Photoinduced Strain‐Assisted Synthesis of a Stiff‐Stilbene Polymer by Ring‐Opening Metathesis Polymerization

Developing a novel strategy to synthesize photoresponsive polymers is of significance owing to their potential applications. We report a photoinduced strain‐assisted synthesis of main‐chain stiff‐stilbene polymers by using ring‐opening metathesis polymerization (ROMP), activating a macrocyclic π‐bond connected to a stiff‐stilbene photoswitch through a linker. Since the linker acts as an external constraint, the photoisomerization to the E‐form leads to the stiff‐stilbene being strained and thus reactive to ROMP. The photoisomerization of Z‐form to E‐form was investigated using time‐dependent NMR studies and UV/Vis spectroscopy. The DFT calculation showed that the E‐form was less stable due to a lack of planarity. By the internal strain developed due to the linker constraint through photoisomerization, the E‐form underwent ROMP by a second generation Grubbs catalyst. In contrast, Z‐form did not undergo polymerization under similar conditions. The MALDI‐TOF spectrum of E‐form after polymerization showed the presence of oligomers of >5.2 kDa

Self‐Healable and Recyclable Tactile Force Sensors with Post‐Tunable Sensitivity

It is challenging to post‐tune the sensitivity of a tactile force sensor. Herein, a facile method is reported to tailor the sensing properties of conductive polymer composites by utilizing the liquid‐like property of dynamic polymer matrix at low strain rates. The idea is demonstrated using dynamic polymer composites (CB/dPDMS) made via evaporation‐induced gelation of the suspending toluene solution of carbon black (CB) and acid‐catalyzed dynamic polydimethylsiloxane (dPDMS). The dPDMS matrices allow CB to redistribute to change the sensitivity of materials at the liquid‐like state, but exhibit typical solid‐like behavior and thus can be used as strain sensors at normal strain rates. It is shown that the gauge factor of the polymer composites can be easily post‐tuned from 1.4 to 51.5. In addition, the dynamic polymer matrices also endow the composites with interesting self‐healing ability and recyclability. Therefore, it is envisioned that this method can be useful in the design of various novel tactile sensing materials for many applications

Modification of Capacitive Charge Storage of TiO2 with Nickel Doping

For practical deployment of supercapacitors characterized by high energy density, power density and long cycle life, they must be realized using low cost and environmentally benign materials. Titanium dioxide (TiO2) is largely abundant in the earth's crust; however, they show inferior supercapacitive electrochemical properties in most electrolytes for practical deployment. In this paper, we show that nickel doped TiO2 (Ni:TiO2) nanowires developed by electrospinning showed five times larger capacitance (∼200 F g−1) than the undoped analogue (∼40 F g−1). Electrochemical measurements show that the Ni:TiO2 nanowires have 100% coulombic efficiency. The electrodes showed no appreciable capacitance degradation for over 5000 cycles. The superior charge storage capability of the Ni:TiO2 could be due to its high electrical conductivity that resulted in five orders of magnitude higher ion diffusion as determined by cyclic voltammetry and electrochemical impedance spectroscopy measurements

Design, Synthesis and Characterization of Vitrimers with Low Topology Freezing Transition Temperature

Vitrimers are crosslinked polymeric materials that behave like fluids when heated, regulated by the kinetics of internal covalent bond-exchange that occurs rapidly at or above the topology freezing transition temperature (Tv) of the vitrimer, making these materials readily reprocessable and recyclable. We report two novel multiphase vitrimeric materials prepared by the cross-linking of two polymers, namely poly(triethylene glycol sebacate) and poly(2-hydroxyethyl acrylate), using zinc acetate or tin(II) 2-ethylhexanoate as catalysts, which exhibit significantly low Tv temperatures of 39 °C and 29 °C, respectively. The transesterification reactions allow rapid and pronounced stress relaxation at high temperatures, following the Arrhenius law. The lower Tv of these vitrimers could be attributable to the flexible long chains of these polymers and the significant excess of OH moieties present along the main chain of the polymer. The design of such multiphase vitrimers is not only useful for the practical application of vitrimers to reduce plastic waste but could also facilitate further development of functional polymer materials that can be reprocessed at low temperatures

Topochemical Azide–Alkyne Cycloaddition Reaction in Gels: Size-Tunable Synthesis of Triazole-Linked Polypeptides

Though topochemical reactions are attractive, the difficulty associated with crystallization such as low yield, unsuitability for large-scale synthesis, etc. warranted the exploitation of other self-assembled media for topochemical reactions. We synthesized a dipeptide gelator decorated with azide and alkyne at its termini, N₃-Ala-Val-NHCH₂-CCH, which is designed to self-assemble through intermolecular hydrogen bonds to β-sheets thereby placing the azide and alkyne motifs in proximity. As anticipated, this peptide forms gels in organic solvents and water via hydrogen-bonded β-sheet assembly as evidenced from IR spectroscopy and PXRD profiling. The microscopic fibers present in organogel and hydrogel have different morphology as was evident from scanning electron microscopy (SEM) imaging of their xerogels, XG_h (xerogel made from hydrogel) and XG_o (xerogel made from organogel). Heating of xerogels at 80 °C resulted in the topochemical azide–alkyne cycloaddition (TAAC) polymerization to 1,4-triazole-linked oligopeptides. Under identical conditions, XG_o produced larger oligopeptides, and XG_h produced smaller peptides, as evidenced from MALDI-TOF spectrometry. We have also shown that degree of TAAC polymerization can be controlled by changing gel fiber thickness, which in turn can be controlled by concentration. SEM studies suggested the morphological intactness of the fibers even after the reaction, and their PXRD profiles revealed that both XG_h and XG_o undergo fiber-to-fiber oligomerization without losing their crystallinity. In contrast to crystals, the xerogels undergo TAAC polymerization in two distinct stages as shown by DSC analyses. Interestingly, XG_h and XG_o undergo spontaneous TAAC polymerization at room temperature; the latter shows faster kinetics. This is not only the first demonstration of the use of xerogels for thermally induced topochemical polymerization but also the first report on a spontaneous topochemical reaction in xerogels

A Spontaneous Single-Crystal-to-Single-Crystal Polymorphic Transition Involving Major Packing Changes

4,6-<i>O</i>-Benzylidene-α-d-galactosyl azide crystallizes into two morphologically distinct polymorphs depending on the solvent. While the α form appeared as thick rods and crystallized in <i>P</i>2₁ space group (monoclinic) with a single molecule in the asymmetric unit, the β form appeared as thin fibers and crystallized in <i>P</i>1 space group (triclinic) with six molecules in the asymmetric unit. Both the polymorphs appeared to melt at the same temperature. Differential scanning calorimetry analysis revealed that polymorph α irreversibly undergoes endothermic transition to polymorph β much before its melting point, which accounts for their apparently same melting points. Variable temperature powder X-ray diffraction (PXRD) experiments provided additional proof for the polymorphic transition. Single-crystal XRD analyses revealed that α to β transition occurs in a single-crystal-to-single-crystal (SCSC) fashion not only under thermal activation but also spontaneously at room temperature. The SCSC nature of this transition is surprising in light of the large structural differences between these polymorphs. Polarized light microscopy experiments not only proved the SCSC nature of the transition but also suggested nucleation and growth mechanism for the transition

Self‐Healable and Recyclable Tactile Force Sensors with Post‐Tunable Sensitivity

It is challenging to post‐tune the sensitivity of a tactile force sensor. Herein, a facile method is reported to tailor the sensing properties of conductive polymer composites by utilizing the liquid‐like property of dynamic polymer matrix at low strain rates. The idea is demonstrated using dynamic polymer composites (CB/dPDMS) made via evaporation‐induced gelation of the suspending toluene solution of carbon black (CB) and acid‐catalyzed dynamic polydimethylsiloxane (dPDMS). The dPDMS matrices allow CB to redistribute to change the sensitivity of materials at the liquid‐like state, but exhibit typical solid‐like behavior and thus can be used as strain sensors at normal strain rates. It is shown that the gauge factor of the polymer composites can be easily post‐tuned from 1.4 to 51.5. In addition, the dynamic polymer matrices also endow the composites with interesting self‐healing ability and recyclability. Therefore, it is envisioned that this method can be useful in the design of various novel tactile sensing materials for many applications

Light-regulated growth from dynamic swollen substrates for making rough surfaces

Natural organic structures form via a growth mode in which nutrients are absorbed, transported, and integrated. In contrast, synthetic architectures are constructed through fundamentally different methods, such as assembling, molding, cutting, and printing. Here, we report a photoinduced strategy for regulating the localized growth of microstructures from the surface of a swollen dynamic substrate, by coupling photolysis, photopolymerization, and transesterification together. Photolysis is used to generate dissociable ionic groups to enhance the swelling ability that drives nutrient solutions containing polymerizable components into the irradiated region, photopolymerization converts polymerizable components into polymers, and transesterification incorporates newly formed polymers into the original network structure. Such light-regulated growth is spatially controllable and dose-dependent and allows fine modulation of the size, composition, and mechanical properties of the grown structures. We also demonstrate the application of this process in the preparation of microstructures on a surface and the restoration of large-scale surface damage

Crystal-to-Crystal Synthesis of Triazole-Linked Pseudo-proteins via Topochemical Azide–Alkyne Cycloaddition Reaction

Isosteric replacement of amide bond(s) of peptides with surrogate groups is an important strategy for the synthesis of peptidomimetics (pseudo-peptides). Triazole is a well-recognized bio-isostere for peptide bonds, and peptides with one or more triazole units are of great interest for different applications. We have used a catalyst-free and solvent-free method, viz., topochemical azide–alkyne cycloaddition (TAAC) reaction, to synthesize pseudo-proteins with repeating sequences. A designed β-sheet-forming l-Ala-l-Val dipeptide containing azide and alkyne at its termini (N₃-Ala-Val-NHCH₂CCH, <b>1</b>) was synthesized. Single-crystal XRD analysis of the dipeptide <b>1</b> showed parallel β-sheet arrangement along the <i>b</i>-direction and head-to-tail arrangement of such β-sheets along the <i>c</i>-direction. This head-to-tail arrangement along the <i>c</i>-direction places the complementary reacting motifs, viz., azide and alkyne, of adjacent molecules in proximity. The crystals of dipeptide <b>1</b>, upon heating at 85 °C, underwent crystal-to-crystal polymerization, giving 1,4-triazole-linked pseudo-proteins. This TAAC polymerization was investigated by various time-dependent techniques, such as NMR, IR, DSC, and PXRD. The crystal-to-crystal nature of this transformation was revealed from polarizing microscopy and PXRD experiments, and the regiospecificity of triazole formation was evidenced from various NMR techniques. The MALDI-TOF spectrum showed the presence of pseudo-proteins >7 kDa

Crystal-to-Crystal Synthesis of Triazole-Linked Pseudo-proteins via Topochemical Azide–Alkyne Cycloaddition Reaction

Isosteric replacement of amide bond(s) of peptides with surrogate groups is an important strategy for the synthesis of peptidomimetics (pseudo-peptides). Triazole is a well-recognized bio-isostere for peptide bonds, and peptides with one or more triazole units are of great interest for different applications. We have used a catalyst-free and solvent-free method, viz., topochemical azide–alkyne cycloaddition (TAAC) reaction, to synthesize pseudo-proteins with repeating sequences. A designed β-sheet-forming l-Ala-l-Val dipeptide containing azide and alkyne at its termini (N₃-Ala-Val-NHCH₂CCH, <b>1</b>) was synthesized. Single-crystal XRD analysis of the dipeptide <b>1</b> showed parallel β-sheet arrangement along the <i>b</i>-direction and head-to-tail arrangement of such β-sheets along the <i>c</i>-direction. This head-to-tail arrangement along the <i>c</i>-direction places the complementary reacting motifs, viz., azide and alkyne, of adjacent molecules in proximity. The crystals of dipeptide <b>1</b>, upon heating at 85 °C, underwent crystal-to-crystal polymerization, giving 1,4-triazole-linked pseudo-proteins. This TAAC polymerization was investigated by various time-dependent techniques, such as NMR, IR, DSC, and PXRD. The crystal-to-crystal nature of this transformation was revealed from polarizing microscopy and PXRD experiments, and the regiospecificity of triazole formation was evidenced from various NMR techniques. The MALDI-TOF spectrum showed the presence of pseudo-proteins >7 kDa