Uttam Manna

Restoration of Superhydrophobicity in Crushed Polymer Films by Treatment with Water: Self-Healing and Recovery of Damaged Topographic Features Aided by an Unlikely Source

The crushing of superhydrophobic polymer multilayers destroys micro/nanoscale topographic features critical for the maintenance of superhydrophobicity. We demonstrate that these surface features can be recovered, and that superhydrophobicity can be fully restored, by treatment of damaged films with liquid water. These polymer-based films can also sustain other forms of severe abuse without loss of superhydrophobicity. This combination of features addresses several important practical issues associated with the durability of artificial superhydrophobic surfaces.

Glucose-triggered drug delivery from borate mediated layer-by-layer self-assembly.

In this study, we report a novel approach for glucose-triggered anticancer drug delivery from the self-assembly of neutral poly(vinyl alcohol) (PVA) and chitosan. In the present study, we have fabricated multilayer thin film of PVA-borate and chitosan on colloidal particle (MF particle) and monitored the layer-by-layer growth using Zeta potential measurements. Formation of multilayer membrane on MF particle has been further characterized with transmission electron microscopy (TEM) and confocal laser scanning microscopy (CLSM). Subsequently, disintegration of multilayer thin film and microcapsules was observed in presence of glucose. We investigated the disassembly of PVA-borate and chitosan self-assembly under CLSM and atomic force microscopy. These results suggest that this multilayer thin film is very efficient for encapsulation and release of DOX molecules above certain concentration of glucose (25 mM). This glucose-sensitive self-assembly is relevant for the application of anticancer therapeutic drug delivery.

Layer-by-Layer Self-Assembly of Modified Hyaluronic Acid/Chitosan Based on Hydrogen Bonding

The fabrication of hydrogen bonded polymer self-assembly for drug delivery has been accomplished via layer-by-layer sequential assembly from aqueous solution. In this study, the self-assembly was constructed based on hydrogen bonding between DNA base (adenine and thymine) pairs substituted on the backbone of chitosan and hyaluronic acid. Chitosan was modified with adenine, whereas hyaluronic acid was modified with thymine. Subsequently, these two polymers were sequentially absorbed on flat substrate by taking advantage of interactions of DNA base pairs via hydrogen bonding. Interlayer hydrogen bonding of these two polymers produces stable multilayer film without using any cross-linking agent. Thin film formation on quartz substrate has been monitored with UV-vis spectra and an AFM study. Formation of multilayer hydrogen-bonded thin film has been further confirmed with SEM. Encapsulation and release behavior of the therapeutic drug from the multilayer thin film at different conditions has been illustrated using UV-vis spectra. Cell viability of modified polymers using MTT assay confirmed no cytotoxic effect.

Synthetic Surfaces with Robust and Tunable Underwater Superoleophobicity

The present invention provides multilayer polymer films, materials and coatings which exhibit robust underwater superoleophobicity and have remarkable structural functional tolerance to a broad range of physical, chemical, and environmental challenges encountered by surfaces deployed in aqueous or aquatic environments. These materials can be fabricated on surfaces of arbitrary shape, size, and composition and provide straightforward means to manipulate surface chemistry and fine-tune other useful features of the interfacial behavior (e.g., underwater oil-adhesiveness). These materials address key obstacles to the application of non-wetting surfaces and anti-fouling ‘super-phobic’ materials in practical, real-world scenarios.

Multilayer Self-Assembly of TiO2 Nanoparticles and Polyaniline-Grafted-Chitosan Copolymer (CPANI) for Photocatalysis

A photocatalytic thin film of TiO₂ nanoparticles and polyaniline-grafted-chitosan (CPANI) was fabricated by layer-by-layer (LbL) approach. The growth of the self-assembly of polymer nanocomposite was monitored by UV-vis spectroscopy and the thin film morphology was analyzed from scanning electron microscopy (SEM). Poly(styrene sulfonate) (PSS) was used as a bridging layer between TiO₂ nanoparticles and CPANI. Incorporation of CPANI within the LbL self-assembly of polymer nanocomposites enhanced the dye degradation ability of the thin film. These results indicate that the presence of CPANI improves the adsorption of dye in the self-assembly. The effect of surface area and the amount of catalyst was also examined. The reusability of the thin films for dye degradation study ensures the stability of the self-assembly.

Borax mediated layer-by-layer self-assembly of neutral poly(vinyl alcohol) and chitosan.

We report a multilayer film of poly(vinyl alcohol) (PVA)-borate complex and chitosan by using a layer-by-layer approach. PVA is an uncharged polymer, but hydroxyl functional groups of PVA can be cross-linked by using borax as a cross-linking agent. As a result electrostatic charges and intra- and interchain cross-links are introduced in the PVA chain and provide physically cross-linked networks. The PVA-borate was then deposited on a flat substrate as well as on colloidal particles with chitosan as an oppositely charged polyelectrolyte. Quartz crystal microbalance, scanning electron microscopy, and atomic force microscopy were used to follow the growth of thin film on flat substrate. Analogous experiments were performed on melamine formaldehyde colloidal particles (3-3.5 microm) to quantify the process for the preparation of hollow microcapsules. Removal of the core in 0.1 N HCl results in hollow microcapsules. Characterization of microcapsules by transmission electron microscopy revealed formation of stable microcapsules. Further, self-assembly of PVA-borate/chitosan was loaded with the anticancer drug doxorubicin, and release rates were determined at different pH values to highlight the drug delivery potential of this system.

Dual Drug Delivery Microcapsules via Layer-by-Layer Self-Assembly

The integration of hydrophobic and hydrophilic drugs in the polymer microcapsule offers the possibility of developing a new drug delivery system that combines the best features of these two distinct classes of material. Recently, we have reported the encapsulation of an uncharged water-insoluble drug in the polymer membrane. The hydrophobic drug is deposited using a layer-by-layer (LbL) technique, which is based on the sequential adsorption of oppositely charged polyelectrolytes onto a charged substrate. In this paper, we report the encapsulation of two different drugs, which are invariably different in structure and in their solubility in water. We have characterized these dual drug vehicular capsules by confocal laser scanning microscopy, atomic force microscopy, visible microscopy, and transmission electron microscopy. The growth of a thin film on a flat substrate by LbL was monitored by UV-vis spectra. The desorption kinetics of two drugs from the thin film was modeled by a second-order rate model.

Fabrication of Liquid‐Infused Surfaces Using Reactive Polymer Multilayers: Principles for Manipulating the Behaviors and Mobilities of Aqueous Fluids on Slippery Liquid Interfaces

The design of slippery liquid-infused porous surfaces (SLIPS) using nanoporous and chemically reactive polymer multilayers is reported. This approach permits fabrication of slippery anti-fouling coatings on complex surfaces and provides new means to manipulate the mobilities of contacting aqueous fluids. The results expand the range of tools that can be used to manipulate the behaviors of SLIPS and open the door to new applications of this emerging class of soft materials.

Encapsulation of uncharged water-insoluble organic substance in polymeric membrane capsules via layer-by-layer approach.

We report a general and versatile method for the encapsulation of electrically uncharged organic substance in polymeric capsules by using a layer-by-layer (LbL) approach. Electrical charge was induced on the surface of pyrene (uncharged organic substance) with an amphiphilic surfactant (sodium dodecyl sulfate, SDS) by micellar solubilization. The SDS micellar solution of pyrene in water was then deposited on a flat substrate as well as colloidal particles with chitosan as an oppositely charged polyelectrolyte. Pyrene was used as a model drug because it displayed intrinsic fluorescence that allowed us to monitor LbL growth by fluorescence and under confocal laser scanning microscopy (CLSM). To examine the proof of concept, multilayers were coated on the planar support by the LbL method. UV-vis spectroscopy showed regular growth of each layer deposited. Thin film formation was evidenced by scanning electron microscopy. The LbL method was extended to particles where fluorescence spectroscopy revealed LbL growth and transmission electron microscopy (TEM) provided evidence of particle coating. The quantification of dye in each deposited layer further proved LbL growth. The removal of sacrificial core provided thin capsules. The capsules were characterized by TEM and CLSM. The capsules showed potential as a drug delivery system, which is suggested by the slow release of entrapped dye by concentration-dependent diffusion in isotonic saline solution. The kinetics of desorption of pyrene from this thin film was modeled by a pseudo-second-order model.

Multilayer single-component thin films and microcapsules via covalent bonded layer-by-layer self-assembly

Fabrication of single-component multilayer thin films still remains a challenging task via the layer-by-layer (LbL) approach. In this communication, we report the self-assembly of single-component multilayer thin films on flat and colloidal substrates through glutaraldehyde mediated covalent bonding.