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 β 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 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.

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.

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 (N-l-Ala-l-Val-NHCHC≡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, N-d-Ala-d-Val-NHCHC≡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 () a mechanical response due to a thermal reaction and () a spontaneous mechanical response in crystals and () explains the role of molecular chirality in the handedness of the macroscopic mechanical response.

As an important research tool, peptide have received prominence in molecular biology, clinical research, instrumentation, study of protein structure and functioning, smart biomaterials etc. This has encouraged to develop synthetic peptides (by replacing enzyme sensitive amide linkage) i.e. Peptidomimetics having enhanced stability and attractive properties. 1,2,3-triazole motif is widely accepted isosteric group to surrogate such linkages present in biopolymers. Instead of using classical approach to peptide synthesis leading to poor yield, bad control over the stereo-and regioselectivity, solubility issues, slow reaction rate, use of toxic catalysts, difficult purification etc., we have used Topochemical Azide-Alkyne Cycloaddition (TAAC, lattice controlled) reaction. Utilizing the principle of crystal engineering, we have synthesized a structurally modified dipeptide (using alanine and valine) which undergoes heat induced topochemical 1,3-dipolar cycloaddition reaction to give triazole-linked pseudopolypeptide. Also, the crystals underwent cracking due to the packing strain generated at higher temperature due to thermal topochemical polymerization. Systematic characterization is carried out to study the following TAAC reaction. [1] Biradha, K. et al. (2013) Chem. Rev. 42, 950-967.

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, N-Ala-Val-NHCH-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 (xerogel made from hydrogel) and XG (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 produced larger oligopeptides, and XG 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 and XG 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 and XG 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.