Kinetics and mechanism of formic acid decomposition on Ru(001)

The steady-state rate of decomposition of formic acid on Ru(001) has been measured as a function of surface temperature, parametric in the pressure of formic acid. The products of the decomposition reaction are C0_2, H_2, CO, and H_2)0, i.e., both dehydrogenation and dehydration occur on Ru (001). A similar product distribution has been observed on Ni(110), Ni(100), Ru(100), Fe(100), and Ni(111) surfaces; whereas only dehydrogenation to C0_2 and H_2 occurs on the Cu(100), Cu(110), and Pt(111) surfaces. Only reversible adsorption and desorption of formic acid is observed on the less reactive Ag(110) surface at low temperatures, whereas the more reactive Mo(100) surface is oxidized by formic acid at low temperatures with the products of this reaction being H_2, CO, and H_(2)O (Ref. 10). We report here the confirmation of earlier observations of the occurrence of both dehydrogenation and dehydration of formic acid on Ru(001), and more importantly, we provide a detailed mechanistic description of the steady-state decomposition reaction on this surface in terms of elementary steps

The association between retinal vein ophthalmodynamometric force change and optic disc excavation

Aim: Retinal vein ophthalmodynamometric force (ODF) is predictive of future optic disc excavation in glaucoma, but it is not known if variation in ODF affects prognosis. We aimed to assess whether a change in ODF provides additional prognostic information. Methods: 135 eyes of 75 patients with glaucoma or being glaucoma suspects had intraocular pressure (IOP), visual fields, stereo optic disc photography and ODF measured on an initial visit and a subsequent visit at mean 82 (SD 7.3) months later. Corneal thickness and blood pressure were recorded on the latter visit. When venous pulsation was spontaneous, the ODF was recorded as 0 g. Change in ODF was calculated. Flicker stereochronoscopy was used to determine the occurrence of optic disc excavation, which was modelled against the measured variables using multiple mixed effects logistic regression. Results: Change in ODF (p=0.046) was associated with increased excavation. Average IOP (p=0.66) and other variables were not associated. Odds ratio for increased optic disc excavation of 1.045 per gram ODF change (95% CI 1.001 to 1.090) was calculated. Conclusion: Change in retinal vein ODF may provide additional information to assist with glaucoma prognostication and implies a significant relationship between venous change and glaucoma patho-physiology

Secondary organic aerosol formation from m-xylene, toluene, and benzene

Secondary organic aerosol (SOA) formation from the photooxidation of m-xylene, toluene, and benzene is investigated in the Caltech environmental chambers. Experiments are performed under two limiting NOx conditions; under high-NOx conditions the peroxy radicals (RO2) react only with NO, while under low-NOx conditions they react only with HO2. For all three aromatics studied (m-xylene, toluene, and benzene), the SOA yields (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) under low-NOx conditions substantially exceed those under high-NOx conditions, suggesting the importance of peroxy radical chemistry in SOA formation. Under low-NOx conditions, the SOA yields for m-xylene, toluene, and benzene are constant (36%, 30%, and 37%, respectively), indicating that the SOA formed is effectively nonvolatile under the range of Mo(>10 μg m−3) studied. Under high-NOx conditions, aerosol growth occurs essentially immediately, even when NO concentration is high. The SOA yield curves exhibit behavior similar to that observed by Odum et al. (1996, 1997a, b), although the values are somewhat higher than in the earlier study. The yields measured under high-NOx conditions are higher than previous measurements, suggesting a "rate effect" in SOA formation, in which SOA yields are higher when the oxidation rate is faster. Experiments carried out in the presence of acidic seed aerosol reveal no change of SOA yields from the aromatics as compared with those using neutral seed aerosol

Exterior optical cloaking and illusions by using active sources: a boundary element perspective

Recently, it was demonstrated that active sources can be used to cloak any objects that lie outside the cloaking devices [Phys. Rev. Lett. \textbf{103}, 073901 (2009)]. Here, we propose that active sources can create illusion effects, so that an object outside the cloaking device can be made to look like another object. invisibility is a special case in which the concealed object is transformed to a volume of air. From a boundary element perspective, we show that active sources can create a nearly "silent" domain which can conceal any objects inside and at the same time make the whole system look like an illusion of our choice outside a virtual boundary. The boundary element method gives the fields and field gradients (which can be related to monopoles and dipoles) on continuous curves which define the boundary of the active devices. Both the cloaking and illusion effects are confirmed by numerical simulations

Role of aldehyde chemistry and NO_x concentrations in secondary organic aerosol formation

Aldehydes are an important class of products from atmospheric oxidation of hydrocarbons. Isoprene (2-methyl-1,3-butadiene), the most abundantly emitted atmospheric non-methane hydrocarbon, produces a significant amount of secondary organic aerosol (SOA) via methacrolein (a C_4-unsaturated aldehyde) under urban high-NO_x conditions. Previously, we have identified peroxy methacryloyl nitrate (MPAN) as the important intermediate to isoprene and methacrolein SOA in this NO_x regime. Here we show that as a result of this chemistry, NO_2 enhances SOA formation from methacrolein and two other α, β-unsaturated aldehydes, specifically acrolein and crotonaldehyde, a NO_x effect on SOA formation previously unrecognized. Oligoesters of dihydroxycarboxylic acids and hydroxynitrooxycarboxylic acids are observed to increase with increasing NO_2/NO ratio, and previous characterizations are confirmed by both online and offline high-resolution mass spectrometry techniques. Molecular structure also determines the amount of SOA formation, as the SOA mass yields are the highest for aldehydes that are α, β-unsaturated and contain an additional methyl group on the α-carbon. Aerosol formation from 2-methyl-3-buten-2-ol (MBO232) is insignificant, even under high-NO_2 conditions, as PAN (peroxy acyl nitrate, RC(O)OONO_2) formation is structurally unfavorable. At atmospherically relevant NO_2/NO ratios (3–8), the SOA yields from isoprene high-NO_x photooxidation are 3 times greater than previously measured at lower NO_2/NO ratios. At sufficiently high NO_2 concentrations, in systems of α, β-unsaturated aldehydes, SOA formation from subsequent oxidation of products from acyl peroxyl radicals+NO_2 can exceed that from RO_2+HO_2 reactions under the same inorganic seed conditions, making RO_2+NO_2 an important channel for SOA formation

An Improved Private Mechanism for Small Databases

We study the problem of answering a workload of linear queries $\mathcal{Q}$, on a database of size at most $n = o(|\mathcal{Q}|)$ drawn from a universe $\mathcal{U}$ under the constraint of (approximate) differential privacy. Nikolov, Talwar, and Zhang~\cite{NTZ} proposed an efficient mechanism that, for any given $\mathcal{Q}$ and $n$, answers the queries with average error that is at most a factor polynomial in $\log |\mathcal{Q}|$ and $\log |\mathcal{U}|$ worse than the best possible. Here we improve on this guarantee and give a mechanism whose competitiveness ratio is at most polynomial in $\log n$ and $\log |\mathcal{U}|$, and has no dependence on $|\mathcal{Q}|$. Our mechanism is based on the projection mechanism of Nikolov, Talwar, and Zhang, but in place of an ad-hoc noise distribution, we use a distribution which is in a sense optimal for the projection mechanism, and analyze it using convex duality and the restricted invertibility principle.Comment: To appear in ICALP 2015, Track

Fos co-operation with PTEN loss elicits keratoacanthoma not carcinoma due to p53/p21^WAF-induced differentiation triggered by GSK3b inactivation and reduced AKT activity

To investigate gene synergism in multistage skin carcinogenesis, the RU486-inducible cre/lox system was employed to ablate PTEN function [K14.cre/D5PTENflx] in mouse epidermis expressing activated v-fos [HK1.fos]. RU486-treated HK1.fos/D5PTENflx mice exhibited hyperplasia, hyperkeratosis and tumours that progressed to highly differentiated keratoacanthomas rather than carcinomas, due to re-expression of high p53 and p21WAF levels. Despite elevated MAP kinase activity, cyclin D1/E2 over expression and increased AKT activity forming areas of highly proliferative, papillomatous keratinocytes, increasing levels of GSK3b inactivation exceeded a threshold that induced p53/p21WAF expression to halt proliferation and accelerate differentiation, giving the hallmark keratosis of keratoacanthomas. A pivotal facet to this GSK3b-triggered mechanism centred on increasing p53 expression in basal layer keratinocytes. This reduced activated AKT expression and released inhibition of p21WAF, which accelerated keratinocyte differentiation, as indicated by unique basal layer expression of differentiation-specific keratin K1, alongside premature filaggrin and loricrin expression. Thus, fos synergism with PTEN loss elicited a benign tumour context where GSK3b-induced, p53/p21WAF expression continually switched AKT-associated proliferation into one of differentiation, preventing further progression. This putative compensatory mechanism required the critical availability of normal p53 and/or p21WAF otherwise deregulated fos, Akt and GSK3b associate with malignant progression