Zwitterionic Metal-Enolate or Equivalent: Generation and Capture

Functionalized ketones and their derivatives are very important building blocks in organic synthesis and material chemistry. The development of novel methodology for the chemo-, regio-, diastereo-, stereo- and enantioselective synthesis of functionalized ketones and their derivatives is the continuous endeavor of organic chemists. Herein we highlight the new approach that was recently initiated and developed by our group for the synthesis of (enantioenriched) ketones and related derivatives based on zwitterionic metal-enolate (ZME) chemistry.

Diels–Alder Cycloaddition with CO, CO2, SO2, or N2 Extrusion: A Powerful Tool for Material Chemistry

Phenyl, naphthyl, polyarylphenyl, coronene, and other aromatic and polyaromatic moieties primarily influence the final materials’ properties. One of the synthetic tools used to implement (hetero)aromatic moieties into final structures is Diels–Alder cycloaddition (DAC), typically combined with Scholl dehydrocondensation. Substituted 2-pyranones, 1,1-dioxothiophenes, and, especially, 1,3-cyclopentadienones are valuable substrates for [4 + 2] cycloaddition, leading to multisubstituted derivatives of benzene, naphthalene, and other aromatics. Cycloadditions of dienes can be carried out with extrusion of carbon dioxide, carbon oxide, or sulphur dioxide. When pyranones, dioxothiophenes, or cyclopentadienones and DA cycloaddition are aided with acetylenes including masked ones, conjugated or isolated diynes, or polyynes and arynes, aromatic systems are obtained. This review covers the development and the current state of knowledge regarding thermal DA cycloaddition of dienes mentioned above and dienophiles leading to (hetero)aromatics via CO, CO2, or SO2 extrusion. Particular attention was paid to the role that introduced aromatic moieties play in designing molecular structures with expected properties. Undoubtedly, the DAC variants described in this review, combined with other modern synthetic tools, constitute a convenient and efficient way of obtaining functionalized nanomaterials, continually showing the potential to impact materials sciences and new technologies in the nearest future.

The Role of Soft Robotic Micromachines in the Future of Medical Devices and Personalized Medicine

Developments in medical device design result in advances in wearable technologies, minimally invasive surgical techniques, and patient-specific approaches to medicine. In this review, we analyze the trajectory of biomedical and engineering approaches to soft robotics for healthcare applications. We review current literature across spatial scales and biocompatibility, focusing on engineering done at the biotic-abiotic interface. From traditional techniques for robot design to advances in tunable material chemistry, we look broadly at the field for opportunities to advance healthcare solutions in the future. We present an extracellular matrix-based robotic actuator and propose how biomaterials and proteins may influence the future of medical device design.

Cellulose Ether-Based Liquid Crystal Materials: Review Article

The development of liquid crystal materials via nanotechnology has become an interesting subject of research in optical material chemistry. One of the significant nanomaterials is cellulose-based nanoparticles. In this review article, we highlighted the classification of liquid crystal materials (LCs), and types of cellulose-NPs and their characterization as LCs materials. Finally, we present our promising data on the synergistic effect of cellulose-NPs on liquid crystal behavior of ethyl cellulose- and hydroxypropyl cellulose- nanocomposites.

Resurgence of a Nation’s Radiation Science Driven by Its Nuclear Industry Needs

This article describes the radiation facilities and associated sample preparation, management, and analysis equipment currently in place at the Dalton Cumbrian Facility, a facility which opened in 2011 to support the UK’s nuclear industry. Examples of measurements performed using these facilities are presented to illustrate their versatility and the breadth of research they make possible. Results are presented from research which furthers our understanding of radiation damage to polymeric materials, radiolytic yield of gaseous products in situations relevant to nuclear materials, radiation chemistry in light water reactor cooling systems, material chemistry relevant to immobilization of nuclear waste, and radiation-induced corrosion of fuel cladding elements. Applications of radiation chemistry relevant to health care are also described. Research concerning the mechanisms of radioprotection by dietary carotenoids is reported. An ongoing open-labware project to develop a suite of modular sample handling components suited to radiation research is described, as is the development of a new neutron source able to provide directional beams of neutrons.

Schiff bases and their metal complexes with biologically compatible metal ions; biological importance, recent trends and future hopes

Schiff bases are in the field of medicinal and material chemistry for a long time. There are several advancements from time to time towards facile synthesis and potential applications. As medicines they have been applied as organic molecules as well as their metal complexes. The activities of metal complexes have been found to increase due to increase lipophilicity in comparison to the corresponding free ligand. Besides simple coordination compounds they have been applied as ionic liquid (IL)- supported and IL-tagged species with far enhanced efficiency. Among metal complexes recent advancement deals with photodynamic therapy to treat a number of tumors with fewer side effects. Schiff bases are efficient ligands and their complexes with almost all metal ions are reported. This mini-review article deals with complexes of Schiff bases with biologically compatible metal ions, Co(II), Cu(II), Zn(II), Pd(II), Ag(I), Pt(II) and their potential uses to combat cancerous cells. Strong hopes are associated with photodynamic therapy and IL-tagged and IL-supported Schiff bases and their complexes.

Asymmetric misfit nanotubes: Chemical affinity outwits the entropy at high-temperature solid-state reactions

Asymmetric two-dimensional (2D) structures (often named Janus), like SeMoS and their nanotubes, have tremendous scope in material chemistry, nanophotonics, and nanoelectronics due to a lack of inversion symmetry and time-reversal symmetry. The synthesis of these structures is fundamentally difficult owing to the entropy-driven randomized distribution of chalcogens. Indeed, no Janus nanotubes were experimentally prepared, so far. Serendipitously, a family of asymmetric misfit layer superstructures (tubes and flakes), including LaX-TaX2 (where X = S/Se), were synthesized by high-temperature chemical vapor transport reaction in which the Se binds exclusively to the Ta atoms and La binds to S atoms rather than the anticipated random distribution. With increasing Se concentration, the LaS-TaX2 misfit structure gradually transformed into a new LaS-TaSe2-TaSe2 superstructure. No misfit structures were found for xSe = 1. These counterintuitive results shed light on the chemical selectivity and stability of misfit compounds and 2D alloys, in general. The lack of inversion symmetry in these asymmetric compounds induces very large local electrical dipoles. The loss of inversion and time-reversal symmetries in the chiral nanotubes offers intriguing physical observations and applications.

Recent developments in the synthesis of five- and six-membered N-heterocycles from dicarbonyl compounds

: Various diketones such as 1,2-diketones, 1,3-diketones, 1,4-diketones, β-diketones and dicarbonyl compounds are used in the synthesis of core heterocyclic compounds such as pyrazoles, isoxazoles, triazoles and quinolones. They play an important role in synthetic organic chemistry. The diketones and dicarbonyl compounds also act as chelating ligands for the lanthanides and a large number of transition metals in material chemistry. 50% of drugs contain nitrogen heterocyclic compounds, so organic chemists have made efforts for the synthesis of nitrogen-containing heterocyclic compounds. This review article has compiled different methodologies for the synthesis of five- and six-membered nitrogen-containing heterocyclic compounds.

Multigram Synthesis of Difluoromethylene Phosphonic and Phosphinic Amides and Phosphine Oxides via Formal [2,3]-Sigmatropic Allyl Phosphite – Allylphosphonate Rearrangement

We describe a method for the preparation of CF2-P(V) building blocks and monomers for biological and material chemistry applications in multigram quantities based on a formal [2,3]-sigmatropic phospha-Wittig rearrangement of readily available fluoroallyl bis(amido)phosphites, amido(aryl)phosphonites and diarylphosphinites. The proposed intramolecular phosphorylation approach complements the currently prevailing phosphoryldifluoromethylation methods by providing a straightforward access to difluoromethylene phosphonate analogues bearing dialkylamino and/or aryl substituents at the phosphoryl group. An important advantage of the developed method is that it does not rely on ozone-depleting HCF2Cl and CF2Br2 necessary for the preparation of phosphoryldifluoromethylating reagents. 2,3,3-Trifluoroallyloxy P(III) derivatives substituted with two dialkylamino and/or aryl groups underwent a facile [2,3]-phospha-Wittig rearrangement to give difluoromethylene phosphonic, phosphinic and phosphine oxides on up to a 0.15 mol (30 g) scale. The reaction was extended to P(III) derivatives of 1-substituted 2,3,3-trifluoro- and 3,3-difluoroallylic alcohols readily available from carbonyl compounds and, respectively, 1,1,1,2-tetrafluoroethane and O-protected 2,2,2-trifluoroethanols. Products derived from O-(2-tetrahydropyranyl)-2,2,2-trifluoroethanol were synthesized and deprotected in a one-pot multistep protocol to give phosphonic, phosphinic and phosphine oxide analogues of α,α-difluoro-β-ketophosphonates on a multigram scale.

Multi-material direct ink writing of photocurable elastomeric foams

Developments in additive manufacturing have enabled the fabrication of soft machines that can safely interface with humans, creating new applications in soft robotics, wearable technologies, and haptics. However, designing custom inks for the 3D printing of soft materials with Young’s modulus less than 100 kPa remains a challenge due to highly coupled structure-property-process relationship in polymers. Here, we show a three-stage material chemistry process based on interpenetrating silicone double networks and ammonium bicarbonate particles that decouples the transient behavior during processing from the final properties of the material. Evaporation of ammonium bicarbonate particles at the final stage creates gaseous voids to produce foams with a low effective Young’s modulus in the 25 kPa −90 kPa range. Our photoirradiation-assisted direct ink writing system demonstrates the ability to maintain high resolution while enabling controlled loading of ammonium bicarbonate particles. The resultant multi-material possesses programmed porosity and related properties such as density, stiffness, Shore hardness, and ultimate strength in a monolithic object. Our multi-hardness synthetic hand and self-righting buoyant structure highlight these capabilities.