Chirality-controlled spontaneous twisting of crystals due to thermal topochemical reaction.

Crystals that show mechanical response against various stimuli are of great interest. These stimuli induce polymorphic transitions, isomerizations, or chemical reactions in the crystal and the strain generated between the daughter and parent domains is transcribed into mechanical response. We observed that the crystals of modified dipeptide LL (N3-l-Ala-l-Val-NHCH2C≡CH) undergo spontaneous twisting to form right-handed twisted crystals not only at room temperature but also at 0 °C over time. Using various spectroscopic techniques, we have established that the twisting is due to the spontaneous topochemical azide-alkyne cycloaddition (TAAC) reaction at room temperature or lower temperatures. The rate of twisting can be increased by heating, exploiting the faster kinetics of the TAAC reaction at higher temperatures. To address the role of molecular chirality in the direction of twisting the enantiomer of dipeptide LL, N3-d-Ala-d-Val-NHCH2C≡CH (DD), was synthesized and topochemical reactivity and mechanoresponse of its crystals were studied. We have found that dipeptide DD not only underwent TAAC reaction, giving 1,4-triazole-linked pseudopolypeptides of d-amino acids, but also underwent twisting with opposite handedness (left-handed twisting), establishing the role of molecular chirality in controlling the direction of mechanoresponse. This paper reports (i) a mechanical response due to a thermal reaction and (ii) a spontaneous mechanical response in crystals and (iii) explains the role of molecular chirality in the handedness of the macroscopic mechanical response.

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.

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 ß-sheets thereby placing the azide and alkyne motifs in proximity. As anticipated, this peptide forms gels in organic solvents and water via hydrogen-bonded ß-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, XGh (xerogel made from hydrogel) and XGo (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, XGo produced larger oligopeptides, and XGh 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 XGh and XGo 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, XGh and XGo 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.

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 ß-sheet-forming l-Ala-l-Val dipeptide containing azide and alkyne at its termini (N3-Ala-Val-NHCH2C≡CH, 1) was synthesized. Single-crystal XRD analysis of the dipeptide 1 showed parallel ß-sheet arrangement along the b-direction and head-to-tail arrangement of such ß-sheets along the c-direction. This head-to-tail arrangement along the c-direction places the complementary reacting motifs, viz., azide and alkyne, of adjacent molecules in proximity. The crystals of dipeptide 1, 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.

A Molecular-Level Study of Metamorphosis and Strengthening of Gels by Spontaneous Polymorphic Transitions.

Many weak gels often undergo spontaneous transformation to form a stronger gel upon aging. Herein, the molecular-level changes that occur during the transformation of a weak gel into a strong gel are shown by using various time-dependent techniques. Diol 1 forms a metastable transparent gel (TG) in a mixture of CH2 Cl2 /hexane and undergoes a fast transition to an opaque gel (OG) accompanied by gradual strengthening of the gel, as evidenced from time-dependent Tgel and rheology studies. Differential scanning calorimetry and thermogravimetric analyses suggest that these two gels correspond to two different polymorphs. By using FTIR spectroscopy and powder XRD experiments, it is shown that the TG-containing kinetic polymorph, with weakly hydrogen-bonded self-assembly, spontaneously changes into the OG containing a strongly hydrogen-bonded stable polymorph and this leads to strengthening of the gel and metamorphosis. Time-dependent IR studies prove the gradual change in hydrogen-bonding pattern. This is the first molecular-level study of polymorphic transitions in gels.

Semiconducting Fabrics by In†Situ Topochemical Synthesis of Polydiacetylene: A New Dimension to the Use of Organogels.

A diyne functionalized 4,6-O-benzylidene ß-d-galactopyranoside gelator, which can align its diyne motifs upon self-assembly (gelation) have been synthesized. The organogel formed by this gelator undergoes topochemical polymerization to polydiacetylene (PDA) under photoirradiation. This strategically designed gelator has been used to make semi-conducting fabrics. By developing the organogel on the fabrics, the gelator molecules were made not only to self-assemble on the fibers, but also to adhere to fabrics through hydrogen bonding. UV irradiation of the gel-coated fabric/fiber resulted in the formation of PDA on fibers. The benzylidene motif could be deprotected to get PDA with pendant free sugars that strongly bind to the cotton fibrils through multiple hydrogen bonds. Conductivity measurements revealed the semiconducting nature of these fabrics.

A spontaneous single-crystal-to-single-crystal polymorphic transition involving major packing changes.

4,6-O-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 P21 space group (monoclinic) with a single molecule in the asymmetric unit, the ß form appeared as thin fibers and crystallized in P1 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 ß 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 ß 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.

Reversibly growing crosslinked polymers with programmable sizes and properties.

Growth constitutes a powerful method to post-modulate materials' structures and functions without compromising their mechanical performance for sustainable use, but the process is irreversible. To address this issue, we here report a growing-degrowing strategy that enables thermosetting materials to either absorb or release components for continuously changing their sizes, shapes, compositions, and a set of properties simultaneously. The strategy is based on the monomer-polymer equilibrium of networks in which supplying or removing small polymerizable components would drive the networks toward expansion or contraction. Using acid-catalyzed equilibration of siloxane as an example, we demonstrate that the size and mechanical properties of the resulting silicone materials can be significantly or finely tuned in both directions of growth and decomposition. The equilibration can be turned off to yield stable products or reactivated again. During the degrowing-growing circle, material structures are selectively varied either uniformly or heterogeneously, by the availability of fillers. Our strategy endows the materials with many appealing capabilities including environment adaptivity, self-healing, and switchability of surface morphologies, shapes, and optical properties. Since monomer-polymer equilibration exists in many polymers, we envision the expansion of the presented strategy to various systems for many applications.

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.

Thermomagneto-Responsive Smart Biocatalysts for Malonyl-Coenzyme A Synthesis.

Smart biocatalysts, in which enzymes are conjugated to stimuli-responsive polymers, have gained considerable attention because of their catalytic switchability and recyclability. Although many systems have been developed, they require separate laboratory techniques for their recovery, making them unsuitable for many practical applications. To address these issues, we designed a thermomagneto-responsive biocatalyst by immobilizing an enzyme on the terminal of thermo-responsive polymer brushes tethered on magnetic nanoparticle (NP) clusters. The concept is demonstrated by a system consisting of iron oxide NPs, poly(N-isopropyl-acrylamide), and a malonyl-Coenzyme A synthetase (MatB). By using free malonate and coenzyme A (CoA), the designed catalyst exhibits adequate activity for the production of malonyl-CoA. Thanks to the use of a magnetic NP cluster, whose magnetic moment is high, this system is fully recoverable under the magnetic field at above 32 °C because of the collapse of the thermo-responsive polymer shell in the clusters. In addition, the recycled catalyst maintains moderate activity even after three cycles, and it also shows excellent catalytic switchability, that is, negligible catalytic activity at 25 °C because of the blockage of the active sites of the enzyme by the extended hydrophilic polymer chains but great catalytic activity at a temperatures above the lower critical solution temperature at which the enzymes are exposed to the reaction medium because of the thermo-responsive contraction of polymer chains. Because the azide functionality in our system can be easily functionalized depending upon our need, such catalytically switchable, fully recoverable, and recyclable multiresponsive catalytic systems can be of high relevance for other cell-free biosynthetic approaches.

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.

A Library of Multipurpose Supramolecular Supergelators: Fabrication of Structured Silica, Porous Plastics, and Fluorescent Gels.

Supramolecular gels find applications in various fields. Usually, a specific gelator is useful only for a specific application. This one-gelator-one-application format is one factor that limits the usefulness of supramolecular gels. We report the synthesis of a library of gelators from a common core by using a click-chemistry approach. Thus, the click reaction of ß-azido-4,6-O-benzylidene-galactopyranoside (1) with various alkynes gave 11 different gelators having varying gelation abilities. Whereas gelators having alkyl-chain substituents congealed alkanes and tetraethylorthosilicate (TEOS), the gelators having aromatic substituents congealed aromatic solvents. We exploited this difference in gelling behavior in the templated synthesis of silica rods and porous plastics. The styrene gel of gelator 2 j was polymerized, and the gelator was removed by washing to obtain porous polystyrene. The TEOS gel of gelator 2 b was polymerized to silica, and the gelator template was removed by calcination to give microstructured silica rods. We also developed fluorescent gelator 2 f by this method, which might find applications by virtue of its fluorescence in the assembled state.

Organogel-assisted topochemical synthesis of multivalent glyco-polymer for high-affinity lectin binding.

An organogelator, 2,4-undeca-diynyl-4',6'-O-benzylidene-ß-d-galactopyranoside, which aligns its diacetylene upon gelation, has been synthesized. UV irradiation of its gel resulted in topochemical polymerization of the gelator forming polydiacetylene (PDA). We have used this gel-state reaction for the synthesis of surface-immobilized multi-valent glycoclusters, which showed 1000-fold enhanced binding, compared to monomers, with various galactose-binding lectins.

Supramolecular design of a bicomponent topochemical reaction between two non-identical molecules.

We report the first design of a topochemical reaction between two non-identical reactants using a supramolecular chemistry approach. A coassembly of two sugar-based organogelators with complementary reacting motifs, viz. azides and alkynes, undergoes topochemical Huisgen reaction between them.