Phosphorodithioate [P(S¯)=S] components were employed to investigate directionality of the hole transfer processes between DNA-backbone and -base related. ESR spectroscopy in homogeneous frozen aqueous solutions, pulse radiolysis in aqueous solution at ambient temperature, and density functional theory (DFT) calculations confirmed dithiyl radical (P-2S•) formation. The ionization potential of G-P(S¯)=S was calculated to be slightly lower than that of guanine in 5'-dGMP. ESR and pulse radiolysis confirmed initial formation of G •+ -P(S¯)=S. Subsequent thermally-activated hole transfer from G •+ to P(S¯)=S led to P-2S• formation on ms timescale. ESR investigations at low temperatures and higher G-P(S¯)=S concentrations showed a bimolecular conversion of P-2S• to the σ 2 -σ* 1 -bonded dimer anion radical [-P-2S∸2S-P-]¯ [ΔG (150 K, DFT) = -7.2 kcal/mol]. However, [-P-2S∸2S-P-]¯ formation was not observed by pulse radiolysis [ΔG° (298 K, DFT) = -1.4 kcal/mol]. Neither P-2S• nor [-P-2S∸2S-P-]¯ oxidized guanine base; base-to-backbone hole transfer occurs in phosphorodithioate. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.We report a Ni-catalyzed regioselective α-carbonylalkylarylation of vinylarenes with α-halocarbonyl compounds and arylzinc reagents. The reaction works with primary, secondary and tertiary α-halocarbonyl molecules, and electronically varied arylzinc reagents. The reaction generates γ,γ-diarylcarbonyl derivatives with α-secondary, tertiary and quaternary carbon centers. The products can be readily converted to aryltetralones, including a precursor to Zoloft, an antidepressant drug. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Zeolitic Imidazolate Framework (ZIF) biocomposites show the capacity to protect and deliver bio-therapeutics. To date, the progress in this research area is based on laboratory batch methods. To further explore the potential of ZIF-biocomposites for application to biomedicine and biotechnology, the continuous production of ZIF-biocomposites of specific particle size is desirable. Here we report the first continuous flow synthetic method for the encapsulation of a model protein (bovine serum albumin, BSA) and a clinical therapeutic (α1-antitrypsin, AAT) in ZIF-8. We studied the in situ kinetics of nucleation, growth and crystallization of BSA@ZIF-8 by small angle X-ray scattering. By controlling the injection time of ethanol, we could quench the particle growth via ethanol-induced crystallization from amorphous particles to ZIF-8 crystals. The particle size of the biocomposite was tuned in the 40-100 nm range by varying residence time prior to introduction of ethanol. As a proof-of-concept, we used this protocol for the encapsulation of AAT in ZIF-8.  https://www.selleckchem.com/products/LBH-589.html  Upon release of the bio therapeutic from the composite, the trypsin inhibitor function of AAT was preserved. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Owing to the lack of specific symptoms, diagnosis of head and neck squamous cell carcinoma (HNSCC) may be delayed. We evaluated volatile organic compounds in tumor samples from patients suffering from HNSCC and tested the hypothesis that there is a characteristic altered composition in the headspace of HNSCC compared with control samples from the same patient with normal squamous epithelium. These results provide the basis for future noninvasive breath analysis in HNSCC. Headspace air of suspected tumor and contralateral control samples in 20 patients were analyzed using ion-mobility spectrometry. Squamous cell carcinoma was diagnosed in 16 patients. In total, we observed 93 different signals in headspace measurements. Squamous cell carcinomas revealed significantly higher levels of volatile cyclohexanol (0.54 ppbv , 25th to 75th percentiles 0.35-0.86) compared with healthy squamous epithelium (0.24 ppbv , 25th to 75th percentiles 0.12-0.3; p  less then  0.001). In conclusion, head and neck squamous cell carcinoma emitted significantly higher levels of volatile cyclohexanol in headspace compared with normal squamous epithelium. These findings form the basis for future breath analysis for diagnosis, therapy control and the follow-up of HNSSC to improve therapy and aftercare. © 2020 John Wiley & Sons, Ltd.Photo-redox mediated ring-opening metathesis polymerization (photo-ROMP) is an emerging ROMP technique that uses an organic redox mediator and a vinyl ether initiator, in contrast to metal-based initiators traditionally used in ROMP. The reversibility of the redox-mediated initiation and propagation steps enable spatiotemporal control over the polymerization. Herein, we explore a simple, inexpensive means of controlling molecular weight, using alpha olefins as chain transfer agents. This method enables access to low molecular weight oligomers, and molecular weights between 1 and 30 kDa can be targeted simply by altering the stoichiometry of the reaction. This method of molecular weight control was then used to synthesize a functionalized norbornene copolymer in a range of molecular weights for specific materials applications. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.OBJECTIVES While understanding of complex within-person clustering of health behaviors into meaningful profiles of risk is growing, we still know little about whether and how U.S. adults transition from one profile to another as they age. This study assesses patterns of stability and change in profiles of tobacco and alcohol use and body mass index (BMI). METHOD A nationally representative cohort of U.S. adults 25 years and older was interviewed up to 5 times between 1986 and 2011. Latent transition analysis (LTA) models characterized the most common profiles, patterning of transitions across profiles over follow-up, and assessed whether some were associated with higher mortality risk. RESULTS We identified 5 profiles "health promoting" with normal BMI and moderate alcohol consumption; "overweight"; "current smokers"; "obese"; and "nondrinkers". Profile membership was largely stable, with the most common transitions to death or weight gain. "Obese" was the most stable profile, while "smokers" were most likely to transition to another profile.