakes, and atmospheric aerosols. The aerosol interface, in particular, can play a crucial role in atmospheric chemistry. The adsorption of atmospheric species onto and into aerosols modifies their concentrations and chemistries. Moreover, the aerosol phase allows otherwise unlikely solution-phase chemistry to occur in the atmosphere. The effect of the air-water interface on these processes is not entirely known. This review summarizes recent theoretical investigations of the interactions of atmosphere species with the air-water interface, including reactant adsorption, photochemistry, and the spectroscopy of reactants at the water surface, with an emphasis on understanding differences between interfacial chemistries and the chemistries in both bulk solution and the gas phase. The results discussed here enable an understanding of fundamental concepts that lead to potential air-water interface effects, providing a framework to understand the effects of water surfaces on our atmosphere.

Oxygen intercalation in PVD graphene grown on copper substrates: A decoupling approach.

We investigate the intercalation process of oxygen in-between a PVD-grown graphene layer and different copper substrates as a methodology for reducing the substrate-layer interaction. This growth method leads to an extended defect-free graphene layer that strongly couples with the substrate. We have found, by means of X-ray photoelectron spectroscopy, that after oxygen exposure at different temperatures, ranging from 280 °C to 550 °C, oxygen intercalates at the interface of graphene grown on Cu foil at an optimal temperature of 500 °C. The low energy electron diffraction technique confirms the adsorption of an atomic oxygen adlayer on top of the Cu surface and below graphene after oxygen exposure at elevated temperature, but no oxidation of the substrate is induced. The emergence of the 2D Raman peak, quenched by the large interaction with the substrate, reveals that the intercalation process induces a structural undoing. As suggested by atomic force microscopy, the oxygen intercalation does not change significantly the surface morphology. Moreover, theoretical simulations provide further insights into the electronic and structural undoing process. This protocol opens the door to an efficient methodology to weaken the graphene-substrate interaction for a more efficient transfer to arbitrary surfaces.

Spectroscopic characterization of the on-surface induced (cyclo)dehydrogenation of a N-heteroaromatic compound on noble metal surfaces.

New nanoarchitectures can be built from polycyclic aromatic hydrocarbons (PAHs) by exploiting the capability of some metal surfaces for inducing cyclodehydrogenation reactions. This bottom-up approach allows the formation of nanostructures with a different dimensionality from the same precursor as a consequence of the diffusion and coupling of the PAHs adsorbed on the surface. In this work we present a thorough study, by means of a combination of X-ray photoemission spectroscopy, near-edge X-ray absorption fine structure and scanning tunneling microscopy with first principle calculations of the structural and chemical transformations undergone by pyridyl-substituted dibenzo[5]helicene on three coinage surfaces, namely Cu(110), Cu(111) and Au(111). Upon annealing, on-surface chemical reactions are promoted affecting the adsorbate/substrate and the molecule/molecule interactions. This thermally induced process favours the transformation from diffusing isolated molecules to polymeric nanographene chains and finally to N-doped graphene.

High-quality PVD graphene growth by fullerene decomposition on Cu foils.

We present a new protocol to grow large-area, high-quality single-layer graphene on Cu foils at relatively low temperatures. We use C60 molecules evaporated in ultra high vacuum conditions as carbon source. This clean environment results in a strong reduction of oxygen-containing groups as depicted by X-ray photoelectron spectroscopy (XPS). Unzipping of C60 is thermally promoted by annealing the substrate at 800ºC during evaporation. The graphene layer extends over areas larger than the Cu crystallite size, although it is changing its orientation with respect to the surface in the wrinkles and grain boundaries, producing a modulated ring in the low energy electron diffraction (LEED) pattern. This protocol is a self-limiting process leading exclusively to one single graphene layer. Raman spectroscopy confirms the high quality of the grown graphene. This layer exhibits an unperturbed Dirac-cone with a clear n-doping of 0.77 eV, which is caused by the interaction between graphene and substrate. Density functional theory (DFT) calculations show that this interaction can be induced by a coupling between graphene and substrate at specific points of the structure leading to a local sp3 configuration, which also contribute to the D-band in the Raman spectra.

Association between bone turnover markers, clinical variables, spinal syndesmophytes and bone mineral density in Mexican patients with ankylosing spondylitis.

OBJECTIVES: To compare bone turnover marker (BTM) levels and bone mineral density (BMD) between patients with ankylosing spondylitis (AS) and healthy controls (HC) and to evaluate, in AS, the association between BTM levels and clinical variables, spinal syndesmophytes, and BMD using multivariate analysis. METHOD: Seventy-eight AS patients were compared with 58 HC matched by gender. Spinal syndesmophytes in AS and other characteristics were assessed. C-terminal telopeptide fragments of type I collagen (CTX), bone-specific alkaline phosphatase (BAP), osteocalcin (OC) serum levels, and BMD of the lumbar spine, femoral neck, and forearm were evaluated. RESULTS: AS males and females had lower BAP levels than their respective HC (p < 0.001 and p = 0.001). AS patients with bridging syndesmophytes had higher OC levels than AS patients either with non-bridging syndesmophytes (p = 0.001) or without spinal syndesmophytes (p < 0.001). OC and CTX levels correlated significantly with the modified Stoke Ankylosing Spondylitis Spinal Score (mSASSS). In the multivariate linear regression adjusted by age, gender, the Bath Ankylosing Spondylitis Disease Activity Index (BASDAI), BMD in the lumbar spine, and C-reactive protein (CRP), we observed an association between BAP levels and anti-tumour necrosis factor (anti-TNF) use (p = 0.05) whereas OC levels were associated with mSASSS (p < 0.001) and anti-TNF use (p = 0.05), and CTX levels were exclusively associated with mSASSS (p = 0.03). In the logistic regression analysis, only OC levels were associated with the presence of syndesmophytes in AS [odds ratio (OR) 2.42, 95% confidence interval (CI) 1.19-5.75]. CONCLUSIONS: We observed an increase in OC levels in AS patients with syndesmophytes. BTM levels were associated with the severity of spinal damage. Future longitudinal studies should evaluate whether these BTMs should be included as tools to determine the prognosis and progression of spinal damage.

Association between -174G/C and -572G/C interleukin 6 gene polymorphisms and severe radiographic damage to the hands of Mexican patients with rheumatoid arthritis: a preliminary report.

Several interleukin 6 gene (IL6) polymorphisms are implicated in susceptibility to rheumatoid arthritis (RA). It has not yet been established with certainty if these polymorphisms are associated with the severe radiographic damage observed in some RA patients, particularly those with the development of joint bone ankylosis (JBA). The objective of the present study was to evaluate the association between severe radiographic damage in hands and the -174G/C and -572G/C IL6 polymorphisms in Mexican Mestizo people with RA. Mestizo adults with RA and long disease duration (>5 years) were classified into two groups according to the radiographic damage in their hands: a) severe radiographic damage (JBA and/or joint bone subluxations) and b) mild or moderate radiographic damage. We compared the differences in genotype and allele frequencies of -174G/C and -572G/C IL6 polymorphisms (genotyped using polymerase chain reaction-restriction fragment length polymorphism) between these two groups. Our findings indicated that the -174G/C polymorphism of IL6 is associated with severe joint radiographic damage [maximum likelihood odds ratios (MLE_OR): 8.03; 95%CI 1.22-187.06; P = 0.03], whereas the -572G/C polymorphism of IL6 exhibited no such association (MLE_OR: 1.5; 95%CI 0.52-4.5; P = 0.44). Higher anti-cyclic citrullinated peptide antibody levels were associated with more severe joint radiographic damage (P = 0.04). We conclude that there is a relevant association between the -174G/C IL6 polymorphism and severe radiographic damage. Future studies in other populations are required to confirm our findings.

Comparison of orthologous cytochrome P450 genes relative expression patterns in the bark beetles Dendroctonus rhizophagus and Dendroctonus valens (Curculionidae: Scolytinae) during host colonization.

Bark beetles of the genus Dendroctonus are important components of coniferous forests. During host colonization, they must overcome the chemical defences of their host trees, which are metabolized by cytochrome P450 (CYP or P450) enzymes to compounds that are readily excreted. In this study, we report the relative expression (quantitative real-time PCR) of four orthologous cytochrome P450 genes (CYP6BW5, CYP6DG1, CYP6DJ2 and CYP9Z20) in Dendroctonus rhizophagus and Dendroctonus valens forced to attack host trees at 8 and 24 h following forced attack and in four stages during natural colonization [solitary females boring the bark (T1); both male and female members of couples before oviposition (T2); both male and female members of couples during oviposition (T3), and solitary females inside the gallery containing eggs (T4)]. For both species gene expression was different compared with that observed in insects exposed to single monoterpenes in the laboratory, and the expression patterns were significantly different amongst species, sex, gut region and exposure time or natural colonization stage. The induction of genes (CYP6BW5v1, CYP6DJ2v1 and CYP9Z20v1 from D. rhizophagus, as well as CYP6DG1v3 from D. valens) correlated with colonization stage as well as with the increase in oxygenated monoterpenes in the gut of both species throughout the colonization of the host. Our results point to different functions of these orthologous genes in both species.

Adsorption and Coupling of 4-aminophenol on Pt(111) surfaces.

We have deposited 4-aminophenol on Pt(111) surfaces in ultra-high vacuum and studied the strength of its adsorption through a combination of STM, LEED, XPS and ab initio calculations. Although an ordered (2√3×2√3)R30° phase appears, we have observed that molecule-substrate interaction dominates the adsorption geometry and properties of the system. At RT the high catalytic activity of Pt induces aminophenol to lose the H atom from the hydroxyl group, and a proportion of the molecules lose the complete hydroxyl group. After annealing above 420K, all deposited aminophenol molecules have lost the OH moiety and some hydrogen atoms from the amino groups. At this temperature, short single-molecule oligomer chains can be observed. These chains are the product of a new reaction that proceeds via the coupling of radical species that is favoured by surface diffusion.

Assessment of Serum sRANKL, sRANKL/OPG Ratio, and Other Bone Turnover Markers with the Estimated 10-Year Risk of Major and Hip Osteoporotic Fractures in Rheumatoid Arthritis: A Cross-Sectional Study.

BACKGROUND: Fracture risk assessment tool (FRAX) index was developed for estimating of the 10-year risk of major or hip osteoporotic fracture. To date, there is insufficient information regarding the correlation between FRAX and serum bone turnover markers (BTMs), such as soluble ligand of receptor activator of nuclear factor-κB (sRANKL), osteoprotegerin (OPG), and other molecules related with secondary osteoporosis in rheumatoid arthritis (RA). Therefore, this study is aimed at assessing the correlation between the FRAX and serum levels of sRANKL, OPG, sRANKL/OPG ratio, Dickkopf-1 (DKK-1), and sclerostin (SOST) in RA. METHODS: Cross-sectional study included 156 postmenopausal women with RA. Bone mineral density (BMD) was measured at lumbar spine (L1-L4) and total hip using dual-energy X-ray absorptiometry (DXA). RA patients were divided into (A) RA + osteoporosis and (B) RA without osteoporosis. FRAX scores were calculated including the total hip BMD. Serum sRANKL, OPG, DKK-1, and SOST levels were measured by ELISA. Pearson tests were used for assessing the correlation between serum levels of these molecules and FRAX scores in RA. RESULTS: The RA + osteoporosis group had elevated sRANKL levels (p = 0.005), higher sRANKL/OPG ratio (p = 0.017), decreased DKK-1 (p = 0.028), and lower SOST levels (p < 0.001). Low total hip BMD correlated with high sRANKL (p = 0.001) and sRANKL/OPG ratio (p = 0.005). Total hip and lumbar spine BMD correlated with DKK-1 (p = 0.009 and p = 0.05, respectively) and SOST levels (p < 0.001 and p < 0.001, respectively). Higher sRANKL levels and sRANKL/OPG ratio correlated with estimated 10-year risk of a major osteoporotic fractures (p = 0.003 and p = 0.003, respectively) and hip fracture (p = 0.002 and p = 0.006, respectively). High serum SOST levels were associated with a low estimated 10-year risk of a major osteoporotic fracture (p = 0.003) and hip fracture (p = 0.009). CONCLUSION: High sRANKL levels and sRANKL/OPG ratio can be useful to detect a subgroup of RA patients who has an increased 10-year risk of major and hip osteoporotic fractures.

Platform for establishing interlaboratory reproducibility of selected reaction monitoring-based mass spectrometry peptide assays.

Mass spectrometry (MS) is an attractive alternative to quantification of proteins by immunoassays, particularly for protein biomarkers of clinical relevance. Reliable quantification requires that the MS-based assays are robust, selective, and reproducible. Thus, the development of standardized protocols is essential to introduce MS into clinical research laboratories. The aim of this study was to establish a complete workflow for assessing the transferability and reproducibility of selected reaction monitoring (SRM) assays between clinical research laboratories. Four independent laboratories in North America, using identical triple-quadrupole mass spectrometers (Quantum Ultra, Thermo), were provided with standard protocols and instrumentation settings to analyze unknown samples and internal standards in a digested plasma matrix to quantify 51 peptides from 39 human proteins using a multiplexed SRM assay. The interlaboratory coefficient of variation (CV) was less than 10% for 25 of 39 peptides quantified (12 peptides were not quantified based upon hydrophobicity) and exhibited CVs less than 20% for the remaining peptides. In this report, we demonstrate that previously developed research platforms for SRM assays can be improved and optimized for deployment in clinical research environments.

Understanding atomic-resolved STM images on TiO2(110)-(1 x 1) surface by DFT calculations.

We present a combination of experimental STM images and DFT calculations to understand the atomic scale contrast of features found in high-resolution STM images. Simulating different plausible structural models for the tip, we have been able to reproduce various characteristics previously reported in experimental images on TiO(2)(110)-(1 x 1) under controlled UHV conditions. Our results allow us to determine the influence of different chemical and morphological tip terminations on the atomic-resolution STM images of the TiO(2)(110)-(1 x 1) surface. The commonest images have been properly explained using standard models for a W tip, either clean or with a single O atom located at the apex. Furthermore, a double transfer of oxygen atoms can account for different types of bizarre atomic-resolution features occasionally seen, and not conclusively interpreted before. Importantly, we discuss how typical point-defects are imaged on this surface by different tips, namely bridging O vacancies and adsorbed OH groups.

Theoretical kinetic study of the reactions of cycloalkylperoxy radicals.

Reactions of alkyl radicals with oxygen are key reactions in the low-temperature oxidation of hydrocarbons, but they have not been extensively studied yet in the case of cycloalkanes. Isomerizations of cycloalkylperoxy radicals and formation of cyclic ethers are especially important. In the present work, a theoretical study of the gas-phase reactions of cyclopentylperoxy and cyclohexylperoxy radicals has been carried out by means of quantum chemical calculations at the CBS-QB3 level. Computations on cyclopentylperoxy decomposition pathways are reported here for the first time. Thermochemical data have been obtained by means of isodesmic reactions, and the contribution of hindered rotors has been explicitly taken into account. Transition state theory has been used to calculate rate constants for all the elementary reactions. Three-parameter Arrhenius expressions have been derived in the temperature range 300-1000 K. Tunneling effects have been accounted for in the case of H-atom transfers. Our results compare well with experimental data and previous calculations available in the literature. In particular, the predicted rate constants for processes involving cyclohexylperoxy radicals, which have been introduced in a reaction mechanism scheme proposed before, exhibit excellent agreement with experiments at low and intermediate temperatures.

The structure of chlorophyll a-water complexes: insights from quantum chemistry calculations.

Computations show that chlorophyll a is able to coordinate a maximum of two water molecules in hydrophobic media that form a bridge between the Mg atom and the methyl ester carbonyl group.

Theoretical kinetic study of thermal unimolecular decomposition of cyclic alkyl radicals.

Whereas many studies have been reported on the reactions of aliphatic hydrocarbons, the chemistry of cyclic hydrocarbons has not been explored extensively. In the present work, a theoretical study of the gas-phase unimolecular decomposition of cyclic alkyl radicals was performed by means of quantum chemical calculations at the CBS-QB3 level of theory. Energy barriers and high-pressure-limit rate constants were calculated systematically. Thermochemical data were obtained from isodesmic reactions, and the contribution of hindered rotors was taken into account. Classical transition state theory was used to calculate rate constants. The effect of tunneling was taken into account in the case of CH bond breaking. Three-parameter Arrhenius expressions were derived in the temperature range of 500-2000 K at atmospheric pressure, and the CC and CH bond breaking reactions were studied for cyclic alkyl radicals with a ring size ranging from three to seven carbon atoms, with and without a lateral alkyl chain. For the ring-opening reactions, the results clearly show an increase of the activation energy as the pi bond is being formed in the ring (endo ring opening) in contrast to the cases in which the pi bond is formed on the side chain (exo ring opening). These results are supported by analyses of the electronic charge density that were performed with Atoms in Molecules (AIM) theory. For all cycloalkyl radicals considered, CH bond breaking exhibits larger activation energies than CC bond breaking, except for cyclopentyl for which the ring-opening and H-loss reactions are competitive over the range of temperatures studied. The theoretical results compare rather well with the experimental data available in the literature. Evans-Polanyi correlations for CC and CH beta-scissions in alkyl and cycloalkyl free radicals were derived. The results highlight two different types of behavior depending on the strain energy in the reactant.

Nanomechanical properties of surface-modified titanium alloys for biomedical applications.

The mechanical properties of the oxide layers developed at elevated temperature on three vanadium-free titanium alloys of interest for biomedical applications were investigated by means of the nanoindentation technique. The as-received alloys (Ti-13Nb-13Zr, Ti-15Zr-4Nb and Ti-7Nb-6Al) and their oxide scales formed by reaction with air at 750 degrees C for several oxidation times were analysed comparatively. In particular, the hardness and the Young's modulus exhibit larger values for the thermally oxidized alloys than for the untreated specimens. However, the Ti-7Nb-6Al alloy shows a different tendency to that of the TiNbZr alloys, which seems to be related to a different oxide layer growth as a function of the oxidation time.

Comparison of conventional cytomorphology, flow cytometry immunophenotyping, and automated cell counting of CSF for detection of CNS involvement in acute lymphoblastic leukemia.

BACKGROUND AND OBJECTIVE: Cytospin conventional cytomorphology (CCC) is the standard method for detecting lymphoblasts in cerebrospinal fluid (CSF) of patients with acute lymphoblastic leukemia (ALL) and for guiding treatment decisions. We evaluated flow cytometry immunophenotyping (FCI) performance for improving detection of central nervous system (CNS) involvement in ALL. METHODS: This prospective study included analysis of consecutive CSF samples of patients of all ages with ALL at 3 clinical stages: new diagnosis, relapse suspicion, and after relapse treatment. Manual, cytospin, automated, and FCI methods were compared and their performance statistically assessed. Using FCI as the reference method, optimal CSF cutoff cell count that better correlated with presence of lymphoblasts was established by receiver operating characteristic (ROC) curve analysis. RESULTS: Seventy-seven CSF samples were investigated, 35 (45.4%) from newly diagnosed cases, 30 (39%) suspicion of relapse, and 12 (15.6%) after treatment for relapse. Median manual WBC count in patients with CNS involvement detected by FCI was 3.75 cells/µL (0.0-1280), and this was also the count that best correlated with CNS infiltration (sensitivity, 50.0%; specificity, 82.2%). Compared with FCI, CCC sensitivity and specificity were 28.6% and 100%. Automated CSF WBC count in patients with CNS involvement detected by FCI was 5 (0.0-1578). For automated count, optimal WBC cutoff was 4.5 cells/µL (sensitivity, 62.5%; specificity, 70.5%). CONCLUSION: Flow cytometry immunophenotyping complements conventional cytospin analysis for detection of lymphoblasts in the CSF of ALL patients at any clinical stage.

Effect of kainic acid treatment on insulin-like growth factor-2 receptors in the IGF2-deficient adult mouse brain.

Insulin-like growth factor-2 (IGF2) is a member of the insulin gene family with known neurotrophic properties. The actions of IGF2 are mediated via the IGF type 1 and type 2 receptors as well as through the insulin receptors, all of which are widely expressed throughout the brain. Since IGF2 is up-regulated in the brain after injury, we wanted to determine whether the absence of IGF2 can lead to any alteration on brain morphology and/or in the response of its receptor binding sites following a neurotoxic insult. No morphological differences were observed between the brains of IGF2 knockout (IGF2(-/-)) and wild-type control (IGF2(+/+)) mice. However, our in vitro receptor autoradiography results indicate that IGF2(-/-) mice had lower endogenous levels of [(125)I]IGF1 and [(125)I]insulin receptor binding sites in the hippocampus and cerebellum as compared to IGF2(+/+) mice, while endogenous [(125)I]IGF2 receptor binding showed a decrease only in the cerebellum. Seven days after kainic acid administration, the [(125)I]insulin receptor binding sites were significantly decreased in all brain regions of the IGF2(+/+) mice, while the levels of [(125)I]IGF1 and [(125)I]IGF2 binding sites were decreased only in select brain areas. The IGF2(-/-) mice, on the other hand, showed increased [(125)I]IGF1 and [(125)I]IGF2 and [(125)I]insulin receptor binding sites in selected regions such as the hippocampus and cerebellum. These results, taken together, suggest that deletion of IGF2 gene does not affect gross morphology of the brain but does selectively alter endogenous [(125)I]IGF1, [(125)I]IGF2 and [(125)I]insulin receptor binding sites and their response to neurotoxicity.

Increased biodegradability of Ultracid in aqueous solutions with solar TiO2 photocatalysis.

A study of solar TiO(2) photocatalytic degradation of the insecticide Ultracidtrade mark, a commercial formulation containing methidathion as the active ingredient, is described. Total elimination of methidathion can be achieved in less than 2h of irradiation, although longer solar exposures are needed for complete mineralisation of the solution (7-8h). Activated sludge respirometry shows that when methidathion is eliminated, the solution is detoxified, so further irradiation does not seem necessary. A Zahn-Wellens test also indicates improved biodegradability of the treated sample after abatement of the active ingredient. Finally, analysis of the ions formed indicates that the thiophosphate moiety of the molecule is preferentially attacked in the early stages of the reaction, while the thiadiazole ring is more sluggish to the effect of TiO(2)-photocatalysis.