Organelle-Specific Smart Supramolecular Materials for Bioimaging and Theranostics Application.

In cellular environments, certain synthetic molecules can form nanostructures via self-assembly, impacting molecular imaging, and biomedical applications. Control over the formation of these self-assembled nanostructures in subcellular organelle is challenging. By the action of stimuli, either present in the cellular environment or applied externally, in situ generation of molecular precursors can lead to accumulation and supramolecular nanostructure formation, resulting in efficient bioimaging.

Biochemical Signal-Induced Supramolecular Hydrogelation for Structured Free-Standing Soft Material Formation.

Cells coordinate their activity and regulate biological processes in response to chemical signals. Mimicking natural processes, control over the formation of artificial supramolecular materials is of high interest for their application in biology and medicine. Supramolecular material that can form in response to chemical signals is important for the development of autonomously responsive materials.

Multi-Colored Aqueous Ink for Rewritable Paper.

As sustainable and eco-friendly replacements to conventional paper, rewritable paper is a very attractive alternative for communication, information circulation, and storage. Development is made for rewritable paper using chromogenic materials that change its color in presence of external stimuli. However, the new techniques have faced several major challenges including feasible operational method, eco-friendly approach.

Polynaphthalene-Based Oxazaborinine Complexes Formulated as Red Light Emitters and High-Performance Asymmetric Supercapacitors.

Developing a solid organic emitter based on an oxazaborinine complex with improved photophysical characteristics has become essential to fulfilling the rising need for optical and electrochemical technology. Two oxazaborinine complexes ( (a tri-naphthalene boron complex) and (a di-naphthalene boron complex)) decorated with naphthalene and triphenylamine have been developed, which show emission in the red light region in the solid phase. Their effectiveness as asymmetric supercapacitor electrodes in aqueous electrolytes is also being studied.

Switchable aqueous catalytic systems for organic transformations.

In living organisms, enzyme catalysis takes place in aqueous media with extraordinary spatiotemporal control and precision. The mechanistic knowledge of enzyme catalysis and related approaches of creating a suitable microenvironment for efficient chemical transformations have been an important source of inspiration for the design of biomimetic artificial catalysts. However, in "nature-like" environments, it has proven difficult for artificial catalysts to promote effective chemical transformations.

Switching the Mode of Drug Release from a Reaction-Coupled Low-Molecular-Weight Gelator System by Altering Its Reaction Pathway.

Low-molecular-weight hydrogels are attractive scaffolds for drug delivery applications because of their modular and facile preparation starting from inexpensive molecular components. The molecular design of the hydrogelator results in a commitment to a particular release strategy, where either noncovalent or covalent bonding of the drug molecule dictates its rate and mechanism. Herein, we demonstrate an alternative approach using a reaction-coupled gelator to tune drug release in a facile and user-defined manner by altering the reaction pathway of the low-molecular-weight gelator (LMWG) and drug components through an acylhydrazone-bond-forming reaction.

Alginate-Based Smart Materials and Their Application: Recent Advances and Perspectives.

Nature produces materials using available molecular building blocks following a bottom-up approach. These materials are formed with great precision and flexibility in a controlled manner. This approach offers the inspiration for manufacturing new artificial materials and devices.

Hierarchically Compartmentalized Supramolecular Gels through Multilevel Self-Sorting.

Hierarchical compartmentalization through the bottom-up approach is ubiquitous in living cells but remains a formidable task in synthetic systems. Here we report on hierarchically compartmentalized supramolecular gels that are spontaneously formed by multilevel self-sorting. Two types of molecular gelators are formed in situ from nonassembling building blocks and self-assemble into distinct gel fibers through a kinetic self-sorting process; interestingly, these distinct fibers further self-sort into separated microdomains, leading to microscale compartmentalized gel networks.

Selective activation of organocatalysts by specific signals.

Reminiscent of signal transduction in biological systems, artificial catalysts whose activity can be controlled by physical or chemical signals would be of high interest in the design of chemical systems that can respond to their environment. Self-immolative chemistry offers a generic method for the development of catalysts that can be activated by different signals. To demonstrate the versatility of that concept, we synthesized organocatalysts that can be activated by three different signals and that can be used to control two different reactions.

Dissipative assemblies that inhibit their deactivation.

Dissipative self-assembly is a process in which energy-consuming chemical reaction networks drive the assembly of molecules. Prominent examples from biology include the GTP-fueled microtubule and ATP-driven actin assembly. Pattern formation and oscillatory behavior are some of the unique properties of the emerging assemblies.

Chemical signal activation of an organocatalyst enables control over soft material formation.

Cells can react to their environment by changing the activity of enzymes in response to specific chemical signals. Artificial catalysts capable of being activated by chemical signals are rare, but of interest for creating autonomously responsive materials. We present an organocatalyst that is activated by a chemical signal, enabling temporal control over reaction rates and the formation of materials.

Erratum: Free-standing supramolecular hydrogel objects by reaction-diffusion.

This corrects the article DOI: 10.1038/ncomms15317.

Free-standing supramolecular hydrogel objects by reaction-diffusion.

Self-assembly provides access to a variety of molecular materials, yet spatial control over structure formation remains difficult to achieve. Here we show how reaction-diffusion (RD) can be coupled to a molecular self-assembly process to generate macroscopic free-standing objects with control over shape, size, and functionality. In RD, two or more reactants diffuse from different positions to give rise to spatially defined structures on reaction.

Crosslinker-Induced Effects on the Gelation Pathway of a Low Molecular Weight Hydrogel.

The use of polymeric crosslinkers is an attractive method to modify the mechanical properties of supramolecular materials, but their effects on the self-assembly of the underlying supramolecular polymer networks are poorly understood. Modulation of the gelation pathway of a reaction-coupled low molecular weight hydrogelator is demonstrated using (bio)polymeric crosslinkers of disparate physicochemical identities, providing a handle for control over materials properties.

Synthesis of a Double-Network Supramolecular Hydrogel by Having One Network Catalyse the Formation of the Second.

Self-assembly of biomolecules catalytically controls the formation of natural supramolecular structures, giving highly ordered complex materials. Such desirable hybrid systems are very difficult to design and construct synthetically. A hybrid double-network hydrogel with a maximum storage modulus (G' ) of up to 55 kPa can be synthesized by using a self-assembled hydrogel that catalyses the formation of another kinetically arrested hydrogel network.

Negatively Charged Lipid Membranes Catalyze Supramolecular Hydrogel Formation.

In this contribution we show that biological membranes can catalyze the formation of supramolecular hydrogel networks. Negatively charged lipid membranes can generate a local proton gradient, accelerating the acid-catalyzed formation of hydrazone-based supramolecular gelators near the membrane. Synthetic lipid membranes can be used to tune the physical properties of the resulting multicomponent gels as a function of lipid concentration.

Catalysis of Supramolecular Hydrogelation.

One often thinks of catalysts as chemical tools to accelerate a reaction or to have a reaction run under more benign conditions. As such, catalysis has a role to play in the chemical industry and in lab scale synthesis that is not to be underestimated. Still, the role of catalysis in living systems (cells, organisms) is much more extensive, ranging from the formation and breakdown of small molecules and biopolymers to controlling signal transduction cascades and feedback processes, motility, and mechanical action.

A toolbox for controlling the properties and functionalisation of hydrazone-based supramolecular hydrogels.

In recent years, we have developed a low molecular weight hydrogelator system that is formed in situ under ambient conditions through catalysed hydrazone formation between two individually non-gelating components. In this contribution, we describe a molecular toolbox based on this system which allows us to (1) investigate the limits of gel formation and fine-tuning of their bulk properties, (2) introduce multicolour fluorescent probes in an easy fashion to enable high-resolution imaging, and (3) chemically modify the supramolecular gel fibres through click and non-covalent chemistry, to expand the functionality of the resultant materials. In this paper we show preliminary applications of this toolbox, enabling covalent and non-covalent functionalisation of the gel network with proteins and multicolour imaging of hydrogel networks with embedded mammalian cells and their substructures.

Novel multiporphyrin functionalized single-walled carbon nanotubes.

Porphyrin monomers, 5,15-bis(4-(2,5,8,11-tetraoxatridecan-13-yloxy)phenyl)-10,20-bis(3-iodophenyl)porphyrin zinc (5a) and 5,10-bis(4-(2,5,8,11-tetraoxatridecan-13-yloxy)phenyl)-15,20-bis(3-iodophenyl)porphyrin zinc (5b), and their oligomers 6a and 6b were synthesized and characterized. The titration experiment of the monomers was carried out in THF by changing the solution percent of water. The optical properties (UV-vis and fluorescence spectra) of the monomers that possess slightly red-shifted optical spectra in water compared to the spectra obtained in THF are reported.

Spatial structuring of a supramolecular hydrogel by using a visible-light triggered catalyst.

Spatial control over the self-assembly of synthetic molecular fibers through the use of light-switchable catalysts can lead to the controlled formation of micropatterns made up of hydrogel structures. A photochromic switch, capable of reversibly releasing a proton upon irradiation, can act as a catalyst for in situ chemical bond formation between otherwise soluble building blocks, thereby leading to fiber formation and gelation in water. The use of a photoswitchable catalyst allows control over the distribution as well as the mechanical properties of the hydrogel material.

Nonstationary magnetosonic wave dynamics in plasmas exhibiting collapse.

In a Lagrangian fluid approach, an explicit method has been presented previously to obtain an exact nonstationary magnetosonic-type wave solution in compressible magnetized plasmas of arbitrary resistivity showing competition among hydrodynamic convection, magnetic field diffusion, and dispersion [Chakrabarti et al., Phys. Rev.

Wave-breaking phenomena in a relativistic magnetized plasma.

We study the wave-breaking phenomenon of relativistic upper-hybrid (UH) oscillations in a cold magnetoplasma. For our purposes, we use the electron continuity and relativistic electron momentum equations, together with Maxwell's equations, as well as introduce Lagrangian coordinates to obtain an exact nonstationary solution of the governing nonlinear equations. It is found that bursts in the electron density appear in a finite time as a result of relativistic electron mass variations in the UH electric field, indicating a phase mixing or breaking of relativistic UH oscillations.

Catalytic control over supramolecular gel formation.

Low-molecular-weight gels show great potential for application in fields ranging from the petrochemical industry to healthcare and tissue engineering. These supramolecular gels are often metastable materials, which implies that their properties are, at least partially, kinetically controlled. Here we show how the mechanical properties and structure of these materials can be controlled directly by catalytic action.

Breaking of upper hybrid oscillations in the presence of an inhomogeneous magnetic field.

We present space-time evolution of large-amplitude upper hybrid modes in a cold homogeneous plasma in the presence of an inhomogeneous magnetic field. Using the method of Lagrange variables, an exact space-time-dependent solution is obtained in parametric form. It is found that the magnetic field inhomogeneity causes various nonlinearly excited modes to couple, resulting in phase mixing and eventual breaking of the initially excited mode.

Exact time-dependent nonlinear dispersive wave solutions in compressible magnetized plasmas exhibiting collapse.

Compressional waves in a magnetized plasma of arbitrary resistivity are treated with the lagrangian fluid approach. An exact nonlinear solution with a nontrivial space and time dependence is obtained with boundary conditions as in Harris' current sheet. The solution shows competition among hydrodynamic convection, magnetic field diffusion, and dispersion.