Toward the development of new photolabile protecting groups that can rapidly release bioactive compounds upon photolysis with visible light

The synthesis and characterization of a new photolabile protecting group (caging group) for carboxylic acids, the 2-(dimethylamino)-5-nitrophenyl (DANP) group, is described. This compound has a major absorption band in the visible wavelength region with a maximum near 400 nm (epsilon400 = 9077 M(-1) cm(-1) at pH 7.4 and 21 degrees C). The caging group is attached through an ester linkage to the carboxyl functionality of beta-alanine, which activates the inhibitory glycine receptor in the mammalian central nervous system. Such caged compounds play an important role in transient kinetic investigations of fast cellular processes. Upon photolysis of DANP-caged beta-alanine, the caging group is released within 5 micros. Quantum yields of 0.03 and 0.002 were obtained in the UV region (308 and 360 nm) and the visible region (450 nm), respectively. Laser-pulse photolysis experiments, using 337 or 360 nm light, were performed with the caged compound equilibrated with HEK 293 cells transiently transfected with cDNA encoding the alpha1 homomeric, wild-type glycine receptor. The experiments demonstrated that neither DANP-caged beta-alanine nor its byproducts inhibit or activate the glycine receptors on the cell surface. Under physiological conditions, the DANP-caged beta-alanine is water-soluble and stable and can be used for transient kinetic measurements.     

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. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties.     

3D-Printed Phenacrylate Decarboxylase Flow Reactors for the Chemoenzymatic Synthesis of 4-Hydroxystilbene

Continuous flow systems for chemical synthesis are becoming a major focus in organic chemistry and there is a growing interest in the integration of biocatalysts due to their high regio- and stereoselectivity. Methods established for 3D bioprinting enable the fast and simple production of agarose-based modules for biocatalytic reactors if thermally stable enzymes are available. We report here on the characterization of four different cofactor-free phenacrylate decarboxylase enzymes suitable for the production of 4-vinylphenol and test their applicability for the encapsulation and direct 3D printing of disk-shaped agarose-based modules that can be used for compartmentalized flow microreactors. Using the most active and stable phenacrylate decarboxylase from Enterobacter spec. in a setup with four parallel reactors and a subsequent palladium(II) acetate-catalysed Heck reaction, 4-hydroxystilbene was synthesized from p-coumaric acid with a total yield of 14.7 % on a milligram scale. We believe that, due to the convenient direct immobilization of any thermostable enzyme and straightforward tuning of the reaction sequence by stacking of modules with different catalytic activities, this simple process will facilitate the establishment and use of cascade reactions and will therefore be of great advantage for many research approaches.     

Polyampholytic Graft Copolymers as Matrix for TiO2/Eosin Y/[Mo3S13]2− Hybrid Materials and Light-Driven Catalysis

An effective strategy to enhance the performance of inorganic semiconductors is moving towards organic-inorganic hybrid materials. Here, we report the design of core–shell hybrid materials based on a TiO₂ core functionalized with a polyampholytic (poly(dehydroalanine)-graft-(n-propyl phosphonic acid acrylamide) shell (PDha-g-PAA@TiO₂). The PDha-g-PAA shell facilitates the efficient immobilization of the photosensitizer Eosin Y (EY) and enables electronic interactions between EY and the TiO₂ core. This resulted in high visible-light-driven H₂ generation. The enhanced light-driven catalytic activity is attributed to the unique core–shell design with the graft copolymer acting as bridge and facilitating electron and proton transfer, thereby also preventing the degradation of EY. Further catalytic enhancement of PDha-g-PAA@TiO₂ was possible by introducing [Mo₃S₁₃]²⁻ cluster anions as hydrogen-evolution cocatalyst. This novel design approach is an example for a multi-component system in which reactivity can in future be independently tuned by selection of the desired molecular or polymeric species.     

Herstellung organischer Dünnstschichten

In this paper we present different experiments describing the fabrication and characterisation of self-assembled monolayers of organothiols and also discuss some of the most important applications of these systems. The reader may practise the fabrication and characterisation of self-assembled monolayers with different endgroups by adsorption of CH₃- and Oh-terminated alkanethiols on copper-coins (1 or 2 Pfenningcoins). Then patterned self-assembled monolayers of CH₃- and OH-terminated alkanethiols are produced by applying the microcontact printing technique. When these gratings are wet with water-e.g. by breathing into the surfaces-the water adsorbs onto the hydrophilic OH-terminated areas but not on the hydrophobic CH₃-terminated regions. Illumination with a laser then produces bright diffraction spots which disappear when the water evaporates. Finally, we briefly discuss applications of the self-assembled ultrathin films as sensor-devices and as substrates for CVD (chemical vapour deposition).     

The Chemistry of Cyborgs—Interfacing Technical Devices with Organisms

The term “cyborg” refers to a cybernetic organism, which characterizes the chimera of a living organism and a machine. Owing to the widespread application of intracorporeal medical devices, cyborgs are no longer exclusively a subject of science fiction novels, but technically they already exist in our society. In this review, we briefly summarize the development of modern prosthetics and the evolution of brain–machine interfaces, and discuss the latest technical developments of implantable devices, in particular, biocompatible integrated electronics and microfluidics used for communication and control of living organisms. Recent examples of animal cyborgs and their relevance to fundamental and applied biomedical research and bioethics in this novel and exciting field at the crossroads of chemistry, biomedicine, and the engineering sciences are presented.     

High-throughput Synthesis of Solution-Processable van der Waals Heterostructures through Electrochemistry

Two-dimensional van der Waals heterostructures (2D vdWHs) have recently gained widespread attention because of their abundant and exotic properties, which open up many new possibilities for next-generation nanoelectronics. However, practical applications remain challenging due to the lack of high-throughput techniques for fabricating high-quality vdWHs. Here, we demonstrate a general electrochemical strategy to prepare solution-processable high-quality vdWHs, in which electrostatic forces drive the stacking of electrochemically exfoliated individual assemblies with intact structures and clean interfaces into vdWHs with strong interlayer interactions. Thanks to the excellent combination of strong light absorption, interfacial charge transfer, and decent charge transport properties in individual layers, thin-film photodetectors based on graphene/In₂Se₃ vdWHs exhibit great promise for near-infrared (NIR) photodetection, owing to a high responsivity (267 mA W⁻¹), fast rise (72 ms) and decay (426 ms) times under NIR illumination. This approach enables various hybrid systems, including graphene/In₂Se₃, graphene/MoS₂ and graphene/MoSe₂ vdWHs, providing a broad avenue for exploring emerging electronic, photonic, and exotic quantum phenomena.