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Four-dimensional printing refers to a process through which a 3D printed object transforms from one structure into another through the influence of an external energy input. Self-folding structures have been extensively studied to advance 3D printing technology into 4D using stimuli-responsive polymers. Designing and applying self-folding structures requires an understanding of the material properties so that the structural designs can be tailored to the targeted applications. Poly(N-iso-propylacrylamide) (PNIPAM) was used as the thermo-responsive material in this study to 3D print hydrogel samples that can bend or fold with temperature changes. A double-layer printed structure, with PNIPAM as the self-folding layer and polyethylene glycol (PEG) as the supporting layer, provided the mechanical robustness and overall flexibility to accommodate geometric changes. The mechanical properties of the multi-material 3D printing were tested to confirm the contribution of the PEG support to the double-layer system. The desired folding of the structures, as a response to temperature changes, was obtained by adding kirigami-inspired cuts to the design. An excellent shape-shifting capability was obtained by tuning the design. The experimental observations were supported by COMSOL Multiphysics® software simulations, predicting the control over the folding of the double-layer systems. [ABSTRACT FROM AUTHOR]

Nanostructured materials have enabled new ways of controlling the light–matter interaction, opening new routes for exciting applications, in display technologies and colorimetric sensing, among others. In particular, metallic nanoparticles permit the production of color structures out of colorless materials. These plasmonic structural colors are sensitive to the environment and thus offer an interesting platform for sensing. Here, a self‐assembly of aluminum nanoparticles in close proximity of a mirror is spaced by an ultrathin poly(N‐isopropylacrylamide) (PNIPAM) layer. Hybridizing the plasmonic system with the active polymer layer, a thermoresponsive gap‐plasmon architecture is formed that transduces changes in the temperature and relative humidity of the environment into color changes. By harnessing the environmentally induced structural changes of PNIPAM, it was estimated from the finite difference time domain simulation that the resonance can be tuned 7 nm per every 1 nm change in thickness, resulting in color variation. Importantly, these fully reversible changes can be used for reusable powerless humidity and temperature colorimetric sensing. Crucially if condensation on the structure happens, the polymer layer is deformed beyond recovery and the colors are washed away. We leverage this effect to produce tamper‐proof dew labels that a straightforward smartphone app can read by taking a picture. [ABSTRACT FROM AUTHOR]

In organic solar cells (OSCs), improving the properties at the interface of the bulk heterojunction (BHJ) photoactive layer and the buffer layer is desired, but achieving a high-quality interface between these two layers is inevitably challenging. Herein, a novel (PC61BM)-doped zinc oxide, that is, a (PC61BMZnO) DEZ hybrid thin film, is proposed for application as a cathode buffer layer (CBL) for OSCs based on both fullerene-based acceptors and nonfullerene acceptors. These thin films require low annealing temperatures and can be deposited via a one-step solution-processable method using a hybrid precursor composed of PC61BM and diethylzinc solution (DEZ). The study reveals that the performance of devices with (PC61BM-ZnO)DEZ hybrid thin films as a CBL exceeds that of devices with thin films of conventional ZnO as a CBL. Impedance analysis of the fabricated OSCs suggests improved charge collection efficiency in the devices with (PC61BM-ZnO)DEZ thin film. Optical, electrical, morphological, and compositional characterizations of thin films used as CBLs confirm the presence of a PC61BM-rich phase with traces of d-C61 (fullerene dimer) at the surface of the hybrid (PC61BM-ZnO)DEZ thin film. These phases help in tuning the interfacial properties by ensuring better coupling between the BHJ photoactive layer and the CBL. [ABSTRACT FROM AUTHOR]

Stimulus-responsive polymers have been used in improving the efficacy of medical diagnostics through different approaches including enhancing the contrast in imaging techniques and promoting the molecular recognition in diagnostic assays. This review overviews the mechanisms of stimulus-responsive polymers in response to external stimuli including temperature, pH, ion, light, etc. The applications of responsive polymers in magnetic resonance imaging, capture and purification of biomolecules through protein–ligand recognition and lab-on-a-chip technology are discussed. [ABSTRACT FROM AUTHOR]

The hydrogen-bonded arene ruthenium metalla-rectangle, [(p-cymene)2Ru2(OO⌒OO)(UPy)2]24+, obtained from 1-(4-oxo-6-undecyl-1,4-dihydropyrimidin-2-yl)-3-(pyridin-4-ylmethyl)urea (UPy) and the dinuclear arene ruthenium clip (p-cymene)2Ru2(OO⌒OO)Cl2 (OO⌒OO = 2,5-dioxido-1,4-benzoquinonato), is investigated by means of solution-phase NMR spectroscopy. Rotating frame nuclear Overhauser effect measurements are used to probe the H-bond network that drives the UPy self-assembly as well as the full rectangular supramolecular system. An effective distance that takes into account both intra- and intermolecular polarization-transfer pathways is utilised for data analysis. The experimental findings are corroborated by DFT calculations of NMR parameters and internuclear distances, thus confirming the formation of a very stable tetranuclear metalla-assembly. [ABSTRACT FROM AUTHOR]

The bis(pyrazole)zinc(II) benzoate complexes bis(3,5-diphenylpyrazole)zinc(II) benzoate (1), bis(3,5-diphenylpyrazole)zinc(II) 3,5-dinitrobenzoate (2), bis(3,5-diphenylpyrazole)zinc(II) 4-hydroxybenzoate (3), and bis(3,5-di-tert-butylpyrazole)zinc(II) 2-chlorobenzoate (4) were synthesized from the reaction of 3,5-diphenylpyrazole (L1) or 3,5-di-tert-butylpyrazole (L2), zinc(II) acetate and the appropriate benzene carboxylic acid. The molecular structure of complex 2 confirmed that these zinc(II) benzoate complexes adopt a 4-coordinate tetrahedral geometry. All four complexes were screened as catalysts for the copolymerization of carbon dioxide (CO2) and cyclohexene oxide (CHO) and were found to be active for the formation of poly(cyclohexene carbonate) (PCHC) at CO2 pressures as low as 1.0 MPa under solvent-free conditions and without the use of a co-catalyst. At some reaction condition, most of the catalysts produced PCHC with high carbonate content of up to 98% and a good amount of cyclic cyclohexene carbonate (CCHC). The copolymers produced have low to moderate molecular weights (5200-12300 g/mol) and with polydispersity indices that vary from 1.19 to 2.50. Matrix Assisted Laser Desorption/Ionization-Time of Flight Mass Spectra (MALDI-TOF MS) of these copolymers showed they have benzoate and hydroxyl end groups. [ABSTRACT FROM AUTHOR]

The article discusses the synthesis of fullerene and arene ruthenium moieties by focusing on the merger of the carbon molecule and ruthenium complexes tested by nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry. The article also provides characterization of the carbon molecule and arene ruthenium complexes.

A high-yield, solvent-free approach to the synthesis of 1,3,5-trisubstituted pyrazoles is reported. Four compounds, (3,5-di-tert-butyl-1H-pyrazole, (2-(3,5-dimethyl-1H-pyrazol-1-yl)ethanol, 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethanol, 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethanol were readily prepared by solvent-free condensation of the appropriate diketone and the respective hydrazine. The crystal structures of the three pyrazolyl-ethanols are typical of N-substituted pyrazoles. All three pyrazolyl compounds show interesting inter-molecular hydrogen bonding. For the 3,5-dimethyl compound the molecules form discrete hydrogen bonded dimers within a unit cell, while for the others the hydrogen bonding is in a head-to-tail arrangement resulting in the formation of chains. [ABSTRACT FROM AUTHOR]

Olefin bonds participate in co-reaction with the benzoxazine functionality of the monomer and are one of the strategies used to affect the crosslink density of a polybenzoxazine network. In general, the double bond incorporation in starting material is usually catalyzed by expensive, rare earth metals affecting the sustainability of the reaction. The natural abundance of feedstocks with inherent double bonds may be a powerful platform for the development of novel greener structures, with potential applications in polymers. Here, we report the design, synthesis, and characterization of a biobased non-halogen flame retardant, consisting of naturally occurring phenols, eugenol (E), and cardanol (C). The presence of a covalently linked phosphazene (P) core allowed the synthesis of hexa-functional flame retardant molecules, abbreviated as EP and CP. The chemical structures of the synthesized EP and CP were confirmed by Fourier transform infrared (FTIR), nuclear magnetic resonance ( 1 H, 13 C, 31 P NMR), and single crystal XRD (only in the case of EP). Their polymerization with cardanol sourced tri-oxazine benzoxazine monomer, C-trisapm, was followed by FTIR, NMR, and DSC studies. The thermal stability and flame retardant properties of the hybrid phosphazene-benzoxazine copolymers was determined by thermogravimetry analysis (TGA), limiting oxygen index (LOI), vertical burning, and smoke density analyses. SEM images of the char residues of the polymers with or without the addition of reactive phosphazene molecules confirmed the intumescent flame retarding mechanism. Current work highlights the utility of sustainable origin non-halogen flame retardant (FR) molecules and their utility in polybenzoxazine chemistry., (Copyright © 2020 Appavoo, Amarnath and Lochab.)