Dual sequence definition increases the data storage capacity of sequence-defined macromolecules.

Sequence-defined macromolecules offer applications in the field of data storage. Challenges include synthesising precise and pure sequences, reading stored information and increasing data storage capacity. Herein, the synthesis of dual sequence-defined oligomers and their application for data storage is demonstrated.

Cobalt-Catalyzed α-Arylation of Substituted α-Bromo α-Fluoro β-Lactams with Diaryl Zinc Reagents: Generalization to Functionalized Bromo Derivatives.

A cobalt-catalyzed cross-coupling of α-bromo α-fluoro β-lactams with diarylzinc or diallylzinc reagents is herein disclosed. The protocol proved to be general, chemoselective and operationally simple allowing the C4 functionalization of β-lactams. The substrate scope was expanded to α-bromo lactams and amides, α-bromo lactones and esters as well as N- and O-containing heterocycles.

Enhancing the activity of membrane remodeling epsin-peptide by trimerization.

Modulating the structural dynamics of biomembranes by inducing bilayer curvature and lipid packing defects has been highlighted as a practical tool to modify membrane-dependent cellular processes. Previously, we have reported on an amphipathic helical peptide derived from the N-terminal segment (residues 1-18, EpN18) of epsin-1, which can promote membrane remodeling including lipid packing defects in cell membranes. However, a high concentration is required to exhibit a pronounced effect.

Light-controllable dithienylethene-modified cyclic peptides: photoswitching the in vivo toxicity in zebrafish embryos.

This study evaluates the embryotoxicity of dithienylethene-modified peptides upon photoswitching, using 19 analogues based on the β-hairpin scaffold of the natural membranolytic peptide gramicidin S. We established an in vivo assay in two variations (with ex vivo and in situ photoisomerization), using larvae of the model organism and determined the toxicities of the peptides in terms of 50% lethal doses (LD). This study allowed us to: (i) demonstrate the feasibility of evaluating peptide toxicity with larvae at 3-4 days post fertilization, (ii) determine the phototherapeutic safety windows for all peptides, (iii) demonstrate photoswitching of the whole-body toxicity for the dithienylethene-modified peptides in vivo, (iv) re-analyze previous structure-toxicity relationship data, and (v) select promising candidates for potential clinical development.

Author Correction: Marrying chemistry with biology by combining on-chip solution-based combinatorial synthesis and cellular screening.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Supreme activity of gramicidin S against resistant, persistent and biofilm cells of staphylococci and enterococci.

Three promising antibacterial peptides were studied with regard to their ability to inhibit the growth and kill the cells of clinical strains of Staphylococcus aureus, Enterococcus faecalis and Enterococcus faecium. The multifunctional gramicidin S (GS) was the most potent, compared to the membranotropic temporin L (TL), being more effective than the innate-defence regulator IDR-1018 (IDR). These activities, compared across 16 strains as minimal bactericidal and minimal inhibitory concentrations (MIC), are independent of bacterial resistance pattern, phenotype variations and/or biofilm-forming potency.

Planar Chiral [2.2]Paracyclophane-Based Bisoxazoline Ligands and Their Applications in Cu-Mediated N-H Insertion Reaction.

New catalysts for important C-N bond formation are highly sought after. In this work, we demonstrate the synthesis and viability of a new class of planar chiral [2.2]paracyclophane-based bisoxazoline (BOX) ligands for the copper-catalyzed N-H insertion of α-diazocarbonyls into anilines.

Synthesis, Characterization, and Biological Properties of Steroidal Ruthenium(II) and Iridium(III) Complexes Based on the Androst-16-en-3-ol Framework.

A range of novel cyclometalated ruthenium(II) and iridium(III) complexes with a steroidal backbone based on androsterone were synthesized and characterized by NMR spectroscopy and X-ray crystallography. Their cytotoxic properties in RT112 and RT112 cP (cisplatin-resistant) cell lines as well as in MCF7 and somatic fibroblasts were compared with those of the corresponding nonsteroidal complexes and the noncyclometalated pyridyl complexes as well as with cisplatin as reference. All steroidal complexes were more active in RT112 cP cells than cisplatin, whereby the cyclometalated pyridinylphenyl complexes based on showed high cytotoxicity while maintaining low resistant factors of 0.

Highly soluble fluorine containing Cu(i) AlkylPyrPhos TADF complexes.

Luminescent Cu(i) AlkylPyrPhos complexes with a butterfly-shaped CuI core and halogen containing ancillary ligands, with a special focus on fluorine, have been investigated in this study. These complexes show extremely high solubilities and a remarkable (photo)chemical stability in a series of solvents. A tunable emission resulting from thermally activated delayed fluorescence with high quantum yields was determined by luminescence and lifetime investigations in solvents and solids.

Modification of Starch via the Biginelli Multicomponent Reaction.

An efficient and straightforward modification of starch using renewable and commercially available aromatic aldehydes (benzaldehyde, vanillin, and p-anisaldehyde) and urea via the Biginelli multicomponent reaction is reported in this work. First, starch acetoacetate (SAA) with a degree of substitution ranging from 1.4 to 2.

Suzuki Cross-Coupling of [2.2]Paracyclophane Trifluoroborates with Pyridyl and Pyrimidyl Building Blocks.

We report a new Suzuki cross-coupling protocol for high yielding derivatization of [2.2]paracyclophane with pyridyl and pyrimidyl substituents. The [2.

Turn on of sky-blue thermally activated delayed fluorescence and circularly polarized luminescence (CPL) increased torsion by a bulky carbazolophane donor.

The carbazolophane (Czp) donor unit (indolo[2.2]paracyclophane) is introduced to the design pool of donors in thermally activated delayed fluorescence emitters. The increased steric bulk of the annelated donor unit forces an increased torsion between the carbazole and the aryl bridge resulting in a decreased Δ and an enhancement of the thermally activated delayed fluorescence in the triazine-containing emitter .

Facile and Sustainable Synthesis of Erythritol bis(carbonate), a Valuable Monomer for Non-Isocyanate Polyurethanes (NIPUs).

Recently, R. Mülhaupt et al. introduced the first high yielding synthesis of erythritol bis(carbonate) from erythritol with diphenyl carbonate (DPC) as reagent.

Regioselective Functionalization of [2.2]Paracyclophanes: Recent Synthetic Progress and Perspectives.

[2.2]Paracyclophane (PCP) is a prevalent scaffold that is widely utilized in asymmetric synthesis, π-stacked polymers, energy materials, and functional parylene coatings that finds broad applications in bio- and materials science. In the last few years, [2.

Synthesis of Functionalized Azobiphenyl- and Azoterphenyl- Ditopic Linkers: Modular Building Blocks for Photoresponsive Smart Materials.

Modular synthesis of structurally diverse functionalized azobiphenyls and azoterphenyls for the realization of optically switchable materials has been described. The corresponding synthesis of azobiphenyls and azoterphenyls by stepwise Mills/Suzuki-Miyaura cross-coupling reaction, proceeds with high yields and provides facile access to a library of functionalized building blocks. The synthetic methods described herein allow combining several distinct functional groups within a single unit, each intended for a specific task, such as 1) the -N=N- azobenzene core as a photoswitchable moiety, 2) aryls and heteroaryls, functionalized with carboxylic acids or pyridine at its peripheries, as coordinating moieties and 3) varying substitution, size and length of the backbone for adaptability to specific applications.

Marrying chemistry with biology by combining on-chip solution-based combinatorial synthesis and cellular screening.

Drug development often relies on high-throughput cell-based screening of large compound libraries. However, the lack of miniaturized and parallelized methodologies in chemistry as well as strict separation and incompatibility of the synthesis of bioactive compounds from their biological screenings makes this process expensive and inefficient. Here, we demonstrate an on-chip platform that combines solution-based synthesis of compound libraries with high-throughput biological screenings (chemBIOS).

Occurrence, synthesis and applications of natural and designed [3.3.3]propellanes.

Covering: 1978 to 2019 The synthetically challenging [3.3.3]propellane core has caught a lot of attention over the last 50 years.

Rising Up: Hierarchical Metal-Organic Frameworks in Experiments and Simulations.

Controlled synthesis across several length scales, ranging from discrete molecular building blocks to size- and morphology-controlled nanoparticles to 2D sheets and thin films and finally to 3D architectures, is an advanced and highly active research field within both the metal-organic framework (MOF) domain and the overall material science community. Along with synthetic progress, theoretical simulations of MOF structures and properties have shown tremendous progress in both accuracy and system size. Further advancements in the field of hierarchically structured MOF materials will allow the optimization of their performance; however, this optimization requires a deep understanding of the different synthesis and processing techniques and an enhanced implementation of material modeling.

A de novo strategy for predictive crystal engineering to tune excitonic coupling.

In molecular solids, the intense photoluminescence (PL) observed for solvated dye molecules is often suppressed by nonradiative decay processes introduced by excitonic coupling to adjacent chromophores. We have developed a strategy to avoid this undesirable PL quenching by optimizing the chromophore packing. We integrated the photoactive compounds into metal-organic frameworks (MOFs) and tuned the molecular alignment by introducing adjustable "steric control units" (SCUs).

Miniaturized and Automated Synthesis of Biomolecules-Overview and Perspectives.

Chemical synthesis is performed by reacting different chemical building blocks with defined stoichiometry, while meeting additional conditions, such as temperature and reaction time. Such a procedure is especially suited for automation and miniaturization. Life sciences lead the way to synthesizing millions of different oligonucleotides in extremely miniaturized reaction sites, e.

Photoconductivity in Metal-Organic Framework (MOF) Thin Films.

Photoconductivity is a characteristic property of semi-conductors. Herein, we present a photo-conducting crystalline metal-organic framework (MOF) thin film with an on-off photocurrent ratio of two orders of magnitude. These oriented, surface-mounted MOF thin films (SURMOFs), contain porphyrin in the framework backbone and C guests, loaded in the pores using a layer-by-layer process.

Toward Design of Novel Materials for Organic Electronics.

Materials for organic electronics are presently used in prominent applications, such as displays in mobile devices, while being intensely researched for other purposes, such as organic photovoltaics, large-area devices, and thin-film transistors. Many of the challenges to improve and optimize these applications are material related and there is a nearly infinite chemical space that needs to be explored to identify the most suitable material candidates. Established experimental approaches struggle with the size and complexity of this chemical space.

Bridging the Green Gap: Metal-Organic Framework Heteromultilayers Assembled from Porphyrinic Linkers Identified by Using Computational Screening.

In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico.

Design and Applications of Photoresponsive Hydrogels.

Hydrogels are the most relevant biochemical scaffold due to their tunable properties, inherent biocompatibility, and similarity with tissue and cell environments. Over the past decade, hydrogels have developed from static materials to "smart" responsive materials adapting to various stimuli, such as pH, temperature, chemical, electrical, or light. Light stimulation is particularly interesting for many applications because of the capability of contact-free remote manipulation of biomaterial properties and inherent spatial and temporal control.