Combining Fullerenes and Zwitterions in Non‐Conjugated Polymer Interlayers to Raise Solar Cell Efficiency

Polymer zwitterions were synthesized by nucleophilic ring‐opening of 3,3′‐(but‐2‐ene‐1,4‐diyl)bis(1,2‐oxathiolane 2,2‐dioxide) (a bis‐sultone) with functional perylene diimide (PDI) or fullerene monomers. Integration of these polymers into solar cell devices as cathode interlayers boosted efficiencies of fullerene‐based organic photovoltaics (OPVs) from 2.75 % to 10.74 %, and of non‐fullerene‐based OPVs from 4.25 % to 10.10 %, demonstrating the versatility of these interlayer materials in OPVs. The fullerene‐containing polymer zwitterion ( C₆₀‐PZ ) showed a higher interfacial dipole (Δ) value and electron mobility than its PDI counterpart ( PDI‐PZ ), affording solar cells with high efficiency. The power of PDI‐PZ and C₆₀‐PZ to improve electron injection and extraction processes when positioned between metal electrodes and organic semiconductors highlights their promise to overcome energy barriers at the hard‐soft materials interface of organic electronics.     

Crochelins: Siderophores with an Unprecedented Iron‐Chelating Moiety from the Nitrogen‐Fixing Bacterium Azotobacter chroococcum

Microbes use siderophores to access essential iron resources in the environment. Over 500 siderophores are known, but they utilize a small set of common moieties to bind iron. Azotobacter chroococcum expresses iron‐rich nitrogenases, with which it reduces N₂. Though an important agricultural inoculant, the structures of its iron‐binding molecules remain unknown. Here, the “chelome” of A. chroococcum is examined using small molecule discovery and bioinformatics. The bacterium produces vibrioferrin and amphibactins as well as a novel family of siderophores, the crochelins. Detailed characterization shows that the most abundant member, crochelin A, binds iron in a hexadentate fashion using a new iron‐chelating γ‐amino acid. Insights into the biosynthesis of crochelins and the mechanism by which iron may be removed upon import of the holo‐siderophore are presented. This work expands the repertoire of iron‐chelating moieties in microbial siderophores.     

The EcoScale as a framework for undergraduate green chemistry teaching and assessment

An upper-year undergraduate practical examination is presented that utilizes the EcoScale (a semi-quantitative tool) and several established mass metrics to assess student understanding of green chemistry principles. This activity focuses on the straightforward preparation of a benzodiazepine via three different catalytic methods, and the analysis of individual experimental data during laboratory time. Students learn about the structure of the EcoScale, apply it as a simplistic life cycle assessment, and critique it as a scientific model. The examination complements more traditional expository and self-design experiments within a synthetic course where green chemistry and sustainability are central themes.     

Hecke correspondences for smooth moduli spaces of sheaves

Publications mathématiques de l'IHÉS - We define functors on the derived category of the moduli space ℳ of stable sheaves on a smooth projective surface (under Assumptions A and...     

Statistical Characterization of the Phytochemical Characteristics of Edible Mushroom Extracts

The antioxidant activity, total phenolic content, and total flavonoid content of 10 edible mushrooms species, including cultivated (Pleurotus ostreatus, Agaricus bisporus white and brown) and wild (P. ostreatus, Macrolepiota procera, Cantharellus cibarius, Russula vesca, Russula alutacea, Boletus edulis and Agaricus campestris), were determined. The extraction was performed using water and 50% water–ethanol and the caps and stipe were investigated separately. Water was the most appropriate solvent for phenolic compounds regardless of the sample. In contrast, the presence of ethanol in the solvent increased the extraction of flavonoids for cultivated P. ostreatus (caps and stipe), and wild R. alutacea, R. vesca, A. campestris, P. ostreatus (only caps) and C. cibarius, M. procera (only stipe). Significant differences between the antioxidant activities of the samples were registered in relationship with the different solvents. The antioxidant activity of water extract of dried A. bisporus brown (cultivated) showed the strongest 1,1-diphenyl-2-picrylhydrazyl radicals-scavenging assay (88.64%), while the B. edulis hydroalcoholic extract contained 74.93%. A detailed investigation into the functional group of phenolics and other organic compounds responsible with the antioxidant activity has been performed using Fourier transform infrared spectroscopy. The infrared spectra showed that the solvent-type directly influences the extraction process and, hence, the antioxidant activity. The present study contributes to information concerning mushrooms as sources of biologically active compounds. To investigate the correlations between phytochemical characteristics (i.e., phenolics, flavonoids and antioxidant activity) closely related to nature of solvents, the statistical analysis was performed.     

Two-Dimensional Liquid Chromatography (2D-LC) in Pharmaceutical Analysis: Applications Beyond Increasing Peak Capacity

One-dimensional liquid chromatography (1D-LC) is not always capable of efficiently separating complex samples. This drawback is not solely due to the lack of column efficiency, but is mainly due to insufficient selectivity and the need to separate the analytes of interest with orthogonal retention mechanisms. In this regard, two-dimensional liquid chromatography (2D-LC) is currently attracting much interest for its markedly higher resolving power compared to one-dimensional separation. In this work, three applications of 2D-LC from the pharmaceutical industry are presented with the goal not only to increase peak capacity, but also to support investigations. In the first application, the retention times of peaks of interest are matched under different mobile phase conditions for the purpose of transferring the method from a mass spectrometry (MS) incompatible buffer to an MS compatible buffer. The second application includes developing a method for simultaneous detection and quantitation of degradants and aggregates in a biologics and small molecule combination product. The third application supports method development by confirming the purity of separated peaks using orthogonal separation conditions in the first and second dimensions and to investigate mass balance issues where some peaks are expected to elute in the solvent front.     

Bifurcations of Poiseuille flow between parallel plates: Three-dimensional solutions with large spanwise wavelength

The spatial dynamics approach is applied to the analysis of bifurcations of the three-dimensional Poiseuille flow between parallel plates. In contrast to the classical studies, we impose time periodicity as well as spatial periodicity with period 2/ in the streamwise direction. However, we make no assumptions on the behavior in the spanwise direction, except the uniform closeness of the bifurcating solution to the basic flow. In an abstract setting it is shown how the dimension of the critical eigenspace of the spatial dynamics analysis can be uniquely determined from the classical linear stability problem. For the three-dimensional Poiseuille problem we are able to find all relevant coefficients from the analysis of the purely two-dimensional problem. Moreover, we are able to analyze precisely the influence of a spanwise pressure gradient and the associated spanwise mass flux. The study of the reduced problem shows that there are two different kinds of solutions (spirals and ribbons) which are 2p/ periodic in the spanwise direction, as in the Couette-Taylor problem, and both of them bifurcate in the same direction.     

Titanocene-Catalyzed Reduction of Lactones to Lactols

A convenient method for the conversion of lactones to lactols is described. The hydrosilylation to lactols is carried out via air-stable titanocene difluoride or a titanocene diphenoxide precatalyst using inexpensive polymethylhydrosiloxane (PMHS) as the stoichiometric reductant. These procedures have been demonstrated with a variety of substrates and proceed in good to excellent yield.