Die photodynamische Therapie hat die traditionellen Krebsbehandlungsmethoden ergänzt. Trotz ihres Erfolgs sind die klinisch eingesetzten Photosensibilisatoren nicht ideal. Um diese Beschränkungen zu überwinden, werden zunehmend Forschungsbemühungen auf die Einbindung von Metallionen gerichtet. In diesem Kurzaufsatz wird der klinische Status von metallhaltigen Verbindungen als Photosensibilisatoren für die photodynamische Therapie untersucht.

This review highlights advances in the characterization and dynamic rearrangements of σ-bond complexes, most notably alkane and zincane complexes, but also different geometries of silane and borane complexes. We set out a selection of catalytic and stoichiometric examples of the σ-complex assisted metathesis mechanism that are supported by strong experimental and/or computational evidence.

Scanning tunneling microscopy and spectroscopy are powerful techniques to visualize the topographic and electronic structures of metal halide perovskites with atomic-level resolution. These techniques can also be used to reveal the dynamics of surface defects and charge carriers as well as on-surface reactions and optoelectronic properties at the surface and interfaces of perovskite materials.

An interesting aggregation-enhanced sonodynamic activity (AESA) effect was first observed based on the studies of phthalocyanine–artesunate conjugates and common organic sonosensitizers, which arose from boosted ultrasonic cavitation caused by nanostructured aggregates. We believed that the AESA effect in this work could open up a new avenue for the development of efficient sonosensitizers.

The microscopic channel structure–diffusivity relationships in zeolites were unraveled using a combination of single-molecule localization microscopy and uniformly oriented zeolite thin films. New insights into the mechanism of the enhanced diffusion in hierarchical zeolites were obtained.

A two-photon fluorescent probe for CYP3A was developed using a rational design strategy that optimized the key binding domain of the fluorophore. The probe semi-quantitatively detects and images CYP3A activity in various living systems, thereby providing a high-throughput screening system facilitating the evaluation of MBI-associated hepatotoxicity by CYP3A.

Cage 1^P, which selectively encapsulates BPh₄⁻ over a wide range of temperatures, can be quantitatively oxidized to cage 1^PO with more negative enthalpy (ΔH°) and entropy (ΔS°) that releases the captured BPh₄⁻ anions at high temperature but strongly encapsulates BPh₄⁻ at low temperature.

The electrochemical in situ reconstruction of Cu₂P₂O₇ during CO₂ electroreduction generates highly porous Cu with abundant defects and low-coordinated sites, which facilitate CO adsorption with bridge and atop configurations, thus resulting in a high-rate production of C₂₊ fuels and chemicals.

A series of bright NIR-II brush macromolecular fluorophores (FBP) with high renal-clearance efficiency and long-blood circulation time has been developed. These achieve real-time in vivo NIR-II imaging of renal ischemia-reperfusion injury, tumor passive targeted imaging and renal cell carcinoma active targeted imaging with higher signal-to-noise ratio and extended retention time.

A near-infrared photoacoustic (PA) probe Cypate-CBT was designed for specific imaging and real-time tracking of cathespin B (CTSB) activity in CTSB-overexpressing cells and tumors. After Cypate-CBT entered into CTSB-overexpressing cells, it underwent glutathione reduction and CTSB cleavage to generate cypate nanoparticles Cypate-CBT-NPs, which enhanced both the intensity and retention time of the PA signal in tumor sites.

A series of highly potent dual-mode RIPK1 inhibitors occupying both the allosteric and the ATP binding pockets were developed, exemplified by compound 21 (ZB-R-55), which is about 10-fold more potent than GSK2982772, and exhibits excellent kinase selectivity, good oral pharmacokinetics and good therapeutic effects in the LPS-induced sepsis model.

The orienting of an organic semiconductor, a heptamer of poly(p-phenylene vinylene) (HPV), into DNA 3D arrays was achieved by rational design. Addressed with covalent bonds in a DNA tensegrity triangle motif, the quasi-one-dimensional molecules were well-aligned inside the crystalline lattices, as indicated by polarized fluorescent emission. This experiment demonstrated a simple approach to constructing photonic crystals with DNA-templated band-gap materials.

Phthalocyanines are polymerized via a solid ionothermal Scholl reaction in the presence of carbon nanotubes, resulting in an ultrathin conjugated microporous polymer sheath containing single-atom CoN₄ as catalytic sites and H₂Pc units as proton/electron donors, both of which interplay to enhance the electrocatalytic reduction of CO₂ to CO.

A hydrophobic cavity of chiral spherical micelles was used as the chiral space to encapsulate hydrophobic emitters and endow them with circularly polarized luminescence (CPL) properties in the aqueous phase. Particularly, through breaking the “C=N” bonds of Nile Red molecules, we have observed white CPL emission.

The clinically important tricyclic prostaglandin D₂ metabolite (PGDM) methyl ester was synthesized in eight steps from a readily available known compound. The synthesis features Z-selective cross-metathesis to form the challenging Z β,γ-unsaturated ester, palladium-catalyzed carbonylative spirolactonization to build the oxaspirolactone moiety, and nickel-catalyzed Ueno–Stork-type dicarbofunctionalization to form two key C−C bonds and stereocenters.

Die Sortase-vermittelte Ligation (SML) von mehreren Peptidfragmenten wird durch Umschalten der Ligationsstelle ermöglicht. Ein aktives Sortiermotiv, welches standardmäßig in das Ligationsprodukt eingebaut ist, wird von einem aktiven in einen inaktiven Zustand überführt, während ein latentes Nukleophil im Ligationsprodukt für SML aktiviert wird. Wiederholte Zyklen von SML und das Umschalten von Ligationsstellen ermöglichen die Zusammenfügung mehrerer Fragmente mit Wildtyp-Sortase.

Eine effiziente Fragmentverschmelzungs- und -wachstumsstrategie mit einfacher Chemie führte zu einem fragmentartigen Inhibitor des Virulenzaktors LasB aus Pseudomonas aeruginosa mit einer 12-fachen Aktivitätssteigerung. Unsere optimierte Verbindung zeigt verbesserte in vivo Wirksamkeit, was die Bedeutung der Nutzung alternativer Bindungsmodi für erfolgreiche Fragmentverschmelzung hervorhebt. Die Abbildung wurde mit dem Programm BioRender (www.biorender.com) kreiert.

Die kooperative katalytische Rolle von Natrium- und Silberatomen bei der Steuerung der Oberflächenpolymerisation von Hexaazatriphenylenmolekülen auf Ag(111) wird demonstriert. Durch die Kombination von hochauflösender Rastersondenmikroskopie mit Dichtefunktionaltheorie-Berechnungen wird aufgeklärt, wie komplexe Oberflächenprozesse durch das Hinzufügen atomarer Spezies, die für die Katalyse spezifischer Reaktionsschritte verantwortlich sind, ermöglicht werden können.

The generation of permeable porous-cage nanospaces in solution by a highly charged cationic [Pd₆(RuL₃)₈]²⁸⁺ cage for multirole and multi-way supramolecular catalysis is reported.

Complementary biochemical methods and molecular modeling reveal how NPY and its natural analogues bind to the Y₅ GPCR, filling in the gap in the knowledge of the Y multiligand/multireceptor system. This provides the first base for the rational design of selective Y₅R ligands with therapeutic potential.

A metallacycle-based supramolecular photosensitizer (1⊃2) for in vivo image-guided photodynamic inactivation of bacteria is reported. Through host-guest interaction, the assembly 1⊃2, with improved fluorescence signals and ROS production capabilities, is employed for in vivo fluorescence tracking as well as accurate image-guided treatment of S. aureus infection without noticable side effects.

The two-electron reduced, luminescent forms of perylene diimides can be employed for thermodynamically challenging photoredox reactions in aqueous and in organic solution.

Whole-cell E. coli platform enables directed evolution campaigns with ArMs containing an abiotic Ir-porphyrin cofactor involving the generation of more than 4000 mutants to develop an enantioselective insertion of a simple acyclic carbene from a diazo ester into the N−H bond of N-methyl aniline that has formed product with poor enantioselectivity when catalyzed by prior enzyme systems.

Faujasite (FAU) zeolites (with Si/Al ratio of ca. 1.7) undergo mild dealumination at moderate ion exchange conditions (0.01 to 0.6 M of NH₄NO₃ solutions) resulting in protons circumscribed by sodalite cages becoming accessible for reaction. The ratio of protons in sodalite cages (H_SOD) to supercages (H_SUP) can be manipulated by adjusting ammonium concentrations used in ion exchange.

Photoredox catalysis has emerged as a powerful approach for site-selective peptide functionalization. Herein, we report a highly N-termini-specific method to rapidly access itaconated peptide derivatives under mild photoredox conditions. Distinct from conventional methods that rely on residue nucleophilicity, this method proceeds through a highly reactive carbamoyl radical intermediate to achieve excellent selectivity. Itaconated peptides can be further functionalized to access peptide-protein conjugates.

A chemoselective electrooxidative heterocoupling of two different enamines is reported for the synthesis of unsymmetrically substituted NH-pyrroles. A „magic effect“ of the additive trifluoroethanol is utilized to achieve the desired chemoselectivity by tuning the oxidation potentials and controlling the activation energy of the rate-determining step.

The solution phase structure of five bimetallic Cu^I/Ru^II/Os^II complexes was revealed by high-energy X-ray scattering and pair distribution function analysis (HEXS/PDF). Assisted by computational simulation, conformational differences of the complexes in the solution and solid states were identified with sub-Ångström resolution.

Tunable and hydrolytically stable electrophiles are reported for the chemo-selective labeling of lysine with mass sensitive probes. These tunable amine-reactive electrophiles (TAREs) were used to label proteins in various subcellular compartments inside cells and for global identification of lysine in the human proteome.

A family of ¹⁸O₂-phosphoramidites facilitates synthetic access on gram-scale to various isotopically pure ¹⁸O-labelled phosphate products, like nucleotides, inositol phosphates, polyphosphates, and DNA. The utility of these ¹⁸O-natural products is underlined in the assignment of various metabolites from biological matrices using capillary electrophoresis electrospray ionisation triple quadrupole mass spectrometry.

A short and flexible total synthesis of antifungal and antiparasitic sphingofungins A–D and congeners was developed by combining a versatile decarboxylative coupling reaction and a cross metathesis protocol.

A photocatalytic method for the synthesis of amides and peptides is reported. Synergistic cooperation between a cobaloxime and a photoredox catalyst removes the elements of H₂O through the use of PPh₃ as a gentle organic reductant. The deoxygenative method is compatible with gram-scale peptide synthesis and applicable to peptide fragment condensation and SPPS, which may find applications in both organic synthesis and pharmaceutical production.

Nano-impact electrochemistry revealed an anomalously high capacitance for Pt nanoparticles and to a lower extent for Au nanoparticles at potentials more negative than their potential of zero charge. MD calculations showed that the strong interaction of metal with water molecules leads to water chemisorption and accumulation of ions in the Helmholtz layer beyond expectation, resulting in a higher interface charge storage ability.

Hot-electron transfer at Au–graphene interfaces has been investigated in situ with atomic layer accuracy, and it is shown that hot electrons can be injected from plasmonic Au nanoparticles to graphene and penetrate up to four layers of graphene.

A modular synthesis of trimetallo-substituted polyanions enables the preparation of designer catalysts. Here this approach was used to prepare electrocatalysts for the selective reduction of CO₂ to CO using a tri-copper-substituted polyanion. In contrast, Fe–Ni-substituted polyanions preferably catalyzed the oxidation of CO to CO₂, showing a reactivity profile reminiscent of the reactivity of Fe–Ni-based carbon monoxide dehydrogenase enzymes.

Low concentration CO₂ is adsorbed in zinc containing CHA-type zeolites with a high capacity of 0.67 mmol CO₂/g-zeolite. The materials exhibit higher CO₂ capacity, faster kinetics, lower desorption energy than low-silica 13X zeolites. Zeolite framework and the states and locations of zinc ions play crucial roles in the adsorption performance.

We describe Apotracker Red as a single fluorescent activatable probe for robust quantification of cancer cell death in fluorescence-based assays and in vivo using multiphoton intravital imaging in mouse models of breast cancer.

Linearly B←N Lewis pair extended anthracenes are prepared by highly regioselective N-directed electrophilic borylation. Their LUMOs are higher in energy and their HOMO–LUMO gaps are significantly larger compared to those of the respective laterally functionalized species. Photooxygenation studies reveal effective singlet oxygen sensitization with a largely reduced tendency for self-sensitized endoperoxide formation.

A molecularly engineered cyclobutane-based hole-transporting material synthesised using simple and green-chemistry-inspired protocols achieves an impressive efficiency of 21 % in perovskite solar cells and over 19 % in perovskite solar module with an active area of 30.24 cm².

Based on strained oligoparaphenylene loops and a flexible cyclooctatetrathiophene moiety, a fully conjugated bis-macrocycle is efficiently constructed, and possesses rigid and guest-adaptive cavities. Its peanut-like 1:2 host–guest complexes with C₆₀ or C₇₀ have been isolated and characterized, respectively.

We describe the nanostructural and conformational versatility of the biologically active peptide PEP-1, which self-assembles into up to six different aggregate morphologies and forms up to four different secondary structures in a controlled manner depending on pH, concentration, and temperature.

Combined scanning tunneling microscopy and X-ray photoelectron spectroscopy studies provide evidence for thermally activated abiotic formation of amide bonds between adsorbed precursors through direct carboxyl–amine coupling under ultrahigh-vacuum conditions by means of on-surface synthesis.

For acetone to propane electrohydrogenation, we unveiled how the local environmental pH determines the adsorption configuration of acetone, and further, the efficiency of the catalytic process. Moreover, it is showed that the reaction efficiency of the reaction can be improved by simply adjusting local pH instead of complex catalyst engineering.

The steric demand exerted by the peripheral side chains of the reported azobenzene dyads impedes their hierarchical self-assembly from nanotoroids into nanotubes. In contrast, they organize into 2D porous networks on substrate upon solution processing. Photoisomerization of azobenzene moieties allows efficient dissociation/reorganization of nanotoroids in solution, demonstrating their potential as photoresponsive 2D porous nanosheets.

Various diammonium spacer cations are used to construct 2D/3D perovskite. The mechanism of molecular configuration-induced regulation of crystal orientation and carrier dynamics is investigated. 2D/3D perovskite solar cells based on 2,2′-(ethylenedioxy)bis(ethylamine) achieve device efficiency of 22.68 % and excellent moisture stability, retaining 82 % of initial efficiency after aging at 50±5 % relative humidity for 1560 h.

A kind of functionalizing exfoliation agent has been selected to simultaneously modify and exfoliate bulk COFs into functional nanosheets and the obtained materials can be applied in highly selective CO₂ electroreduction into CH₄.

A distannyne supported by a pincer ligand featuring pendant CH₂NⁱPr₂ arms is capable of reversibly activating E−H bonds at one or both of the tin centres through dissociation of the hemi-labile N–Sn donor/acceptor interactions. This chemistry can be exploited to sequentially (and reversibly) assemble mixed-valence chains of tin atoms of the type ArSn{Sn(Ar)H}_nSnAr (n=1,2).

An atom-economic polymerization of five-membered propylene carbonate (PC) for preparation of polyester and polycarbonate simultaneously is reported. The key premise of our strategy is the careful elaboration of the mechanism of direct ring-opening polymerization of PC, which emphasizes the importance of the in situ released propylene oxide.

A new complex photonic structure, bridged lamellae, with intriguing color reflections is successfully fabricated through well-controlled co-assembly of lipophilic and amphiphilic bottlebrush block copolymers within shrinking droplets. Self-assembled Janus microspheres with precisely tunable dual light reflections are facilely obtained through the manipulation of the co-assembly at a molecular level.

A universal calibration curve for molecular weight determination is presented. Diffusion coefficients of poly(styrene) and poly(ethylene glycol) standards are measured via diffusion-ordered NMR spectroscopy. These diffusion/molecular weight relationships are calibrated to be solvent-independent. This universal calibration creates a novel platform wherein molecular weights of unknown polymers can be found using the universal calibration curve independent of what solvent is used.

Dibenzo[hi,st]ovalene-based covalent organic frameworks form 2D ABC stacking sp² carbon lattices with robust olefin linkage. The resulting 2D unique structure exhibits high photoconductivity, charge-carrier mobility and photocatalytic activity in hydroxylation attributed to the narrow-energy-gap nanographene cores as active sites.

In dieser Arbeit wird eine photokatalysierte Ringerweiterung für eine C₂-Homologisierung von cyclischen Carbonylverbindungen zu mittelgroßen Ringsystemen vorgestellt. Diese gelingt mit Hilfe des Katalysators fac-[Ir(CF₃-pmb)₃] (E_T=73.3 kcal mol⁻¹), der eine selektive Aktivierung der substöchiometrischen Enolspezies ermöglicht. Der Mechanismus wurde durch zeitaufgelöste Spektroskopie untersucht und ermöglicht eine vollständige kinetische Analyse des dynamischen kinetischen Sensibilisierungsszenarios.

Das neutrale homozyklische Silylen 2 wurde ausgehend vom bizyklischen Silicium(I)-Amid J erhalten. Diese Reaktion verläuft über die anionische homoaromatische Ringverbindung 1. Das zweifach-koordinierte Si-Atom in 1 wird durch eine 3-Zentren-2-Elektronen-π-Bindung stabilisiert und das in 2 durch eine allyl-artige π-Elektronendelokalisation. Silylen 2 geht Cycloadditionen mit Alkenen und Alkinen und eine oxidative Addition mit Methanol ein. Die Reaktion mit Ethen führt zu einer trizyklischen Ringspezies.