Complex Pathways Drive Pluripotent Fmoc-Leucine Self-Assemblies.

Nature uses complex self-assembly pathways to access distinct functional non-equilibrium self-assemblies. This remarkable ability to steer same set of biomolecules into different self-assembly states is done by avoiding thermodynamic pit. In synthetic systems, on demand control over 'Pathway Complexity' to access self-assemblies different from equilibrium structures remains challenging. Here we show versatile non-equilibrium assemblies of the same monomer via alternate assembly pathways. The assemblies nucleate using non-classical or classical nucleation routes into distinct metastable (transient hydrogels), kinetic (stable hydrogels) and thermodynamic structures [(poly)-crystals and 2D sheets]. Initial chemical and thermal inputs force the monomers to follow different assembly pathways and form soft-materials with distinct molecular arrangements than at equilibrium. In many cases, equilibrium structures act as thermodynamic sink which consume monomers from metastable structures giving transiently formed materials. This dynamics can be tuned chemically or thermally to slow down the dissolution of transient hydrogel, or skip the intermediate hydrogel altogether to reach final equilibrium assemblies. If required this metastable state can be kinetically trapped to give strong hydrogel stable over days. This method to control different self-assembly states can find potential use in similar biomimetic systems to access new materials for various applications.

Stabilization of a Photoradiated Naphthalene Diimide-Based Organic Radical Anion Inside a Peptide-Based Gel Matrix with an Improvement of Optoelectronic Properties.

An amino acid-conjugated naphthalene diimide (NDI)-based highly red fluorescent radical anion has been found in a water medium under the photoradiated condition. This molecule has failed to form the radical anion in the monomeric state; however, the J aggregation in the aqueous medium has ensured the formation of radical anion in the ambient condition after the irradiation of both sunlight and UV light exposure. Electron paramagnetic resonance (EPR) studies clearly suggest the formation of radical anions. Herein, the stability of the radical anion in the aqueous medium is only a few minutes as a small amount of shaking is enough to quench the radical anion in the solution state. Furthermore, the incorporation of this molecule into a peptide-based hydrogel matrix and the consequent photoirradiation have not only helped to develop radical anion in the gel matrix but also increased the enormous stability of the radical anion inside the hydrogel matrix even for 30 days. It is envisaged that the formation of the radical anion within the gel matrix prevents the free movement of the NDI molecules and restricts the diffusion of molecular oxygen in the system, which leads to the stability of the radical anions in the gel. Moreover, the stability of the radical anion within the gel has helped to enhance the conductivity of the hybrid gel to a great extent. Interestingly, the radical anion-containing hybrid hydrogel has shown a potential photoswitching property.

Carbon Dot as Visible-Light Photoredox Catalysts for a Myriad of Organic Transformations.

Metal-free catalysts for various organic transformations are of high demand now. In this study, we present a new carbon dot as an efficient metal-free nanophotocatalyst for carrying out a series of organic bond formation reactions. Using a single photocatalyst carbon dot, Csp2-Csp2, Csp2-B, Csp2-S, Csp2-Se, and C-P bond formation reactions were performed with a high yield of the corresponding products. Moreover, Csp2-H activation of the aromatic ring was achieved by merging the carbon dot photocatalyst with a transition metal. Interestingly, these carbon nanodot-based catalysts show good recyclability a few times without any significant loss of catalytic activity. The development of catalytic systems based on carbon dots has its merits vested in the advantageous properties of this nanomaterial, such as a robust chemical nature and cheap cost of preparation. This report demonstrates that a carbon dot indeed holds the potential to replace expensive metal-based catalysts as well as organic dyes in five different photoredox reactions.

Yellow-Emitting Carbon Dots for Selective Fluorescence Imaging of Lipid Droplets in Living Cells.

This study shows a one-pot preparation of carbon dots by a solvothermal method in ethylene glycol. The carbon dots show yellow-colored fluorescence emission in water. The carbon dots showed distinct preference to be present in the hydrophobic environment which was evident from their efficient transfer from aqueous phase to organic phase. They were also found to locate themselves in the vesicle bilayer and micelle core. This inherent lipophilic character of these carbon dots has been successfully utilized for the selective imaging of lipid droplets inside the living cells. The selective imaging of lipid droplets was confirmed by similar staining patterns with other staining dyes and the starvation study.

Solvent-Directed Transformation of the Self-assembly and Optical Property of a Peptide-Appended Core-Substituted Naphthelenediimide and Selective Detection of Nitrite Ions in an Aqueous Medium.

This study vividly displays the different self-assembling behavior and consequent tuning of the fluorescence property of a peptide-appended core-substituted naphthalenediimide (N1) in the aliphatic hydrocarbon solvents (n-hexane/n-decane/methyl cyclohexane) and in an aqueous medium within micelles. The N1 is highly fluorescent in the monomeric state and self-aggregates in a hydrocarbon solvent, exhibiting "H-type" or "face-to-face" stacking as indicated by a blue shift of absorption maxima in the UV-vis spectrum. In the H-aggregated state, the fluorescence emission of N1 changes to green from the yellow emission obtained in the monomeric state. In the presence of a micelle-forming surfactant, cetyl trimethylammonium bromide (CTAB), the N1 is found to be dispersed in a water medium. Interestingly, upon encapsulation of N1 into the micelle, the molecule alters its self-assembling pattern and optical property compared to its behavior in the hydrocarbon solvent. The N1 exhibits "edge-to-edge" stacking or J aggregates inside the micelle as indicated by the UV-vis spectroscopic study, which shows a red shift of the absorption maxima compared to that in the monomeric state. The fluorescence emission also differs in the water medium with the NDI derivative exhibiting red emission. FT-IR studies reveal that all amide NHs of N1 are hydrogen-bonded within the micelle (in the J-aggregated state), whereas both non-bonding and hydrogen-bonding amide NHs are present in the H-aggregated state. This is a wonderful example of solvent-mediated transformation of the aggregation pattern (from H to J) and solvatochromism of emission over a wide range from green in the H-aggregated state to yellow in the monomeric state and orangish-red in the J-aggregated state. Moreover, the J aggregate has been successfully utilized for selective and sensitive detection of nitrite ions in water even in the presence of other common anions (NO3-, SO42-, HSO4-, CO32-, and Cl-).

Tuning of the optoelectronic properties of peptide-appended core-substituted naphthalenediimides: the role of self-assembly of two positional isomers.

This study demonstrates how the self-assembly pattern of two different and isomeric peptide-appended core-substituted naphthalenediimides (NDIs) affects the modulation of their optoelectronic properties. Two isomeric peptide-attached NDIs were synthesized, purified and characterized. Interchanging the position of attachment of the peptide units and the alkyl chains in the NDI has altered the respective self-assembling patterns of these isomeric molecules in the aggregated states. The isomer having a peptide moiety in the core position and the alkyl chain in the imide position (compound N1) forms face to face stacking or 'H' aggregates in aliphatic solvents including n-hexane, and n-decane, whereas compound N2, in which the peptide moiety is at the imide position and the alkyl chain is attached at the core position of NDI exhibits edge to edge stacking or J aggregates under the same conditions as it is evident from their UV-vis studies. The H aggregated species (obtained from N1) show inter-connected nanofibers, whereas the J aggregated species (obtained from N2) exhibit the morphology of helical nanoribbons. FT-IR and X-ray diffraction studies are in favor of the same aggregation behavior. The individual packing patterns of these two peptide-based isomers have a direct impact on their respective electrical conductivity. Interestingly, the H aggregated species shows 100 times greater current conductivity than that of the J aggregate. Moreover, it is only the H aggregated species that exhibits a photocurrent, and no such photocurrent response is observed with the J aggregates. Computational studies also support that different types of aggregation patterns are formed by these two isomeric molecules in the same solvent system. This unique example of tuning of optoelectronic behavior holds future promise for the development of new peptide-conjugated π-functional materials.

The aging effect on the enhancement of thermal stability, mechanical stiffness and fluorescence properties of histidine-appended naphthalenediimide based two-component hydrogels.

A histidine attached naphthalenediimide (NDI)-containing amphiphilic molecule (NDIP) self-assembles into nanotubes in aqueous solution at pH 6.6 as revealed by high-resolution transmission electron microscopy studies. This histidine-appended NDI forms a two-component hydrogel in the presence of tartaric acid at a molar ratio of 1 : 2. A morphological transformation was observed from a nanotube structure in the non-gel aggregated state of histidine appended NDI to interconnected cross-linked nanofibers of the two-component hydrogel in the presence of tartaric acid. Interestingly, the gel exhibits an unusual behavior upon aging compared to the fresh gel. It is found that the thermal stability and gel stiffness increase very significantly upon aging. Another important feature noted is that the very weak fluorescence of the fresh gel is transformed into bright greenish fluorescence upon aging. These results suggest that intermolecular interactions among the gelator molecules and tartaric acid in the gel phase slowly increase with time to form a mechanically very stiff and thermally robust gel.

Assembly of amino acid containing naphthalene diimide-based molecules: the role of intervening amide groups in self-assembly, gelation, optical and semiconducting properties.

Two naphthalene diimide containing molecules, one with a covalently linked peptide (P1) and the other with a covalently attached amino acid residue and a diamine moiety (P2), have been chosen in such a way that the number of intervening amide groups and the centrally located imide moieties are the same, and their molecular formulae are also identical. However, the positions of the amide groups are different in these two molecules and this can dictate a different behaviour in molecular assembly and gelation processes for each of the individual NDI-appended peptide (P1) and pseudo-peptide (P2). The molecule P1 with an attached peptide moiety and the intervening -CO-NH groups forms an organogel in a mixture of chloroform-methylcyclohexane at a very rapid rate and the mechanical strength of the gel is quite high, whereas the molecule P2, containing the amino acid and diamide moieties, and with the intervening -NH-CO groups forms an organogel in a relatively much slower rate in chloroform-methylcyclohexane mixture. The mechanical strength of the P2 gel is significantly lower compared to that of the P1 gel at the same concentration and solvent system. The minimum gelation concentration of P1 is much smaller than that of P2 in the same solvent system. The thermal stability of the P1 gel is higher than that of the P2 gel at the same concentration and solvent system. However, both of these gels form J-type aggregates in a mixture of chloroform-methylcyclohexane with a red shift in the UV-vis spectrum. The gelator P1 exhibits enhanced fluorescence compared to that of P2 at a fixed concentration and in the same solvent system (mixture of chloroform-methylcyclohexane, 5 : 95 (v/v)). The lifetime and quantum yield of the P1 gel are also significantly higher than those of the P2 gel under similar gelation conditions. Moreover, both P1 and P2 are found to exhibit significant semiconducting behaviours in their dried/xerogel states. It is important to note that the stronger gel P1 exhibits relatively better semiconducting behaviour than the weak gel P2. Interestingly, the self-assembly, gelation, photoluminescence and electrical conductivity are different for the gels obtained from these two molecules. This indicates the role of the amide bond and its linkage (whether -CONH/-NHCO) in the self-assembly, gelation and optoelectronic behaviour of these molecules in their assembled states.

A Self-Assembled Peptide-Appended Naphthalene Diimide: A Fluorescent Switch for Sensing Acid and Base Vapors.

A histidine-containing bola-amphiphilic molecule (NDIP) containing a peptide-appended naphthalenediimide (NDI) forms fluorescent hydrogels in phosphate buffer and organogels with benzenoid solvents. These gels were characterized by several spectroscopic and microscopic techniques including FT-IR, HR-TEM, powder X-ray diffraction and small-angle X-ray scattering, UV-Vis and fluorescence studies. The gelator molecule exhibits no significant fluorescence in the xerogel state, while it shows a significant fluorescence (bright cyan) in the presence of volatile organic/inorganic acid vapors; this cyan color vanishes in presence of base (ammonia vapors). A reusable paper-strip-based method based on this self-assembled fluorescent material can be used to easily detect hazardous volatile acid and base vapors with the naked eye.

Carbon nanodot-induced gelation of a histidine-based amphiphile: application as a fluorescent ink, and modulation of gel stiffness.

This is a unique example of fluorescent carbon dot-induced hydrogelation of an amino acid-based amphiphile. The carbon dot-to-amphiphile ratio dictates the gel stiffness. Moreover, this hydrogel can be used as a prominent fluorescent ink and the dried gel shows a remarkable, unusual green fluorescence in the solid state.

Amino-Acid-Based Metallo-Hydrogel That Acts Like an Esterase.

A histidine-based amphiphile containing a C14 fatty acyl chain, N- histidyl N'-myristry ethyl amine (AM1, 14.7 mM) forms hydrogels in the presence of Fe3+ (within the range 1.47 to 4.41 mM) and Hg2+ (within the range 3.67 to 11.02 mM) ions in aqueous dispersions at pH 6.6 (27 °C). The imidazole ring of the histidine residue plays a vital role to interact with these metal-ions. The thermal and mechanical stability of these metallo-hydrogels can be tuned by changing the proportion of amphiphile to metal ion ratio (1:0.1 to 1:0.3 for Fe3+-containing gel and 1:0.25 to 1:0.75 for Hg2+-containing gel). The metallo-hydrogels were characterized by different spectroscopic and microscopic techniques, low- and wide-angle powder X-ray diffraction, and small-angle X-ray scattering studies. FT-IR and NMR spectroscopic studies indicate the participation of the imidazole ring in metal-ion binding. Low- and wide-angle powder X-ray diffraction and small-angle X-ray scattering data are in favor of a layered structure of the supramolecular assembly of the AM1 in the presence of metal-ions. Both, the amphiphiles and the metal ion induced hydrogels reveal catalytic activity of p-nitrophenyl esters hydrolysis for the acetyl, n-butyl and n-octyl esters . Ferric ion containing metallo-hydrogel exhibits higher catalytic activity than the corresponding AM1 aggregate in the absence of metal ions.

Amphiphilic Peptide-Based Supramolecular, Noncytotoxic, Stimuli-Responsive Hydrogels with Antibacterial Activity.

A series of peptides with a long fatty acyl chain covalently attached to the C-terminal part and a free amine (-NH2) group at the N-terminus have been designed so that these molecules can be assembled in aqueous medium by using various noncovalent interactions. Five different peptide amphiphiles with a general chemical formula [H2N-(CH2)nCONH-Phe-CONHC12 (n = 1-5, C12 = dodecylamine)] have been synthesized, characterized, and examined for self-assembly and hydrogelation. All of these molecules [P1 (n = 1), P2 (n = 2), P3 (n = 3), P4 (n = 4), P5 (n = 5)] form thermoresponsive hydrogels in water (pH 6.6) with a nanofibrillar network structure. Interestingly, the hydrogels obtained from compounds P4 and P5 exhibit potential antimicrobial activity against Gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis) and Gram-negative bacteria (Escherichia coli). Dose-dependent cell-viability studies using MTT assay (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) by taking human lung carcinoma (A549) cells vividly demonstrates the noncytotoxic nature of these gelator molecules in vitro. Hemolytic studies show nonsignificant or little hemolysis of human erythrocyte cells at the minimum inhibitory concentration (MIC) of these tested bacteria. Interestingly, it has been found that these antibacterial noncytotoxic hydrogels exhibit proteolytic resistance toward the enzymes proteinase K and chymotrypsin. Moreover, the gel strength and gel recovery time have been successfully modulated by varying the alkyl chain length of the N-terminally located amino acid residues. Similarly, the thermal stability of these hydrogels has been nicely tuned by altering the alkyl chain length of the N-terminally located amino acid residues. In the era of antibiotic-resistant strains of bacteria, the discovery of this new class of peptide-based antibacterial, proteolytically stable, injectable, and noncytotoxic soft materials holds future promise for the development of new antibiotics.