CB[6]/ZnO Chelated Superoleophobic-Hydrophilic PVDF Membranes for One-step Remediation of Multi-Contaminant in Wastewater.

Industrial wastewater, despite undergoing primary and secondary treatments with conventional methods, continues to pose challenges due to the presence of multiple contaminants. Membrane separation has emerged as an effective solution to streamline the treatment process, yet it often results in surface fouling. This study introduces a single platform designed for simultaneous removal of dyes, oils, and proteins during the tertiary treatment stage, thereby eliminating the need for multiple separation steps. To enhance membrane robustness and address common fouling issues, polyvinylidene fluoride-montmorillonite-cucurbit[6]uril/zinc oxide (PV-M-CB[6]ZnO) mixed-matrix membranes have been developed. The incorporation of montmorillonite (M), cucurbit[6]uril (CB[6]) host-guest encapsulation, and zinc metal chelation significantly improves the membrane's capability in eliminating cationic dyes, treating oil-water emulsions, and separating bovine serum albumin. With an optimal CB[6]/ZnO loading of 1.6 wt%, the PV-M-CB[6]ZnO membranes exhibit superior performance with high water permeability (4114 L/m2.h.bar) and exceptional separation efficiencies: 95.5% for malachite green, 93.2% for methylene blue, and 98.2% for crystal violet, compared to pristine PVDF membranes. Additionally, these membranes demonstrate an impressive oil-water rejection rate of 97.6% and a bovine serum albumin rejection rate of 76%, with a flux recovery ratio exceeding 86% after seven filtration cycles. Thus, the PV-M-CB[6]ZnO membranes offer enhanced hydrophilicity, improved antifouling properties, and increased efficiency for the removal of multiple contaminants from industrial wastewater, providing a promising solution for sustainable environmental remediation.

Two decades of two-photon lithography: Materials science perspective for additive manufacturing of 2D/3D nano-microstructures.

Two-photon lithography (TPL) is a versatile technology for additive manufacturing of 2D and 3D micro/nanostructures with sub-wavelength resolved features. Recent advancement in laser technology has enabled the application of TPL fabricated structures in several fields such as microelectronics, photonics, optoelectronics, microfluidics, and plasmonic devices. However, the lack of two-photon polymerizable resins (TPPRs) induces bottleneck to the growth of TPL to its true potential, and hence continuous research efforts are focused on developing efficient TPPRs. In this article, we review the recent advancements in PI and TPPR formulation and the impact of process parameters on fabrication of 2D and 3D structures for specific applications. The fundamentals of TPL are described, followed by techniques used for achieving improved resolution and functional micro/nanostructures. Finally, a critical outlook and future prospects of TPPR formulation for specific applications are presented.

Bacillussp. based nano-bio hybrids for efficient water remediation.

Macroalgae are a diverse group of primary producers that offer indispensable ecosystem services towards bacterial colonization and proliferation in aquatic biomes. Macroalgae/bacteria interactions are complex in natural biomes and contribute mutually to their growth and biotechnological outcomes. Most findings on macroalgae-associated bacteria and their secreted enzymes have largely been limited to nutraceutical applications. Here, in this study, we demonstrate and investigate the growth of Bacillus sp. (macroalgae-associated bacteria) with the substitution of its associated macroalgae (Gracilaria corticata) on graphene oxide (GO). The findings indicated that the presence of wrinkles of GO nanosheets resulted in cell proliferation and adherence without causing mechanical damage to the cell membrane. Furthermore, the assembly of GO-marine bacteria was explored for organic pollutant treatment using methylene blue (MB) as a model dye. The degradation results suggest the breakdown of MB into non-toxic byproducts as suggested by the phytotoxicity assay.

Modified PVA membrane for separation of micro-emulsion.

Release of liquefied hydrocarbons in domestic and industrial effluents, along with oil spills cause significant adverse effects on the soil, water, aquatic ecosystem, and humans. Thus, selective and cost-effective technology to address this challenge is highly desirable. Here, we report the fabrication of electrospun polyvinyl alcohol (PVA) membrane, modified with glutaraldehyde (GA) and a device thereof, for treatment of oil emulsions and recovery of precious fossil fuel. The modified PVA membranes are super-oleophobic with a high static underwater oil contact angle of 163 ± 3° for motor oil. Investigation of wetting properties suggests that the membrane can efficiently separate different oils such as sesame oil, motor oil, mustard oil, and sunflower oil from their emulsions. The motor oil emulsion with separation efficiency of >99% at an excellent permeate flux of 5128 L/m2·h·bar has been achieved. Thus, the prepared modified PVA membrane construes an easy solution for not only effective treatment of oily wastewater but also for oil recovery with high flux.

Additive-Free All-Carbon Composite: A Two-Photon Material System for Nanopatterning of Fluorescent Sub-Wavelength Structures.

The major bottleneck in fabrication of engineered 3D nanostructures is the choice of materials. Adding functionality to these nanostructures is a daunting task. In order to mitigate these issues, we report a two-photon patternable all carbon material system which can be used to fabricate fluorescent 3D micro/nanostructures using two-photon lithography, with subwavelength resolution. The synthesized material system eliminates the need to use conventional two-photon absorbing materials such as two-photon dyes or two-photon initiators. We have used two different trifunctional acrylate monomers and carbon dots, synthesized hydrothermally from a polyphenolic precursor, to formulate a two-photon processable resin. Upon two-photon excitation, photogenerated electrons in the excited states of the carbon dots facilitate the free radical formation at the surface of the carbon dots. These radicals, upon interaction with vinyl moieties, enable cross-linking of acrylate monomers. Free-radical induced two-photon polymerization of acrylate monomers without any conventional proprietary two-photon absorbing materials was accomplished at an ultrafine subwavelength resolution of 250 nm using 800 nm laser excitation. The effect of critical parameters such as average laser power, carbon dot concentration, and radiation exposure were determined for the fabrication of one-, two-, and three-dimensional functional nanostructures, applicable in a range of domains where fluorescence and toxicity are of the utmost importance. A fabrication speed as high as 100 mm/s was achieved. The ability to fabricate functional 3D micro-/nanostructures is anticipated to instigate a paradigm shift in various areas such as metamaterials, energy storage, drug delivery, and optoelectronics to name a few.

Surface Engineering of Graphene Oxide Shells Using Lamellar LDH Nanostructures.

The discovery of graphene oxide (GO) has made a profound impact on varied areas of research due to its excellent physicochemical properties. However, surface engineering of these nanostructures holds the key to enhanced surface properties. Here, we introduce surface engineering of reduced GO (rGO) shells by radially grafting Ni-Co layered double hydroxide (LDH) lamella on rGO shells to form Ni-Co LDH@rGO. The morphology of synthesized Ni-Co LDH@rGO mimics dendritic cell-like three-dimensional (3D) hierarchical morphologies. Silica nanospheres form self-sacrificial templates during the reduction of GO shells to form rGO shells during the template-assisted synthesis. The radial growth of LDH lamellae during hydrothermal process on GO shells provides access to a significantly larger number of additional active redox sites and overcompensates the loss of pseudocapacitive charge storage centers during the reduction of GO to form rGO shells. This enables in the synthesis of novel surface-engineered rGO nanoshells, which provide large surface area, enhanced redox sites, high porosity, and easy transport of ions. These synthesized 3D dendritic cell-like morphologies of Ni-Co LDH@rGO show a high capacitance of ∼2640 F g-1. A flexible hybrid device fabricated using this nanomaterial shows a high energy density of ∼35 Wh kg-1 and a power density of 750 W kg-1 at 1 A g-1. No appreciable compromise in device performance is observed under bending conditions. This synthesis strategy may be used in the development of functional materials useful for potential applications, including sensors, catalysts, and energy storage.

Rationally engineered 3D-dendritic cell-like morphologies of LDH nanostructures using graphene-based core-shell structures.

Functionalization of graphene-based materials using chemical moieties not only modify the electronic structure of the underlying graphene but also enable in limited enhancement of targeted properties. Surface modification of graphene-based materials using other nanostructures enhances the effective properties by minimally modifying the properties of pristine graphene backbone. In this pursuit, we have synthesized bio-inspired hierarchical nanostructures based on Ni-Co layered double hydroxide on reduced graphene oxide core-shells using template based wet chemical approach. The material synthesized have been characterized structurally and electrochemically. The fabricated dendritic morphology of the composite delivers a high specific capacity of 1056 Cg-1. A cost effective solid state hybrid supercapacitor device was also fabricated using the synthesized electrode material which shows excellent performance with high energy density and fast charging capability.

Predicting double negativity using transmitted phase in space coiling metamaterials.

Metamaterials are engineered materials that offer the flexibility to manipulate the incident waves leading to exotic applications such as cloaking, extraordinary transmission, sub-wavelength imaging and negative refraction. These concepts have largely been explored in the context of electromagnetic waves. Acoustic metamaterials, similar to their optical counterparts, demonstrate anomalous effective elastic properties. Recent developments have shown that coiling up the propagation path of acoustic wave results in effective elastic response of the metamaterial beyond the natural response of its constituent materials. The effective response of metamaterials is generally evaluated using the 'S' parameter retrieval method based on amplitude of the waves. The phase of acoustic waves contains information of wave pressure and particle velocity. Here, we show using finite-element methods that phase reversal of transmitted waves may be used to predict extreme acoustic properties in space coiling metamaterials. This change is the difference in the phase of the transmitted wave with respect to the incident wave. This method is simpler when compared with the more rigorous 'S' parameter retrieval method. The inferences drawn using this method have been verified experimentally for labyrinthine metamaterials by showing negative refraction for the predicted band of frequencies.

Optical properties of stanene.

Successful synthesis of graphene has created a runaway effect in the exploration of other similar two-dimensional materials. These materials are important as they provide large surface areas and have led to the exploration of new physical phenomena. Even though graphene has exotic electronic properties, its spin-orbit coupling is very weak. Tin, being one of the heaviest elements in this group, is expected to have enhanced spin-orbit coupling in addition to other exotic properties of graphene. Here we report optical signatures of free standing stanene obtained using UV-vis absorption spectroscopy. Raman measurements were performed on a transmission electron microscope (TEM) grid. Interlayer spacing, phonon frequencies and the imaginary part of the complex dielectric function obtained using first principles methods are in good agreement with the experimental data. Occurrence of parallel bands suggests the possibility of the presence of excitonic effects in stanene.

Double Negativity in 3D Space Coiling Metamaterials.

Metamaterials displaying negative refractive index has remarkable potential to facilitate the manipulation of incident waves for wide variety of applications such as cloaking, superlensing and the like. Space-coiling approach is a recently explored technique to achieve extreme properties. The space coiling phenomena cause less energy absorption as compared to local resonating phenomena for obtaining extreme parameters. Here we show extreme properties in doubly negative 3D space coiling acoustic metamaterials. Frequency dispersive spectrum of extreme constitutive parameters has been calculated for 2D maze and 3D space coiling labyrinthine structure. This is in good agreement to the calculated acoustic band dispersion.

Stanene: Atomically Thick Free-standing Layer of 2D Hexagonal Tin.

Stanene is one of most important of 2D materials due to its potential to demonstrate room temperature topological effects due to opening of spin-orbit gap. In this pursuit we report synthesis and investigation of optical properties of stanene up to few layers, a two-dimensional hexagonal structural analogue of graphene. Atomic scale morphological and elemental characterization using HRTEM equipped with SAED and EDAX detectors confirm the presence of hexagonal lattice of Sn atoms. The position of Raman peak along with the inter-planar 'd' spacing obtained from SAED for prepared samples are in good agreement with that obtained from first principles calculations and confirm that the sheets are not (111) α-Sn sheets. Further, the optical signature calculated using density functional theory at ~191 nm and ~233 nm for low buckled stanene are in qualitative agreement with the measured UV-Vis absorption spectrum. AFM measurements suggest interlayer spacing of ~0.33 nm in good agreement with that reported for epitaxial stanene sheets. No traces of oxygen were observed in the EDAX spectrum suggesting the absence of any oxidized phases. This is also confirmed by Raman measurements by comparing with oxidized stanene sheets.

3D Oxidized Graphene Frameworks for Efficient Nano Sieving.

The small size of Na(+) and Cl(-) ions provides a bottleneck in desalination and is a challenge in providing alternatives for continuously depleting fresh water resources. Graphene by virtue of its structural properties has the potential to address this issue. Studies have indicated that use of monolayer graphene can be used to filter micro volumes of saline solution. Unfortunately it is extremely difficult, resource intensive and almost impractical with current technology to fabricate operational devices using mono-layered graphene. Nevertheless, graphene based devices still hold the key to solve this problem due to its nano-sieving ability. Here we report synthesis of oxidized graphene frameworks and demonstrate a functional device to desalinate and purify seawater from contaminants including Na(+) and Cl(-) ions, dyes and other microbial pollutants. Micro-channels in these frameworks help in immobilizing larger suspended solids including bacteria, while nano-sieving through graphene enables the removal of dissolved ions (e.g. Cl(-)). Nano-sieving incorporated with larger frameworks has been used in filtering Na(+) and Cl(-) ions in functional devices.

Plasmonic micro lens for extraordinary transmission of broadband light.

Extraordinary transmittance and focusing of light in quasi far field region using miniaturized optical devices is a daunting task. A polarization independent, broadband, planar metallic transmissive micro aperture capable of achromatically focusing visible light in quasi far field region is proposed. The calculated enhancement factor of transmission efficiency was about ~2.2. The total transmission after the aperture is about 60%. This high throughput focusing device will open new avenues for focusing electromagnetic energy in the wide area of sensors and energy concentration.

Subwavelength direct laser patterning of conductive gold nanostructures by simultaneous photopolymerization and photoreduction.

This article presents a new method for fabricating highly conductive gold nanostructures within a polymeric matrix with subwavelength resolution. The nanostructures are directly written in a gold precursor-doped photoresist using a femtosecond pulsed laser. The laser energy is absorbed by a two-photon dye, which induces simultaneous reduction of gold in the precursor and polymerization of the negative photoresist. This results in gold nanoparticle-doped polymeric lines that exhibit both plasmonic effects, due to the constituent gold nanoparticles, and relatively high conductivity (within an order of magnitude of the bulk metal), due to the high density of particles within these lines. Line widths from 150 to 1000 nm have been achieved with this method. Various optically functional structures have been prepared, and their structural and optical properties have been characterized. The influence of laser intensity and scan speed on feature size have been studied and found to be in agreement with predictions of a mathematical model of the process.

Fabrication and characterization of gold-polymer nanocomposite plasmonic nanoarrays in a porous alumina template.

A facile, cost-effective, and manufacturable method to produce gold-polymer nanocomposite plasmonic nanorod arrays in high-aspect-ratio nanoporous alumina templates is reported, where the formation of gold nanoparticles and the polymerization of a photosensitive polymer by ultraviolet light are simultaneously performed. Transverse mode coupling within a two-dimensional array of the nanocomposite rods results in a progression of resonant modes in the visible and infrared spectral regions when illuminated at normal incidence, a phenomenon previously observed in nanoarrays of solid gold rods in an alumina template. Finite element full-wave analysis in a three-dimensional computational domain confirms our hypothesis that nanoparticles, arranged in a columnar structure, will show a response similar to that of solid gold rods. These studies demonstrate a new simple method of plasmonic nanoarray fabrication, apparently obviating the need for a cumbersome electrochemical process to grow nanoarrays.

Large-area, near-infrared (IR) photonic crystals with colloidal gold nanoparticles embedding.

A polymeric composite material composed of colloidal gold nanoparticles (<10 nm) and SU8 has been utilized for the fabrication of large-area, high-definition photonic crystal. We have successfully fabricated near-infrared photonic crystal slabs from composite materials using a combination of multiple beam interference lithography and reactive ion etching processes. Doping of colloidal gold nanoparticles into the SU8 photopolymer results in a better definition of structural features and hence in the enhancement of the optical properties of the fabricated photonic crystals. A 2D air hole array of triangular symmetry with a hole-to-hole pitch of approximately 500 nm has been successfully fabricated in a large circular area of 1 cm diameter. Resonant features observed in reflectance spectra of our slabs are found to depend on the exposure time, and can be tuned over a range of near-infrared frequencies.

Synthesis and properties of quantum dot-polypyrrole nanotube composites for photovoltaic application.

A novel method for the fabrication of polypyrrole nanotubes (PPyNTs) possessing quantum dots (QDs) was developed for optoelectronic devices. PbSe QDs were effectively attached to the thiolated PPyNT-SH without affecting the dispersion stability of QDs and hence ensuring their homogeneous distribution in the polymer. Transmission electron microscopic images showed a large number of PbSe QDs absorbed in PPyNT-SH. The polymer nanotube composites were also investigated for the application of photovoltaic cells. An open circuit voltage (V(oc)) of 0.45 V and short-circuit photocurrent density (I(sc)) of 2.4 microA cm(-2) were found in P3HT/PPyNT-PbSe polymeric solar cells. Further optimization will be provided by changing various parameters and conditions.

Spectroscopic investigations of carious tooth decay.

We report on the elemental composition of healthy and infected part of human tooth using laser induced breakdown spectroscopy (LIBS). We have used prominent constituent transitions in laser-excited tooth to diagnose the state of the tooth. A nanosecond laser pulse (355nm, 5ns) was used as an ablating pulse and the sodium (3s2S-3p2P) at 588.99 and (3s2S-3p2P) at 589.99nm, strontium (5s21S-1s5P) at 460.55nm, and calcium (3d3D-4f 3F0) at 452.55nm transitions for spectroscopic analysis. The spectroscopic observations in conjunction with discriminate analysis showed that calcium attached to the hydroxyapatite structure of the tooth was affected severely at the infected part of the tooth. The position-time plots generated from two-dimensional (2D) images conclusively showed a decrease in calcium concentration in the infected region of the irradiated tooth. Using the technique, we could distinguish between the healthy and carious parts of the tooth with significant accuracy.