This review presents precisely defined amphiphilic dendrons, their self-association properties, and their different uses. Dendrons, also named dendritic wedges, are composed of a core having two different types of functions, of which one type is used for growing or grafting branched arms, generally multiplied by 2 at each layer by using 1→2 branching motifs. A large diversity of structures has been already synthesized. In practically all cases, their synthesis is based on the synthesis of known dendrimers, such as poly(aryl ether), poly(amidoamine) (in particular PAMAM), poly(amide) (in particular poly(L-lysine)), 1→3 branching motifs (instead of 1→2), poly(alkyl ether) (poly(glycerol) and poly(ethylene glycol)), poly(ester), and those containing main group elements (poly(carbosilane) and poly(phosphorhydrazone)). In most cases, the hydrophilic functions are on the surface of the dendrons, whereas one or two hydrophobic tails are linked to the core. Depending on the structure of the dendrons, and on the experimental conditions used, the amphiphilic dendrons can self-associate at the air-water interface, or form micelles (eventually tubular, but most generally spherical), or form vesicles. These associated dendrons are suitable for the encapsulation of low-molecular or macromolecular bioactive entities to be delivered in cells. This review is organized depending on the nature of the internal structure of the amphiphilic dendrons (aryl ether, amidoamine, amide, quaternary carbon atom, alkyl ether, ester, main group element). The properties issued from their self-associations are described all along the review.

Supramolecular Self-Associations of Amphiphilic Dendrons and Their Properties.

Eco-friendly polymers exhibit distinctive physiochemical properties after their transformation in metal nanocomposites. Significant attention by the researchers have been paid in developing polymeric metal composites at nano scale molecular size due to their promising potential for energy storage, environmental remediation, electromagnetic absorption, environment safety etc. and thus green metal nanocomposites have applications in resolving both energy and environmental issues. Easy processing and low cost production of these polymeric materials also attract green chemists to develop novel polymeric metal composites. The significant progress in processing, characterization and modelling of nano sized materials create many opportunities for technical support in the development and designing of biodegradable polymers with metal nancomposite systems. But still there are lots of challenges viz. limited availability of high-quality nanofillers, their high production cost, difficulties to scale up, lack of deep knowledge, understanding and predictive capability in the area of key processes, structures and properties, which are needed to fully utilization of these materials for the commercial benefits which are remained unaddressed. Keeping in view to provide a comprehensive details for researchers to find a better solution of above challenges, in this chapter, centre of attention has been created on the latest and advanced field of research in which designing of green materials of biodegradable polymers with metal nanocomposites and their utilization for different devices such as development of electrochemical cells and batteries for energy storage, electro-chromic devices for conservation of energy, gaseous capturing devices for safety of environment have been discussed. 

Green Polymers Decorated with Metal Nanocomposites: Application in Energy Storage, Energy Economy and Environmental Safety

The reversible nature of disulfide functionality has been exploited to design intelligent materials such as nanocapsules, micelles, vesicles, inorganic nanoparticles, peptide and nucleic acid nanodevices. Herein, we report a new chemical methodology for the construction redox-sensitive protein assemblies using monodisperse facially amphiphilic protein-dendron bioconjugates. The disulfide functionality is strategically placed between the dendron and protein domains. The custom designed bioconjugates self-assembled into nanoscopic objects of a defined size dictated by the nature of dendron domain. The stimuli-responsive behavior of the protein assemblies is demonstrated using a suitable redox trigger.

Rational Design of Programmable Monodisperse Semi-Synthetic Protein Nanomaterials Containing Engineered Disulfide Functionality**

Self-assembly of a monomeric protease to form a multi-subunit protein complex "proteasome" enables targeted protein degradation in living cells. Naturally occurring proteasomes serve as an inspiration and blueprint for the design of artificial protein-based nanoreactors. Here we disclose a general chemical strategy for the design of proteasome-like nanoreactors. Micelle-assisted protein labeling (MAPLab) technology along with the N-terminal bioconjugation strategy is utilized for the synthesis of a well-defined monodisperse self-assembling semi-synthetic protease. The designed protein is programmed to self-assemble into a proteasome-like nanostructure which preserves the functional properties of native protease.

A Universal Chemical Method for Rational Design of Protein-Based Nanoreactors*.

The present invention discloses monodisperse protein-dendron conjugates that self-assemble to generation-dependent supramolecular protein assemblies of different size and surface charges. The invention further provides a process for synthesis of protein-dendron conjugates containing hydrophobic dendron of different generations.

Generation-Dependent Supramolecular Assemblies of Protein-Dendron Conjugates

The design of well-defined monodispersed self-assembling semi-synthetic proteins is emerging as a promising research avenue. These proteins hold great potential to be used as scaffolds for various protein nanotechnology applications. Currently, there are very few chemical methods reported; however, they suffer from elaborate multistep organic synthesis. Herein, we report a new chemical methodology for the rapid synthesis of a diverse set of semi-synthetic protein families, which include protein amphiphiles, facially amphiphilic protein-dendron conjugates, and pH-sensitive protein-dendron conjugates. This chemical method holds great potential to access a wide variety of semi-synthetic proteins in a short time.

Rapid Chemical Synthesis of Self-Assembling Semi-Synthetic Proteins.

Self-assembling artificial proteins (SAPs) have gained enormous interest in recent years due to their applications in different fields. Synthesis of well-defined monodisperse SAPs is accomplished predominantly through genetic methods. However, the last decade witnessed the use of few chemical technologies for that purpose. In particular, micelle-assisted protein labeling technology (MAPLabTech) has made huge progress in this area. The first generation MAPLabTech focused on site-specific labeling of the active-site residue of serine proteases to make SAPs. Further, this methodology was exploited for labeling of N-terminal residue of a globular protein to make functional SAPs. In this study, we describe the synthesis of novel SAPs by developing a chemical method for site-specific labeling of a surface-exposed cysteine residue of globular proteins. In addition, we disclose the synthesis of redox- and pH-sensitive SAPs and their systematic self-assembly and dis-assembly studies using complementary biophysical studies. Altogether these studies further expand the scope of MAPLabTech in different fields such as vaccine design, targeted drug delivery, diagnostic imaging, biomaterials, and tissue engineering.

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Rational Design of Self-assembling Artificial Proteins Utilizing a Micelle-Assisted Protein Labeling Technology (MAPLabTech): Testing the Scope

The present invention discloses hydrophobin mimics of formula (I) comprising a protein head group, hydrophilic linker and hydrophobic tail and to a process for synthesis of library of hydrophobin mimics thereof. The hydrophobin mimics of the present invention self-assemble to form protein nanoparticles/nanocontainer either alone or in a specified chemical environment. The hydrophobin mimics (I) of the present invention find application in area of bio-nanotechnology.

Pavankumar Janardhan Bhandari

Papers

Rapid Chemical Synthesis of Self-Assembling Semi-Synthetic Proteins.

Rational Design of Self-assembling Artificial Proteins Utilizing a Micelle-Assisted Protein Labeling Technology (MAPLabTech): Testing the Scope

Hydrophobin mimics: process for preparation thereof