Ultraviolet B Wavelength Dependence for the Regulation of Two Major Matrix-Metalloproteinases and Their Inhibitor TIMP-1 in Human Dermal Fibroblasts

Abstract— The wavelength dependence for the regulation of two major matrix-metalloproteinases, interstitial collagenase (MMP-1) and stromelysin-1 (MMP-3), and their major inhibitor, tissue inhibitor of metalloproteinases (TIMP-1), was studied in human dermal fibroblasts in vitro. Monochromatic irradiation at 302, 307, 312 and 317 nm with intensities ranging from 20 to 300 J/m² increased MMP-1 and MMP-3 mRNA steady-state levels and the secretion of the corresponding proteins up to 4.4-fold, whereas almost no increase was observed at wavelengths <290 nm. In contrast, the synthesis of TIMP-1 increased only marginally. This unbalance may contribute to the severe connective tissue damage related to photoaging of the skin. The wavelengths responsible for MMP-1 and MMP-3 induction reported here are distinct from the absorption spectrum of DNA and are different from results previously reported in the literature. Importantly, they overlap with wavelengths whose intensity is predicted to increase on the earth's surface upon ozone depletion. Intensities and particular wavelengths used in our studies in vitro can be absorbed readily by fibroblasts within the skin in vivo and, thus, are relevant for risk assessment and development of protective agents.     

Xylose-DNA Containing the Four Natural Bases

Oligonucleotides containing (2′-deoxy-β-D -xylofuranosyl)guanine have been prepared. For this purpose 2-aminoadenosine ( 5 ) was synthesized and converted to 2′-deoxy-β-D -xyloguanosine ( 1 ). The related 2′-deoxy-β-D -xyloisoguanosine ( 3 ) and 2′-deoxy-β-D -xyloxanthosine ( 4 ) were also synthesized. Compound 1 was converted to the phosphonate and phosphoramidite building blocks 10 and 11 , respectively. The oligodeoxynucleotide (5′-3′)d(xG-xT-xA-xG-xA-xA-xT-xT-xC-xT-xA-xC-T) ( 18 ) formed a duplex with the same T_m as the parent (5′-3′)-(G-T-A-G-A-A-T-T-C-T-A-C) ( 19 ), but with an inverted CD spectrum.     

Doping‐Induced Absorption Bands in P3HT: Polarons and Bipolarons

In this work, we focus on the formation of different kinds of charge carriers such as polarons and bipolarons upon p‐type doping (oxidation) of the organic semiconductor poly(3‐ hexylthiophene‐2,5‐diyl) (P3HT). We elucidate the cyclic voltammogram during oxidation of this polymer and present spectroscopic changes upon doping in the UV/Vis/near‐IR range as well as in the mid‐IR range. In the low‐oxidation regime, two absorption bands related to sub‐gap transitions appear, one in the UV/Vis range and another one in the mid‐IR range. The UV/Vis absorption gradually decreases upon further doping while the mid‐IR absorption shifts to lower energy. Additionally, electron paramagnetic resonance (EPR) measurements are performed, showing an increase of the EPR signal up to a certain doping level, which significantly decreases upon further doping. Furthermore, the absorption spectra in the UV/Vis range are analyzed in relation to the morphology (crystalline vs. amorphous) by using theoretical models. Finally, the calculated charge carriers from cyclic voltammogram are linked together with optical transitions as well as with the EPR signals upon p‐type doping. We stress that our results indicate the formation of polarons at low doping levels and the existence of bipolarons at high doping levels. The presented spectroscopic data are an experimental evidence of the formation of bipolarons in P3HT.     

Formaldehyde Formation on Vanadium Oxide Surfaces V2O3(0001) and V2O5(001): How does the Stable Methoxy Intermediate Form?

Hydroxy‐mediated methoxy formation or stabilization is probably an important process in many methanol adsorption systems. Hydrogen atoms originating from the scission of the methanol O? H bond react with the substrate and form water. This process may result 1) in the production of additional surface defects as reactive centers for methoxy formation and 2) in the stabilization of methoxy groups by suppression of methanol formation.

     

Quantitative Depth Profiling Using Online-Laser Ablation of Solid Samples in Liquid (LASIL) to Investigate the Oxidation Behavior of Transition Metal Borides

The increased demand for sustainability requires, among others, the development of new materials with enhanced corrosion resistance. Transition metal diborides are exceptional candidates, as they exhibit fascinating mechanical and thermal properties. However, at elevated temperatures and oxidizing atmospheres, their use is limited due to the fact of their inadequate oxidation resistance. Recently, it was found that chromium diboride doped with silicon can overcome this limitation. Further improvement of this protective coating requires detailed knowledge regarding the composition of the forming oxide layer and the change in the composition of the remaining thin film. In this work, an analytical method for the quantitative measurement of depth profiles without using matrix-matched reference materials was developed. Using this approach, based on the recently introduced online-LASIL technique, it was possible to achieve a depth resolution of 240 nm. A further decrease in the ablation rate is possible but demands a more sensitive detection of silicon. Two chromium diboride samples with different Si contents suffering an oxidation treatment were used to demonstrate the capabilities of this technique. The concentration profiles resembled the pathway of the formed oxidation layers as monitored with transmission electron microscopy. The stoichiometry of the oxidation layers differed strongly between the samples, suggesting different processes were taking place. The validity of the LASIL results was cross-checked with several other analytical techniques.     

2,2-Dioxo-1H-thieno[3,4-c][1,2]thiazines. Synthesis and some reactions of a new heterocycle

The first synthesis of substituted 2,2-dioxo-1-phenyl-1H-thieno[3,4-c][1,2]thiazines 2 and some of their reactions are achieved. Compounds 2 were prepared from the 3,5-dimethyl-1,1-dioxo-1,2-thiazine-4-carbaldehydes 1 by reaction with sulfur and triethyl amine in dimethylformamide under mild conditions. They were characterized spectroscopically and by X-ray structure analysis. The formylation, chlorination and oxidation of 2 are reported.     

Correlation between thermal and mass spectral techniques for the characterization of allenylidene and carbene complexes

The fragmentation pathways of allenylidene and carbene complexes have been studied using FAB mass spectrometry in comparison with thermal analyses (TGA, DrTG and DTA). Both the decomposition modes are investigated and the possible fragmentation pathways are suggested. The use of mass and thermal analyses (TGA and DTA) in the analyses of allenylidene and carbene complexes allowed the characterization of the fragmentation pathways in MS. The major pathway includes successive loss of carbon monoxide followed by fragmentation of the organic part of the allenylidene or carbene molecules. This is also confirmed by thermogravimetric analysis (TGA) where the first step involves the loss of carbon monoxide followed by the organic ligand. The nature of each step; exothermic or endothermic, is also studied using DTA technique. The kinetic parameters of the thermal decomposition are also studied using the Coates-Redfern method.