Uncertainty evaluation of the spectral UV irradiance evaluated by using the UVSPEC radiative transfer model

The radiative transfer models allow calculating the spectral UV irradiance from some set of measured input quantities linked with the surface reflectivity, the solar zenith angle, the ozone column and the characteristics of clouds and aerosols. The spectral irradiance yielded by a model is influenced by errors in the measurement of the input quantities. In this paper, the influences of these errors are characterized and compared with other systematic effects through an uncertainty analysis. We evaluated the uncertainty of the spectral UV irradiance rendered by the UVSPEC model, under cloudless sky conditions. In order to express the uncertainty of the output quantities (the global, direct and diffuse irradiances) in terms of the standard uncertainties of the input quantities, we used a Monte Carlo-based uncertainty propagation technique. We found that the uncertainty of the irradiance in the UV-B part of the spectrum was strongly influenced by the uncertainty attributed to the ozone column datum. Moreover, the uncertainities associated with the aerosol parameters accounted for most of the UV-A global irradiance uncertainty; the latter increased from about 4% under low aerosol conditions, up to about 14% in case of polluted air. We conclude that the UV irradiance evaluation through radiative transfer models requires paying special attention to the assessment of the aerosols properties.     

On Inexact Relative-Error Hybrid Proximal Extragradient,Forward-Backward and Tseng’s Modified Forward-Backward Methods with Inertial Effects

Set-Valued and Variational Analysis - For solving monotone inclusion problems, we propose an inertial under-relaxed version of the relative-error hybrid proximal extragradient method. We study the...     

Euler's relation,möbius functions and matroid identities

We give a short combinatorial proof of the Euler relation for convex polytopes in the context of oriented matroids. Using counting arguments we derive from the Euler relation several identities holding in the lattice of flats of an oriented matroid. These identities are proven for any matroid by Möbius inversion.     

Exploring the thermochromism of sulfite-embedded polyoxometalate capsules

The Dawson-type polyanion [α-Mo(18)O(54)(SO(3))(2)](4-), with two SO(3)(2-) templates embedded inside a polyoxomolybdate(vi) cage, exhibits thermochromism over an exceptionally wide temperature range (～500 K). The temperature dependence of the cluster structure, established from X-ray crystallography, IR and Raman spectroscopy and DFT calculations, is related to a decreasing HOMO-LUMO gap in the near UV with increasing temperature. We postulate this is due to geometrical changes that affect both the occupied and unoccupied frontier molecular orbitals of this cluster anion.     

CE methods for analysis of isoforms of prostate-specific antigen compatible with online derivatization for LIF detection

Prostate-specific antigen (PSA) is the usual biomarker for prostate cancer (PCa). However, its lack of selectivity has lead to the search for new biomarkers. PSA glycosylation seems to depend on the pathophysiological conditions of the individual. Thus, methods to separate PSA isoforms (peaks) to study their role as PCa markers are needed. In this work, CE methods for PSA isoforms separation, based on the use of different dynamic coatings, are developed using UV detection. Three complementary CE methods allowing the separation of 8 or 9 PSA isoforms are selected. The longest method takes only 17?min, while the shortest one separates 9 isoforms in < 8?min. Depending on the isoforms of interest for their use as PCa biomarker, the CE method to be used can be chosen or various of them can be combined. A remarkable aspect of these methods is that the BGEs employed are devoid of compounds with primary amino groups, making the CE methods compatible with fluorescent on-column derivatization through amino residues. As a proof-of-concept, a preliminary result shows that LIF detection of labeled PSA analyzed by one of the three developed methods permits detection of glycoprotein isoforms.     

Production of Cellulolytic Enzymes by Fungi Acrophialophora nainiana and Ceratocystis paradoxa Using Different Carbon Sources

Although a number of filamentous fungi, such as Trichoderma and Aspergillus, are well known as producers of cellulases, xylanases, and accessory cellulolytic enzymes, the search for new strains and new enzymes has become a priority with the increase in diversity of biomass sources. Moreover, according to the type of pretreatment applied, biomass of the same type may require different enzyme blends to be efficiently hydrolyzed. This study evaluated cellulases, xylanases, and β-glucosidases produced by two fungi, the thermotolerant Acrophialophora nainiana and Ceratocystis paradoxa. Cells were grown in submerged culture on three carbon sources: lactose, wheat bran, or steam-pretreated sugarcane bagasse, a commonly used cattle feed in Brazil. Xylanase and endo-1-4-β-glucanase (CMCase) highest production were found in A. nainiana growing on lactose and reached levels of 2,200 and 2,016 IU/L, respectively. C. paradoxa showed highest activity for xylanase when grown on wheat bran and for β-glucosidase when grown on steam-treated bagasse, at levels of 12,728 and 1,068 IU/mL, respectively.     

Novel Capsular Aggregates from Flexible Tripodal Triureas with Cs Symmetry

Tris(2‐ and 3‐ureidobenzyl)amines with C_s symmetry self‐assemble in solution forming mixtures of regioisomeric capsular aggregates, one of which is chiral and the other centrosymmetric. Under certain conditions, a predominance of the centrosymmetric regioisomer is found before equilibrium, that is, a mixture close to the statistical ratio of the two species is reached. In the solid state, there is a preference for the centrosymmetric capsules. Molecular models of both regioisomeric aggregates have been built and analyzed for comparison. Guests inside capsules formed by self‐assembly of desymmetrized tris(3‐ureidobenzyl)amines feel different magnetic environments, depending on whether they are inside a chiral or an achiral regioisomeric container. Of special significance are the experiments with a more flexible triurea endowed with an ureidopropylic arm, which self‐assembles with the same efficiency as the more rigid tris(ureidobenzyl)amines.     

New Rare‐Earth Metal Germanides RE2Ge9 (RE = Nd,Sm) by Thermal Decomposition of High‐Pressure Phases REGe5

The rare‐earth metal germanides RE₂Ge₉ (RE = Nd, Sm) have been prepared by thermal decomposition of the metastable high‐pressure phases REGe₅ at ambient pressure. The compounds adopt an orthorhombic unit cell with a = 396.34(4) pm; b = 954.05(8) pm and c = 1238.4(1) pm for Nd₂Ge₉ and a = 395.46(7) pm; b = 946.4(2) pm and c = 1232.1(3) pm for Sm₂Ge₉. Crystal structure refinements reveal space group Pmmn (No. 59) for Nd₂Ge₉. The atomic pattern resembles an ordered defect variety of the pentagermanide motif REGe₅ (RE = La; Nd, Sm, Gd, Tb) comprising corrugated germanium layers. These condense into a three‐dimensional network interconnected by eight‐coordinated germanium atoms. The resulting framework channels along [100] enclose the neodymium atoms. With respect to the atomic arrangement of the pentagermanides, half of the interlayer germanium atoms are eliminated in an ordered way so that occupied and empty germanium columns alternate along [001]. The rare‐earth metal atoms of both types of compounds, REGe₅ and RE₂Ge₉, exhibit the electronic states 4f ³ and 4f ⁵ (oxidation state +3) for neodymium and samarium, respectively, evidencing that the modification of the germanium network leaves the electron configuration of the metal atoms unaffected.     

Kinetic investigation of the reactions of S-4-nitrophenyl 4-substituted thiobenzoates with secondary alicyclic amines in aqueous ethanol

The reactions of S-4-nitrophenyl 4-X-substituted thiobenzoates (X = H, Cl, and NO(2): 1, 2, and 3, respectively) with a series of secondary alicyclic amines (SAA) were subjected to a kinetic investigation in 44 wt % ethanol-water, at 25.0 degrees C and an ionic strength of 0.2 M (KCl). The reactions were followed spectrophotometrically by monitoring the release of 4-nitrobenzenethiolate anion at 420-425 nm. Under excess amine, pseudo-first-order rate constants (k(obsd)) are obtained for all reactions. The plots of k(obsd) vs [SAA] at constant pH are linear with the slope (k(N)) independent of pH. The statistically corrected Br?nsted-type plots (log k(N)/q vs pK(a) + log p/q) for the reactions of 1 and 2 are nonlinear with slopes at high pK(a), beta(1) = 0.27 and 0.10, respectively, and slopes at low pK(a), beta(2) = 0.86 and 0.84, respectively. The Br?nsted curvature is centered at pK(a) (pK(a)(0)) 10.0 and 10.4, respectively. The reactions of SAA with 3 exhibit a linear Br?nsted-type plot of slope 0.81. These results are consistent with a stepwise mechanism, through a zwitterionic tetrahedral intermediate (T(+/-)). For the reactions of 1 and 2, there is a change in rate-determining step with amine basicity, from T(+/-) breakdown to products at low pK(a), to T(+/-) formation at high pK(a). For the reactions of 3, breakdown to products of T(+/-) is rate limiting for all the SAA series (pK(a)(0) > 11). The increasing pK(a)(0) value as the substituent in the acyl group becomes more electron withdrawing is attributed to an increasing nucleofugality of SAA from T(+/-). The greater pK(a)(0) value for the reactions of SAA with 1, relative to that found in the pyridinolysis of 2,4-dinitrophenyl benzoate (pK(a)(0) = 9.5), is explained by the greater nucleofugality from T(+/-) of the former amines, compared to isobasic pyridines, and the greater leaving ability from T(+/-) of 2,4-dinitrophenoxide relative to 4-nitrobenzenethiolate.