Chemoselective Heterogeneous Hydrogenation of Sulfur Containing Quinolines under Mild Conditions.

Sulfur, alongside oxygen and nitrogen, holds a prominent position as one of the key heteroatoms in nature and medicinal chemistry. Its significance stems from its ability to adopt different oxidation states, rendering it valuable as both a polarity handle and a hydrogen bond donor/acceptor. Nevertheless, the poisonous nature of its free electron pairs makes sulfur containing substrates inaccessible for many catalytic protocols. Strong and (at low temperatures) irreversible chemisorption to the catalyst's surface is in particular detrimental for heterogeneous catalysts, possessing only few catalytically active sites. Herein, we present a novel heterogeneous Ru-S catalyst that tolerates multiple sulfur functionalities, including thioethers, thiophenes, sulfoxides, sulfones, sulfonamides, and sulfoximines, in the hydrogenation of quinolines. The utility of the products was further demonstrated by subsequent diversifications of the sulfur functionalities.

Multi-Stimuli-Responsive Water-Dispersible Magnetite Nanoparticles Using Arylazopyrazole-Modified Polymer Ligands.

In order to design new nanomaterials with improved functionalities, magnetite nanoparticles (MNP) modified with arylazopyrazole (AAP) molecular photoswitches are presented. Water dispersibility is achieved by using poly(acrylic acid) (pAA) as a multidentate ligand, which is modified with AAP by amide coupling. The polymer ligand stabilizes the MNP, allows for E-Z isomerization of the photoswitch, and provides pH responsiveness. Three different AAP are synthesized and attached to pAA via amide coupling giving pAA-AAP with photoswitches substituted statistically along the hydrophilic polymer backbone. MNP are synthesized by coprecipitation and pAA-AAP is introduced as a stabilizing agent in situ. Photoisomerization of pAA-AAP and pAA-AAP@MNP is investigated showing good photostationary states and cyclability. The MNP can be assembled and dispersed reversibly in water either by applying a magnetic field or by a change in pH.

cis-Selective Hydrogenation of Aryl Germanes: A Direct Approach to Access Saturated Carbo- and Heterocyclic Germanes.

A catalytic approach of synthesizing the cis-selective saturated carbo- and heterocyclic germanium compounds (3D framework) is reported via the hydrogenation of readily accessible aromatic germanes (2D framework). Among the numerous catalysts tested, Nishimura's catalyst (Rh2O3/PtO2·H2O) exhibited the best hydrogenation reactivity with an isolated yield of up to 96%. A broad range of substrates including the synthesis of unprecedented saturated heterocyclic germanes was explored. This selective hydrogenation strategy could tolerate several functional groups such as -CF3, -OR, -F, -Bpin, and -SiR3 groups. The synthesized products demonstrated the applications in coupling reactions including the newly developed strategy of aza-Giese-type addition reaction (C-N bond formation) from the saturated cyclic germane product. These versatile motifs can have a substantial value in organic synthesis and medicinal chemistry as they show orthogonal reactivity in coupling reactions while competing with other coupling partners such as boranes or silanes, acquiring a three-dimensional structure with high stability and robustness.

Patterning of Hydrophilic and Hydrophobic Gold and Magnetite Nanoparticles by Dip Pen Nanolithography.

Nanoparticles offer unique physical and chemical properties. Dip pen nanolithography of nanoparticles enables versatile patterning and nanofabrication with potential application in electronics and sensing, but is not well studied yet. Herein, the patterned deposition of various nanoparticles onto unmodified silicon substrates is presented. It is shown that aqueous solutions of hydrophilic citrate and cyclodextrin functionalized gold nanoparticles as well as poly(acrylic) acid decorated magnetite nanoparticles are feasible for writing nanostructures. Both smaller and larger nanoparticles can be patterned. Hydrophobic oleylamine or n-dodecylamine capped gold nanoparticles and oleic acid decorated magnetite nanoparticles are deposited from toluene. Tip loading is carried out by dip-coating, and writing succeeds fast within 0.1 s. Also, coating with longer tip dwell times, at different relative humidity and varying frequency are studied for deposition of nanoparticle clusters. The resulting feature size is between 300 and 1780 nm as determined by scanning electron microscopy. Atomic force microscopy confirms that the heights of the deposited structures correspond to a single or double layer of nanoparticles. Higher writing speeds lead to smaller line thicknesses, offering possibilities to more complex structures. Dip pen nanolithography can hence be used to pattern nanoparticles on silicon substrates independent of the surface chemistry.

Versatile Surface Patterning with Low Molecular Weight Photoswitches.

Surface patterning of functional materials is a key technology in various fields such as microelectronics, optics, and photonics. In micro- and nanofabrication, polymers are frequently employed either as photoreactive or thermoresponsive resists that enable further fabrication steps, or as functional adlayers in electronic and optical devices. In this article, a method is presented for imprint lithography using low molecular weight arylazoisoxazoles photoswitches instead of polymer resists. These photoswitches exhibit a rapid and reversible solid-to-liquid phase transition upon photo-isomerization at room temperature, making them highly suitable for reversible surface functionalization at ambient conditions. Beyond photo-induced imprint lithography with multiple write-and-erase cycles, prospective applications as patterned matrix for nanoparticles and etch resist on gold surfaces are demonstrated.

Mediating Oxidation of Thioethers with Iodine-A Mild and Versatile Pathway to Trigger the Formation of Peptide Hydrogels.

The development of redox-triggerable peptide hydrogels poses fundamental challenges, since the highly specific peptide architectures required inevitably limit the versatility of such materials. A powerful, yet rarely applied approach to bypass those barriers is the application of a mediating redox reaction to gradually decrease the pH during hydrogel formation. We report a versatile strategy to trigger the formation of peptide hydrogels from readily accessible acid-triggerable gelators by generating protons by oxidation of thioethers with triiodide. Adding thiodiglycol as a readily available thioether auxiliary to the basic precursor solution of a peptide gelator efficiently yielded hydrogels after mixing with triiodide, as studied in detail for Nap-FF and demonstrated for other peptides. Furthermore, incorporation of the thioether moiety in the gelator backbone via the amino acid methionine, as shown for the tailormade Nap-FMDM peptide, reduces the number of required additives.

Access to Unexplored 3D Chemical Space: cis-Selective Arene Hydrogenation for the Synthesis of Saturated Cyclic Boronic Acids.

A new class of saturated boron-incorporated cyclic molecules has been synthesized employing an arene-hydrogenation methodology. cis-Selective hydrogenation of easily accessible, and biologically important molecules comprising benzoxaborole, benzoxaborinin, and benzoxaboripin derivatives is reported. Among the various catalysts tested, rhodium cyclic(alkyl)(amino)carbene [Rh-CAAC] (1) pre-catalyst revealed the best hydrogenation activity confirming turnover number up to 1400 with good to high diastereoselectivity. A broad range of functional groups was tolerated including sensitive substituents such as -F, -CF3 , and -silyl groups. The utility of the synthesized products was demonstrated by the recognition of diols and sugars under physiological conditions. These motifs can have a substantial importance in medicinal chemistry as they possess a three-dimensional structure, are highly stable, soluble in water, form hydrogen bonds, and interact with diols and sugars.

Photoresponsive Block Copolymer Nanostructures through Implementation of Arylazopyrazoles.

Responsive nanomaterials that can undergo reversible changes in morphology are interesting for the development of functional materials that interact with and respond to their environment. Amphiphilic block copolymers are well-known for their ability to create a wide range of supramolecular nanostructures in solution. Arylazopyrazoles (AAPs) are versatile molecular photoswitches, which change their configuration and hydrophobicity upon irradiation with UV light (365 nm, Z isomer, less hydrophobic) and green light (520 nm, E isomer, more hydrophobic). In this work, photoswitchable block copolymers containing arylazopyrazole tetraethylene glycol methacrylate (AAPMA) and oligo(ethylene glycol) methacrylate (OEGMA) forming amphiphilic POEGMA-b-PAAPMA with varying block lengths are prepared by RAFT polymerization. The photochemical properties of AAP persist in the polymers. Due to their amphiphilic structure, the polymers self-assemble into supramolecular morphologies in water. Remarkably, photoisomerization results in a reversible change in the self-assembly behavior. Specifically, spherical and cylindrical micelles are observed for POEGMA33-b-PAAPMA47 when illuminated with green or UV light during assembly. Furthermore, the morphology of assembled structures can be reversibly switched by subsequent irradiation with UV and green light.

Spatial and temporal diffusion-control of dynamic multi-domain self-assembled gels.

The dynamic assembly of a pH-responsive low-molecular-weight gelator (LMWG) within the pre-formed matrix of a second LMWG has been achieved via diffusion of an acid from a reservoir cut into the gel. Self-assembly of the acid-triggered LMWG as it converts from micellar aggregates at basic pH into gel nanofibers at lower pH values can be both spatially and temporally controlled. The pH-responsive LMWG has an impact on the stiffness of the pre-formed gel in the domains in which it assembles. When low acid concentrations are used, LMWG assembly is transient - after the initial proton diffusion phase, the pH rises and disassembly occurs as the system equilibrates. Re-application of additional acid as 'fuel' can then re-assemble the LMWG network. Using glucono-δ-lactone (which slowly hydrolyses to gluconic acid) instead of HCl gives slower, more spatially-restricted assembly, and creates longer-lasting pH gradients within the gel. The presence of an agarose polymer gel network improves the mechanical strength of the gels and appears to slightly enhance the rate of proton diffusion. More sophisticated reservoir shapes can be cut into these more mechanically robust gels, enabling the creation of diffusion waves with different geometries, and hence different patterns of LMWG activation. Multiple reservoirs can be used to create overlapping proton diffusion waves, hence achieving differentiated pH patterns in the gel. Using acid diffusion in this way within gels is an intriguing and powerful way of dynamic patterning. The ability to temporally-evolve spatially-resolved patterns using biocompatible weak acids, and the change in rheological performance of the triggered domains, suggest potential future applications of this strategy in tissue engineering.

Double diffusion for the programmable spatiotemporal patterning of multi-domain supramolecular gels.

To achieve spatial resolution of a multi-component gel, a double diffusion approach is used which enables the precise programming of self-assembled patterned domains with well-defined shapes and sizes. The low-molecular-weight gelators (LMWGs) used in this study are pH-responsive DBS-CO2H and thermally-responsive DBS-CONHNH2 (both based on 1,3:2,4-dibenzylidenesorbitol, DBS). A DBS-CONHNH2 gel was initially assembled in a tray, and then loaded at carefully-selected positions with either basified DBS-CO2H (i.e. DBS-carboxylate) or an acid. These soluble components subsequently diffuse through the pre-formed gel matrix, and in the domains when/where they mix, protonation of the DBS-carboxylate induces self-assembly of the DBS-CO2H network, leading to a patterned gel-in-gel object with well-defined shape and dimensions. Using a strong acid achieves fast gelation kinetics, creating smaller, better-defined macroscale objects but with less nanoscale order. Using a weak acid source with slow kinetics, gives slightly larger objects, but on the nanoscale the DBS-CO2H network formation is better controlled, giving more homogeneous nanoscale structures and stiffer objects. The patterned objects can be further reinforced by the presence of agarose polymer gelator. The shape of the patterning is programmed by both the shape of the central reservoir and the starting geometry in which the reservoirs are organised, with the balance between factors depending on assembly kinetics, as dictated by the choice of acid. This simple methodology therefore enables programming of patterned gels with spatiotemporal control and emergent patterning characteristics.