Synthesis and Characterization of the (5′ → 5″)-Ester of Adenosine 5′-diphosphate with α-D-ribofuranose cyclic 1″,2″-phosphate: A NAD derivative produced during tRNA splicing

The synthesis and spectroscopic properties of the (5′ → 5″)-ester of adenosine 5′-diphosphate with ribofuranose cyclic 1″, 2″-phosphate 3 , a recently discovered metabolite produced during tRNA splicing, are reported.     

Controlled pinewood fractionation with supercritical ethanol: A prerequisite toward pinewood conversion into chemicals and biofuels

The objective of this work was to investigate the ability of supercritical (SC) ethanol conditions to attack preferentially the lignin fraction against the carbohydrate fraction and their effects on the product distribution among gases, light products, bio-oils, and chars. In this study, the conversion of each pinewood component was determined by the analysis of solid residues to quantify cellulose, hemicellulose, lignin, and char contents. It is shown that, by tuning the temperature, hemicellulose and lignin are already transformed in subcritical ethanol conditions, lignin being more reactive than hemicellulose. In contrast, native wood cellulose is recalcitrant to liquefaction in SC ethanol near the critical point (T_c = 241 °C and P_c = 61 bar), but 20% of native wood cellulose is converted in SC ethanol at 280 °C. Besides, the severity of the conditions, in terms of temperature and treatment time, does not significantly influence the yields of gases, light products, and bio-oils but strongly enhances char formation. Interestingly, the increase in SC ethanol density does not change the conversion of biomass components but has a marked effect on bio-oil yield and prevents char formation. The optimum fractionation conditions to convert the lignin component, while keeping unattacked the cellulose fraction with a minimum formation of char, are dense SC ethanol, at 250 °C for 1 h, in batch conditions. However, although lignin is more reactive than hemicellulose under these conditions, these fractions are converted, in a parallel way, to around 50% and 60%, respectively.     

Incorporation of a minimal nucleotide into DNA

Abasic sites are amongst the most frequent DNA lesions and result from spontaneous hydrolysis of the glycosidic bond or from the removal of damaged nucleobases. These depurination events can also occur on free deoxyribonucleoside triphosphates present in cells and lead to the formation of an abasic site triphosphate of which very little is known. Herein, we report the synthesis and biochemical characterization of the minimal triphosphate dФTP. Unexpectedly, dФTP is tolerated by various DNA polymerases and the incorporation efficiency obeys the A-rule. Single incorporation of dФMP units were also observed opposite abasic sites and the addition of prosthetic molecules mimicking base-pairs do not seem to favor the process.     

An Exceptionally Close,Non‐Bonded Hydrogen–Hydrogen Contact with Strong Through‐Space Spin–Spin Coupling

Condensation of 1,8,13‐tris(mercaptomethyl)triptycene and tris(bromomethyl)methane yields an in,in‐cyclophane with two inwardly directed methine groups. Based on X‐ray analysis and DFT and MP2 calculations, the hydrogen–hydrogen non‐bonded contact distance is estimated to be 1.50–1.53 Å. Furthermore, the two in‐hydrogen atoms show obvious spin–spin coupling with J=2.0 Hz.     

Repair of (6‐4) Lesions in DNA by (6‐4) Photolyase: 20 Years of Quest for the Photoreaction Mechanism

Exposure of DNA to ultraviolet (UV) light from the Sun or from other sources causes the formation of harmful and carcinogenic crosslinks between adjacent pyrimidine nucleobases, namely cyclobutane pyrimidine dimers and pyrimidine(6–4)pyrimidone photoproducts. Nature has developed unique flavoenzymes, called DNA photolyases, that utilize blue light, that is photons of lower energy than those of the damaging light, to repair these lesions. In this review, we focus on the chemically challenging repair of the (6–4) photoproducts by (6–4) photolyase and describe the major events along the quest for the reaction mechanisms, over the 20 years since the discovery of (6‐4) photolyase.     

Inverse gas chromatography of lignocellulosic fibers coated with a thermosetting polymer: Use of peak maximum and conder and young methods

The Conder and Young (CY) and the peak maximum (PM) methods were used to estimate the retention time of n-alkane probes on chemithermomechanical pulp (CTMP) wood fibers treated with a low molecular weight grade phenol-formaldehyde resin (PFR). Thermodynamic functions (ΔH_a^o, ΔG_a^o, and ΔS_a^o) and the London dispersive component of the surface energy were derived from these retention times. Treated wood fibers show a high energy surface due to the presence of the thermoset resin on their surface. Values of ΔH_a^o obtained from the CY method were higher than those obtained with the PM method at relatively high temperatures and with relatively low molecular weight alkanes. The results from the two methods were identical at low temperature (293 K) and with the relatively high molecular weight alkane n-undecane.