Life is a non‐equilibrium state of matter maintained at the expense of energy. Nature uses predominantly chemical energy stored in thermodynamically activated, but kinetically stable, molecules. These high‐energy molecules are exploited for the synthesis of other biomolecules, for the activation of biological machinery such as pumps and motors, and for the maintenance of structural order. Knowledge of how chemical energy is transferred to biochemical processes is essential for the development of artificial systems with life‐like processes. Here, we discuss how chemical energy can be used to control the structural organization of organic molecules. Four different strategies have been identified according to a distinguishable physical‐organic basis. For each class, one example from biology and one from chemistry are discussed in detail to illustrate the practical implementation of each concept and the distinct opportunities they offer. Specific attention is paid to the discussion of chemically fueled non‐equilibrium self‐assembly. We discuss the meaning of non‐equilibrium self‐assembly, its kinetic origin, and strategies to develop synthetic non‐equilibrium systems.

In living systems, dissipative processes are driven by the endergonic hydrolysis of chemical fuels such as nucleoside triphosphates. Now, through a simple model system, a transient self‐assembled state is realized by utilizing the catalytic effect of histidine on the formation and breaking of ester bonds. First, histidine facilitates the ester bond formation, which then rapidly co‐assembles to form a self‐supporting gel. An out‐of‐equilibrium state is realized owing to the cooperative catalysis by the proximal histidines in the assembled state, driving the second pathway and resulting in disassembly to sol. Cooperative effects that use the dual role of imidazoles as nucleophile and as proton donor is utilized to achieve transient assemblies. This simple system mimics the structural journey seen in microtubule formation where the substrate GTP facilitates the non‐covalent assembly and triggers a cooperative catalytic process, leading to substrate hydrolysis and subsequent disassembly.

Thermal coupling between citric acid and Na-salt of glycine, L-valine and L-isolucine produced amino acid surface functionalized fluorescent blue emitting carbon dots (CDs). The same precursor in presence of NaH 2 PO 4 , produced phosphorous doped amino acid functionalized carbon dots which are green emitting. These blue and green emitting carbon dots were utilized for cell imaging.Abstract: Amino acid functionalized carbon dots (CDs) were synthesized in a simple and cost effective bottom up approach. Citric acid was used as the source of carbon core and three amino acids L-isoleucine, L-valine and glycine were used for the surface fabrication of CDs to produce CD iso , CD val and CD gly , respectively. Interestingly these CDs were found to be fluorescent with blue emission. Doping of phosphorus to these CDs (PCDs) tuned the photoemission properties and produced green emitting PCDs. The doping of phosphorous (P) to these CDs improved their fluorescence intensity as well as quantum yields. Both doped and non-doped CDs were characterized by spectroscopic and microscopic techniques. These highly stable CDs were biocompatible in nature and did not exhibit any photobleaching property over a long span of time even under UV exposure. Subsequently, these CDs were exploited as excellent bioimaging probe. Importantly CDs and PCDs illuminated cells in two completely different spectral regions blue and green, respectively in accordance with their fluorescence spectral behaviour. Hence, amino acid functionalized carbon dots based bioimaging probes of different fluorescence character were developed that are widely applicable for cellular imaging in both blue and green spectral regions. Fig. 7 Percentage cell viability of Hela cells incubated with varying concentrations of (a) CDs and (b) PCDs after 24 h incubation. The experimental errors were in the range of 3-5% in triplicate experiments.

A fluorimetric histone sensing technique is developed using quaternized carbon dot-DNA nanobiohybrid. The method is simple, specific, and can detect a minimum of 0.2 ng mL(-1) histone.

The present article delineates the formation of green fluorescent organic nanoparticle through supramolecular aggregation of naphthalene diimide (NDI)-based, carboxybenzyl-protected, l-phenylalanine-appended bola-amphiphile, NDI-1. The amphiphilic molecule is soluble in DMSO, and, with gradual addition of water within the DMSO solution, the amphiphile starts to self-assemble via H-type aggregation to form spherical nanoparticles. These self-assembly of NDI-1 in the presence of a high amount of water exhibited aggregation-induced emission (AIE) through excimer formation. Notably, in the presence of 99% water content, the amphiphile forms spherical aggregated nanoparticles as confirmed from microscopic investigations and dynamic light scattering study. Interestingly, the emission maxima of molecularly dissolved NDI-1 (weak blue fluorescence) red-shifted upon aggregation with increase in water concentration and led to the formation of green-emitting fluorescent organic nanoparticles (FONPs) at 99% water content. These green-emitting FONPs were utilized in cell imaging as well as for efficient transportation of anticancer drug curcumin inside mammalian cells.

Highly dynamic and complex systems of microtubules undergo a substrate‐induced change of conformation that leads to polymerization. Owing to the augmented catalytic potential at the polymerized state, rapid hydrolysis of the substrate is observed, leading to catastrophe, thus realizing the out‐of‐equilibrium state. A simple synthetic mimic of these dynamic natural systems is presented, where similar substrate induced conformational change is observed and a transient helical morphology is accessed. Further, augmented catalytic potential of these helical nanostructures leads to rapid hydrolysis of the substrate providing negative feedback on the stability of the nanostructures and realization of an out‐of‐equilibrium state. This simple system, made from amino acid functionalized lipids, demonstrates a substrate‐induced self‐assembled state, where the fuel‐to‐waste conversion leads to the temporal presence of helical nanostructures.

moved to Italy to join the group of Leonard Prins at the University of Padova as aMarie Curie Seal-of-Excellence@UNIPD fellow to work on the dissipative self-assemblyo f chemical nanoreactors. His research interests include systems chemistry and non-equilibrium supramolecular systems. Luca Gabrielli received his PhD from the University of Milano-Bicocca (2013), under the supervision of Prof L. Cipolla. After postdoctoral research in the groups of Prof.

The present work highlights design and development of noncovalently surface-modified carbon dots by 17β-estradiol hemisuccinate that selectively stains estrogen receptor (ER)-rich cancer cells as well as kill ER (+) cancer cells by target-specific delivery of the anticancer drug doxorubicin. Positively surface-charged blue-emitting and green-emitting cationic carbon dots (CCDs) were prepared. Blue-emitting cationic carbon dots (CCDb) were prepared by the thermal coupling of tris­(hydroxymethyl)­aminomethane and betaine hydrochloride, while green-emitting cationic carbon dots (CCDg) were prepared by the thermal coupling of citric acid and ehylenediamine. Negatively charged estradiol hemisuccinate (E2) was synthesized from 17β-estradiol. Both CCDb and CCDg were noncovalently coupled with E2 through electrostatic interaction to prepare CCDb-E2 and CCDg-E2 hybrids, respectively. These surface-modified carbon dots were characterized by microscopic and spectroscopic techniques. Both CCD-E2 hybrids were highly water soluble. CCDb-E2 and CCDg-E2 exhibited enhanced emissions more than those of the respective native CCDs. Consequently, these CCDb-E2 and CCDg-E2 hybrids were utilized as selective cellular markers of estrogen receptor-rich (ER+) MCF7 cells over estrogen receptor negative (ER-) MDA-MB-231 cells and noncancerous CHO cells. Moreover, the anticancer drug doxorubicin (dox)-loaded CCDb-E2 and CCDg-E2 (CCDb-E2-dox and CCDg-E2-dox, respectively) showed selective killing of ER­(+) MCF7 cells through a late apoptotic pathway by 2-fold higher efficacy compared to ER(−) MDA-MB-231 cells and noncancerous CHO cells.