Brigitte Wex

New organic semiconductors and their device performance as a function of thiophene orientation

We report a first investigation of two new isomer-pure thieno[f,f′]bis[1]benzothiophenes, i.e.syn and anti with respect to the orientation of the thiophenes along the long axis of the molecule, applied as organic semiconductors in organic field-effect transistors. The field-effect mobility of both regioisomers is substantial and reaches up to 0.12 cm2 V−1 s−1, a value that is at most one order of magnitude lower than the best known organic transistors based on silicon dioxide gate insulators.

Perspective on carbazole-based organic compounds as emitters and hosts in TADF applications

The field of organic light-emitting devices (OLEDs) has undergone a remarkable journey since its discovery by Tang and VanSlyke with an alternation of utilizing fluorescence and phosphorescence as the emitting vehicle. The latest generation of thermally activated delayed fluorescence (TADF) materials harvest triplet excited states back into the singlet manifold. This booming field has yielded a large array of new compounds as both emitters and hosts. This review is limited to TADF emitters utilizing at least one carbazole unit as a donor and organized according to the various acceptor building blocks such as cyanophenyl, pyridine, biphenyls, anthraquinone, phenyl(pyridine-2-yl)methanone, benzophenone, xanthon, sulfones, triazines, benzils, dicyanopyrazines, diazatriphenylene, and others. A survey of carbazole-containing host materials follows. Density functional theory (DFT) has carved out a significant role in allowing the theoretical prediction of ground state properties for materials applied in OLED technology. Time-dependent DFT extends the reach to model excited state properties important to rationalize the light-output in OLED technology. For TADF, two fundamental factors are of interest: significant separation of frontier molecular orbitals and minimal singlet–triplet energy gap (ΔEST). In this review, the utilization of DFT calculations to optimize geometries for the visualization of frontier molecular orbital separation was surveyed to find that the B3LYP/6-31G(d) level of theory is the overwhelmingly used approach. In addition, we review the more in-depth approaches to utilizing DFT and time-dependent DFT (TD-DFT) with optimized percentage Hartree–Fock (OHF) and long-range corrected hybrid functionals, tuning procedures and others in an attempt to best quantify the size of ΔEST as well as the nature of the triplet state as locally excited state (LE) and charge-transfer state (CT).

Chemopreventive effects of wild carrot oil against 7,12-dimethyl benz(a)anthracene-induced squamous cell carcinoma in mice.

Context: Daucus carota L. ssp. carota (Apiacea) is widely distributed throughout the world and has many uses in traditional medicine. Objective: The present study investigates the chemopreventive effects of oil extract of D. carota umbels on 7,12-dimethyl benz(a)anthracene (DMBA)-induced skin cancer in mice. Materials and methods: D. carota oil extract (DCOE) was prepared by extracting the dried umbels with 50:50 acetone:methanol. Skin papilloma were initiated by DMBA and promoted by 12-O-tetradecanoyl phorobol-13-acetate (TPA). The extract was administered to animals via gavage (0.02 mL of 100% oil), intraperitoneal (0.3 mL of 2% oil), and topical (0.2 mL of 5, 50, and 100% oil) routes for 20 weeks. Tumor appearance, incidence, yield, and volume were compared with those of a non-treated control group. Results: Topical 100% treatment delayed tumor appearance, and inhibited tumor incidence and yield by 40 and 89%, respectively. Topical 50% treatment inhibited tumor incidence and yield by 30 and 83%, respectively, whereas the 5% treatment inhibited tumor yield by 36%. Tumor volume was decreased by 99, 91, and 70% following topical treatments with 100, 50, and 5% oil, respectively. Intraperitoneal treatment inhibited tumor yield by 43%, and decreased tumor volume by 85%, whereas gavage treatment showed minimal effects on both. Intraperitoneal and topical treatment decreased infiltration and hyperplasia with an increase in the level of hyperkeratosis. Conclusion: These findings demonstrate that DCOE has remarkable antitumor activity against DMBA-induced skin cancer compared with non-treated animals paving the ground for further investigations.

π–π-Stacking and nitro–π-stacking interactions of 1-(4-nitro­phenyl)-4-phenyl-2,4-bis­(phenyl­ethynyl)­buta­diene

The first observed side product, C32H21NO2, in the Sonogashira coupling reaction is reported. The molecular packing shows a high degree of π-stacking interactions in the solid state.

Photocyclization of a naphthyl substituted Y-enyne

Y-enyne 1 undergoes electrocyclic ring closure, via a cumulene intermediate 2, to photoproduct 3 upon irradiation at 350 nm in the presence/absence of air. In non-polar solvents, a [1,5] H-shift affords the photoproduct. In MeOX (X=H/D), protonation/deuteration of the central allenic carbon in 2 occurs. The X-ray structure of 3, the photoproduct upon irradiation of 1 in benzene, is reported.

Structural concept for fluorinated Y-enynes with solvatochromic properties1This paper is dedicated to Professor Dr J. W. Neckers on the occasion of his 100th birthday.

An approach to the development of fluorescent probes to follow polymerizations in situ using fluorinated cross-conjugated enediynes (Y-enynes) is reported. Different substitution patterns in the Y-enynes result in distinct solvatochromic behavior. beta,beta-Bis(phenylethynyl)pentafluorostyrene 7, which bears no donor substituents and only fluorine at the styrene moiety, shows no solvatochromism. Donor substituted beta,beta-bis(3,4,5-trimethoxyphenylethynyl)pentafluorostyrene 8 and beta,beta-bis(4-butyl-2,3,5,6-tetrafluorophenylethynyl)-3,4,5-trimethoxystyrene 9 exhibit solvatochromism upon change of solvent polarity. Y-enyne 8 showed the largest solvatochromic shift (94 nm bathochromic shift) upon changing solvent from cyclohexane to acetonitrile. A smaller solvatochromic response (44 nm bathochromic shift) was observed for 9. Lippert-Mataga treatment of 8 and 9 yields slopes of -10,800 and -6,400 cm(-1), respectively. This corresponds to a change in dipole moment of 9.6 and 6.9 D, respectively. The solvatochromic behavior in 8 and 9 supports the formation of an intramolecular charge transfer (ICT) state. The low fluorescence quantum yields are caused by competitive double bond rotation. The fluorescence decay time of 9 decreases in methyltetrahydrofuran from 2.1 ns at 77 K to 0.11 ns at 200 K. Efficient single bond rotation in 9 was frozen at -50 degrees C in a configuration in which the trimethoxyphenyl ring is perpendicular to the fluorinated rings. 7-9 are photostable compounds. The X-ray structure of 7 shows it is not planar and that its conjugation is distorted. Y-enyne 7 stacks in the solid state showing coulombic, actetylene-arene, and fluorine-pi interactions.

Comparative proteomic analysis of a Candida albicans DSE1 mutant under filamentous and non-filamentous conditions

Candida albicans is a common opportunistic pathogen that causes a variety of diseases in immunocompromised hosts. In a pathogen, cell wall proteins are important virulence factors. We previously characterized Dse1 as a cell wall protein necessary for virulence and resistance to cell surface‐disrupting agents, such as Calcofluor white, chitin deposition, proper adhesion and biofilm formation. In the absence of decomplexation, our objectives were to investigate differential proteomic expression of a DSE1 mutant strain compared to the wild‐type strain. The strains were grown under filamentous and non‐filamentous conditions. The extracted cell proteome was subjected to tryptic digest, followed by generation of peptide profiles using MALDI–TOF MS. Generated peptide profiles were analysed and unique peaks for each strain and growth condition mined against a Candida database, allowing protein identification. The DSE1 mutant was shown to lack the chitin biosynthesis protein Chs5, explaining the previously observed decrease in chitin biosynthesis. The wild‐type strain expressed Pra1, involved in pH response and zinc acquisition, Atg15, a lipase involved in virulence, and Sod1, required for oxidative stress tolerance, in addition to proteins involved in protein biosynthesis, explaining the increase in total protein content observed compared to the mutants strain. The mutant, on the other hand, expressed glucoamylase 1, a cell wall glycoprotein involved in carbohydrate metabolism cell wall degradation and biofilm formation. As such, MALDI–TOF MS is a reliable technique in identifying mutant‐specific protein expression in C. albicans. Copyright

Proteomic analysis of a Candida albicans pir32 null strain reveals proteins involved in adhesion, filamentation and virulence

We have previously characterized Pir32, a Candia albicans cell wall protein that we found to be involved in filamentation, virulence, chitin deposition, and resistance to oxidative stress. Other than defining the cell shape, the cell wall is critical for the interaction with the surrounding environment and the point of contact and interaction with the host surface. In this study, we applied tandem mass spectrometry combined with bioinformatics to investigate cell wall proteome changes in a pir32 null strain. A total of 16 and 25 proteins were identified exclusively in the null mutant strains grown under non-filamentous and filamentous conditions. These proteins included members of the PGA family with various functions, lipase and the protease involved in virulence, superoxide dismutases required for resisting oxidative stress, alongside proteins required for cell wall remodeling and synthesis such as Ssr1, Xog1, Dfg5 and Dcw1. In addition proteins needed for filamentation like Cdc42, Ssu81 and Ucf1, and other virulence proteins such as Als3, Rbt5, and Csa2 were also detected. The detection of these proteins in the mutant and their lack of detection in the wild type can explain the differential phenotypes previously observed.

Proteomic analysis of a Candida albicans pga1 Null Strain

Graphical abstract

Tandem Mass Spectrometric Cell Wall Proteome Profiling of a Candida albicans hwp2 Mutant Strain

BACKGROUND Candida albicans is present as part of the normal gut flora and detected in the oral cavities and GI tracts of around fifty percent of adults. Benign colonization can turn pathogenic causing a variety of mild to severe infections. In a pathogen, the cell wall and cell surface proteins are major antigenic determinants and drug targets as they are the primary structures that contact the host. Cell surface proteins perform a variety of functions necessary for virulence such as adhesion, host degradation, resistance to oxidative stress, and drug resistance. We have previously characterized Hwp2, a C. albicans cell wall adhesin shown to play a major role in the cell wall architecture and function as hwp2 mutants were deficient in chitin deposition, filamentation, adhesion and invasive growth, virulence, and resistance to oxidative stress. OBJECTIVE/METHOD Here, we utilized tandem mass spectrometry coupled with a bioinformatics approach to differentially profile the cell wall proteome of a wild-type strain compared to an hwp2 null mutant to determine key differentially expressed proteins. RESULT Many proteins identified exclusively in the wild-type go a long way in explaining the abovementioned phenotypes. These include virulence factors such as members of the SAP family including Sap4, Sap5, and Sap10, as well as several lipases involved in host degradation. We also identified members of the PGA family of proteins Pga28, Pga32, Pga41 and Pga50, which function in adhesion, Cht2 a chitinase involved in chitin remodeling, and several proteins that function in promoting filamentation such as Phr1, Mts1, and Rbr1.