Chemical Antibody Mimics Inhibit Cadherin-Mediated Cell–Cell Adhesion: A Promising Strategy for Cancer Therapy

One of the most promising strategies to treat cancer is the use of therapeutic antibodies that disrupt cell–cell adhesion mediated by dysregulated cadherins. The principal site where cell–cell adhesion occurs encompasses Trp2 found at the N-terminal region of the protein. Herein, we employed the naturally exposed highly conserved peptide Asp1-Trp2-Val3-Ile4-Pro5-Pro6-Ile7, as epitope to prepare molecularly imprinted polymer nanoparticles (MIP-NPs) to recognize cadherins. Since MIP-NPs target the site responsible for adhesion, they were more potent than commercially available therapeutic antibodies for inhibiting cell–cell adhesion in cell aggregation assays, and for completely disrupting three-dimensional tumor spheroids as well as inhibiting invasion of HeLa cells. These biocompatible supramolecular anti-adhesives may potentially be used as immunotherapeutic or sensitizing agents to enhance antitumor effects of chemotherapy.     

Plasma-Assisted ALD of Highly Conductive HfNx: On the Effect of Energetic Ions on Film Microstructure

Plasma Chemistry and Plasma Processing - In this work, we report on the atomic layer deposition (ALD) of HfNx thin films by employing CpHf(NMe2)3 as the Hf(IV) precursor and Ar–H2 plasma in...     

pH Tuning of Water-Soluble Arylazopyrazole Photoswitches

Arylazopyrazoles are an emerging class of photoswitches with redshifted switching wavelength, high photostationary states, long thermal half-lives and facile synthetic access. Understanding pathways for a simple modulation of the thermal half-lives, while keeping other parameters of interest constant, is an important aspect for out-of-equilibrium systems design and applications. Here, it is demonstrated that the thermal half-life of a water-soluble PEG-tethered arylazo-bis(o-methylated)pyrazole (AAP) can be tuned by more than five orders of magnitude using simple pH adjustment, which is beyond the tunability of azobenzenes. The mechanism of thermal relaxation is investigated by thorough spectroscopic analyses and density functional theory (DFT) calculations. Finally, the concepts of a tunable half-life are transferred from the molecular scale to the material scale. Based on the photochromic characteristics of E- and Z-AAP, transient information storage is showcased in form of light-written patterns inside films cast from different pH, which in turn leads to different times of storage. With respect to prospective precisely tunable materials and time-programmed out-of-equilibrium systems, an externally tunable half-life is likely advantageous over changing the entire system by the replacement of the photoswitch.     

Trifluoromethylation of [AuF3(SIMes)]: Preparation and Characterization of [Au(CF3)xF3−x(SIMes)] (x=1–3) Complexes

Trifluoromethylation of [AuF₃(SIMes)] with the Ruppert–Prakash reagent TMSCF₃ in the presence of CsF yields the product series [Au(CF₃)_xF_3−x(SIMes)] (x=1–3). The degree of trifluoromethylation is solvent dependent and the ratio of the species can be controlled by varying the stoichiometry of the reaction, as evidenced from the ¹⁹F NMR spectra of the corresponding reaction mixtures. The molecular structures in the solid state of trans-[Au(CF₃)F₂(SIMes)] and [Au(CF₃)₃(SIMes)] are presented, together with a selective route for the synthesis of the latter complex. Correlation of the calculated SIMes affinity with the carbene carbon chemical shift in the ¹³C NMR spectrum reveals that trans-[Au(CF₃)F₂(SIMes)] and [Au(CF₃)₃(SIMes)] nicely follow the trend in Lewis acidities of related organo gold(III) complexes. Furthermore, a new correlation between the Au−C_carbene bond length of the molecular structure in the solid state and the chemical shift of the carbene carbon in the ¹³C NMR spectrum is presented.     

The 1:1 glycine zwitterion-water complex: An ab initio electronic structure study

More than a dozen stationary points on the potential energy surface for the 1:1 glycine zwitterion—water complex have been investigated at Hartree-Fock or MP2 levels of theory with basis sets ranging from split valence (4-31G) to split valence plus polarization and diffuse function (6–31 + + G**) quality. Only one true minimum (GLYZWM, C₁ symmetry) could be located on the potential energy surface. GLYZWM features a bridged water molecule acting as both a hydrogen bond acceptor and donor with the NH₃⁻ and CO₂⁻ units of the glycine zwitterion. The total hydrogen bond energy in GLYZWM is computed as 16 kcal/mol (MP2/6–31 ++ G** // 6–31 ++ G**, including corrections for basis set superpositions errors). The computed vibrational frequencies and normal mode forms of the GLYZWM complex resemble in many cases experimental assignments made for the glycine zwitterion in bulk water on the basis of Raman spectroscopy. © 1996 by John Wiley & Sons, Inc.     

GpdA-promoter-controlled production of glucose oxidase by recombinant aspergillus niger using nonglucose carbon sources

The gpdA-promoter-controlled exocellular production of glucose oxidase (GOD) by recombinant Aspergillus niger NRRL-3 (GOD3-18) during growth on glucose and nonglucose carbon sources was investigated. Screening of various carbon substrates in shake-flask cultures revealed that exocellular GOD activities were not only obtained on glucose but also during growth on mannose, fructose, and xylose. The performance of A. niger NRRL-3 (GOD3-18) using glucose, fructose, or xylose as carbon substrate was compared in more detail in bioreactor cultures. These studies revealed that gpdA-promoter-controlled GOD synthesis was strictly coupled to cell growth. The gpdA-promoter was most active during growth on glucose. However, the unfavorable rapid GOD-catalyzed transformation of glucose into gluconic acid, a carbon source not supporting further cell growth and GOD production, resulted in low biomass yields and, therefore, reduced the advantageous properties of glucose. The total (endo- and exocellular) specific GOD activities were lowest when growth occurred on fructose (only a third of the activity that was obtained on glucose), whereas utilization of xylose resulted in total specific GOD activities nearly as high as reached during growth on glucose. Also, the portion of GOD excreted into the culture fluid reached similar high levels (≅ 90%) by using either glucose or xylose as substrate, whereas growth on fructose resulted in a more pelleted morphology with more than half the total GOD activity retained in the fungal biomass. Finally, growth on xylose resulted in the highest biomass yield and, consequently, the highest total volumetric GOD activity. These results show that xylose is the most favorable carbon substrate for gpdA-promoter-controlled production of exocellular GOD.     

Recycling of Primary Lithium Batteries Production Residues

Production waste of primary lithium batteries constitutes a considerable secondary lithium feedstock. Although the recycling of lithium batteries is a widely studied field of research, the metallic residues of non-rechargeable lithium battery production are disposed of as waste without further recycling. The risks of handling metallic Li on a large scale typically prevent the metal from being recycled. A way out of this situation is to handle Li in an aqueous solution, from where it can be isolated as Li₂CO₃. However, the challenge in hydrometallurgical treatment lies in the high energy release during dissolution and generation of H₂. To reduce these process-related risks, the Li sheet metal punching residues underwent oxidative thermal treatment from 300 to 400 °C prior to dissolution in water. Converting Li metal to Li₂O in this initial process step results in an energy release reduction of ∼70 %. The optimal oxidation conditions have been determined by experimental design varying three factors: temperature, Li metal sheet thickness, and residence time. With 96.9±2.6 % almost the entire Li amount is converted to Li₂O, after 2.5 h treatment at 400 °C for a Li sheet thickness of 1.99 mm. Final precipitation with CO₂ yields 85.5±3.0 % Li₂CO₃. Using pure Li sheets, the product Li₂CO₃ is obtained in battery-grade quality (>99.5 %). Non-precipitated Li is recirculated into the process on the stage of dissolving Li₂O, thus avoiding loss of material.     

Novel Methods to Manipulate Autolysis in Sparkling Wine: Effects on Yeast

Sparkling wine made by the traditional method (Méthode Traditionelle) develops a distinct and desirable flavour and aroma profile attributed to proteolytic processes during prolonged ageing on lees. Microwave, ultrasound and addition of β-glucanase enzymes were applied to accelerate the disruption of Saccharomyces cerevisiae, and added to the tirage solution for secondary fermentation in traditional sparkling winemaking. Scanning electron microscopy and flow cytometry analyses were used to observe and describe yeast whole-cell anatomy, and cell integrity and structure via propidium iodide (PI) permeability after 6-, 12- and 18-months post-tirage. Treatments applied produced features on lees that were distinct from that of the untreated control yeast. Whilst control yeast displayed budding cells (growth features) with smooth, cavitated and flat external cell appearances; microwave treated yeast cells exhibited modifications like ‘doughnut’ shapes immediately after treatment (time 0). Similar ‘doughnut’-shaped and ‘pitted/porous’ cell features were observed on progressively older lees from the control. Flow cytometry was used to discriminate yeast populations; features consistent with cell disruption were observed in the microwave, ultrasound and enzyme treatments, as evidenced by up to 4-fold increase in PI signal in the microwave treatment. Forward and side scatter signals reflected changes in size and structure of yeast cells, in all treatments applied. When flow cytometry was interpreted alongside the scanning electron microscopy images, bimodal populations of yeast cells with low and high PI intensities were revealed and distinctive ‘doughnut’-shaped cell features observed in association with the microwave treatment only at tirage, that were not observed until 12 months wine ageing in older lees from the control. This work offers both a rapid approach to visualise alterations to yeast cell surfaces and a better understanding of the mechanisms of yeast lysis. Microwave, ultrasound or β-glucanase enzymes are tools that could potentially initiate the release of yeast cell compounds into wine. Further investigation into the impact of such treatments on the flavour and aroma profiles of the wines through sensory evaluation is warranted.