Reconstruction of Solar Spectral Surface UV Irradiances Using Radiative Transfer Simulations

UV radiation exerts several effects concerning life on Earth, and spectral information on the prevailing UV radiation conditions is needed in order to study each of these effects. In this paper, we present a method for reconstruction of solar spectral UV irradiances at the Earth's surface. The method, which is a further development of an earlier published method for reconstruction of erythemally weighted UV, relies on radiative transfer simulations, and takes as input (1) the effective cloud optical depth as inferred from pyranometer measurements of global radiation (300–3000 nm); (2) the total ozone column; (3) the surface albedo as estimated from measurements of snow depth; (4) the total water vapor column; and (5) the altitude of the location. Reconstructed daily cumulative spectral irradiances at Jokioinen and Sodankylä in Finland are, in general, in good agreement with measurements. The mean percentage difference, for instance, is mostly within ±8%, and the root mean square of the percentage difference is around 10% or below for wavelengths over 310 nm and daily minimum solar zenith angles (SZA) less than 70°. In this study, we used pseudospherical radiative transfer simulations, which were shown to improve the performance of our method under large SZA (low Sun).     

Molecular recognition: minimizing the acid–base interaction of a tunable host–guest system changes the selectivity of binding

Two new receptors incorporating a 4-n-butyl aniline moiety has been designed, synthesized and evaluated for their binding properties towards a series of ureido-glycine derivatives. The host design is based on an urea adamantyl host motif known from large generations of poly(propylene imine) dendrimers functionalized with urea adamantyl moieties on the periphery. The design of the host molecules was directed towards a study of the effects of basicity of an amine function versus the effect of molecular recognition on the binding strength as seen from comparing the results obtained in the present work with previously guest–host studies. The guest–host interaction features an electrostatic interaction and multiple hydrogen binding interactions, where the main difference between the hosts described here and previously described is a substitution from an amine to aniline. Anilines are weaker bases than aliphatic amines and they generally give lower binding constants when treated with acidic guest molecules. The association constants have been measured using NMR titrations and the nature of the guest–host system is discussed based on these results. A general decrease in binding affinities is observed upon changing from the trialkyl amine hosts to the dialkyl aniline based hosts. One exception was observed where the weaker base host had stronger affinity to one of the guests. Thus, when the basicity of the host is decreased other factors influence the binding such as a better geometric fit. A crystal structure of one of the receptors has been solved and it shows no intramolecular hydrogen bonding.     

Differentiation and quantification of synthetic phosphatidylethanol (PEth) homologues by 1H- and 13C-NMR in polar organic solvents

Various phosphatidylethanol (PEth) derivatives, the corresponding reversed positional isomers (RPI-PEths), lyso-PEth-16:0, and penta-deuterium-labeled PEth analogs (d5-PEths), were synthesized by enzyme-independent synthetic routes. A general solvent system consisting of a mixture of acetone-d6 and methanol-d4 (97:3; v/v) was found to provide a good solubilizing capacity and excellent hydrogen-1 NMR (¹H-NMR) peak resolution of various PEth homologues. Analytical differentiation of PEth from the corresponding RPI-PEth by carbon-13 NMR (¹³C-NMR) was demonstrated by comparison of the ¹³C-NMR signals of the carbonyl groups, the allylic positions, and of the β-carbons. An exemplary stable long-term room temperature, DMSO-d6-based, and proton-sensitive quantitative nuclear magnetic resonance (¹H-qNMR) independently quantified calibrator comprising PEth-16:0/18:1 for liquid chromatography (tandem) mass spectrometry (LC-MS/MS) analytical applications were prepared by employment of sodium dodecyl sulfate (SDS) as a solubilizing additive. In summary, novel hypothetically occurring PEth derivatives, e.g., RPI-PEths, have been independently synthesized with regio- and stereochemical control. Use of polar organic solvents, e.g., mixtures of acetone-d6 and methanol-d4 or DMSO-d6, improves spectral line shapes as compared to traditional hydrophobic solvents and allow for analytical differentiation between closely related PEth derivatives, as well as LC-MS/MS-independent concentration determination of dissolved single species by employment of ¹H-qNMR.

N-Aryl Isoleucine Derivatives as Angiotensin?II AT2 Receptor Ligands

A novel series of ligands for the recombinant human AT₂ receptor has been synthesized utilizing a fast and efficient palladium-catalyzed procedure for aminocarbonylation as the key reaction. Molybdenum hexacarbonyl [Mo(CO)₆] was employed as the carbon monoxide source, and controlled microwave heating was applied. The prepared N-aryl isoleucine derivatives, encompassing a variety of amide groups attached to the aromatic system, exhibit binding affinities at best with K_i values in the low micromolar range versus the recombinant human AT₂ receptor. Some of the new nonpeptidic isoleucine derivatives may serve as starting points for further structural optimization. The presented data emphasize the importance of using human receptors in drug discovery programs.     

Environmental exposure assessment framework for nanoparticles in solid waste

Information related to the potential environmental exposure of engineered nanomaterials (ENMs) in the solid waste management phase is extremely scarce. In this paper, we define nanowaste as separately collected or collectable waste materials which are or contain ENMs, and we present a five-step framework for the systematic assessment of ENM exposure during nanowaste management. The framework includes deriving EOL nanoproducts and evaluating the physicochemical properties of the nanostructure, matrix properties and nanowaste treatment processes as well as transformation processes and environment releases, eventually leading to a final assessment of potential ENM exposure. The proposed framework was applied to three selected nanoproducts: nanosilver polyester textile, nanoTiO₂ sunscreen lotion and carbon nanotube tennis racquets. We found that the potential global environmental exposure of ENMs associated with these three products was an estimated 0.5–143 Mg/year, which can also be characterised qualitatively as medium, medium, low, respectively. Specific challenges remain and should be subject to further research: (1) analytical techniques for the characterisation of nanowaste and its transformation during waste treatment processes, (2) mechanisms for the release of ENMs, (3) the quantification of nanowaste amounts at the regional scale, (4) a definition of acceptable limit values for exposure to ENMs from nanowaste and (5) the reporting of nanowaste generation data.     

The influence of the dynamics of ionic multiplets onto electronic transport properties of heavy-fermion systems: a semi-phenomenological approach

We present calculations of the electronic transport properties of heavy-fermion systems within a semi-phenomenological approach to the dynamical mean field theory. In this approach the dynamics of the Hund's rules 4f (5f )-ionic multiplet split in a crystalline environment is taken into account. Within the scope of this calculation we use the linear response theory to reproduce qualitative features of the temperature-dependent resistivity and hall conductivity, the magneto-resistivity and the thermoelectric power typical for heavy-fermion systems. The model calculations are directly compared with experimental results on CeCu ₂ Si ₂. Received 30 June 2000 and Received in final form 15 December 2000     

Reversal of Enantiomeric Retention Order by Using a Single N-Derivatized Dipeptide as Chiral Mobile Phase Additive and Porous Graphitised Carbon as Stationary Phase

In this work the three dipeptides, Z-l-alanyl-l-glutaric acid (Z-l-ala-l-glu), Z-l-phenylanyl-l-glutaric acid (Z-l-phe-l-glu) and Z-glycyl-l-glutaric acid (Z-gly-l-glu) were tested as chiral counter ions for enantiomeric resolution of amino alcohols. The influence of solute and counter ion structure upon retention and enantioselectivity was evaluated. The chiral counter ions were dissolved in a mixture of polar solvents, i.e., ethyl acetate, methanol and acetonitrile and the achiral solid phase used was porous graphitic carbon, marketed as Hypercarb. The enantioselectivities observed for the tested solutes were highly influenced by the used chiral counter ion structure. For example no enantioselectivity was observed for (R,S)-alprenolol using Z-l-ala-l-glu while a separation factor (α) of 1.59 was obtained using Z-l-phe-l-glu as chiral counter ion. High selectivity factors (α > 2.7) were observed between enantiomers of tertiary amines using Z-l-phe-l-glu as counter ion. Interestingly, the structure of the counter ion, as well as the charge on Z-l-phe-l-glu and the mobile phase solvent composition, influenced the retention order of the enantiomers.