Deep eutectic solvents induced changes in the phase transition behavior of smart polymers: a sustainable future approach.

Deep eutectic solvents (DESs) are considered "green" and "sustainable" alternatives to conventional organic solvents and ionic liquids (ILs) due to their characteristic properties and relatively low costs. DESs are considered IL analogs and have attracted consideration as benign media formulations for the synthesis of novel polymers because they satisfy the principle of sustainability. Over the past few years, the use of DESs has resulted in novel pathways for the synthesis of novel materials, biomaterials, functional materials, and ionic soft materials. Furthermore, DESs have been widely applied in the science, industrial, engineering, and technological fields. On the other hand, stimulus-responsive (smart) polymers have been widely utilized in intelligent devices owing to their virtues of good processibility, stimuli and environmental sensitivity, responsivity, and so on. With the introduction of a DES into the smart polymeric matrices, their potential characteristics, biocompatibility, and flexibility endow the corresponding DES-based polymeric materials with intriguing properties, which in turn will broaden their applications in various domains of polymer science and material chemistry. Substantial research has been done in the fabrication of DES-based polymeric materials. Numerous studies have extensively investigated the effects of DESs on biomolecules such as proteins/enzymes and nucleic acids, whereas few have addressed the impact of DESs on the aggregation and phase transition behaviors of smart polymers. This review focuses on mechanistic insights, aggregation behavior, and interactions between smart polymers and DESs. Opportunities and future research perspectives in this blossoming arena are also discussed. It is hoped that this review will pave futuristic pathways for the design and development of advanced DES-based polymeric materials and biomaterials for various applications.

Cancer treatment and toxicity outlook of nanoparticles.

Diversified nanosystems with tunable physicochemical attributes have emerged as potential solution to globally devastating cancer by offering novel possibilities for improving the techniques of cancer detection, imaging, therapies, diagnosis, drug delivery and treatment. Drug delivery systems based on nanoparticles (NPs) with ability of crossing different biological barriers are becoming increasingly popular. Besides, NPs are utilized in pharmaceutical sciences to mitigate the toxicity of conventional cancer therapeutics. However, significant NPs-associated toxicity, off-targeted activities, and low biocompatibility limit their utilization for cancer theranostics and can be hazardous to cancer patients up to life-threatening conditions. NPs interact with the biomolecules and disturb their regular function by aggregating inside cells and forming a protein corona, and the formulation turns ineffective in controlling cancer cell growth. The adverse interactions between NPs and biological entities can lead to life-threatening toxicities. This review focuses on the widespread use of various NPs including zinc oxide, titanium oxide, silver, and gold, which serve as efficient nano-vehicles and demonstrate notable pharmacokinetic and pharmacodynamic advantages in cancer therapy. Subsequently, the mechanism of nanotoxicity attached with these NPs, alternate solutions and their prospect to revolutionize cancer theranostics are highlighted. This review will serve as guide for future developments associated with high-performance NPs with controlled toxicity for establishing them as modern-age nanotools to manage cancer in tailored manner.

Panorama of biogenic nano-fertilizers: A road to sustainable agriculture.

The ever-increasing demand for food from the growing population has augmented the consumption of fertilizers in global agricultural practices. However, the excessive usage of chemical fertilizers with poor efficacy is drastically deteriorating ecosystem health through the degradation of soil fertility by diminishing soil microflora, environment contamination, and human health by inducing chemical remnants to the food chain. These challenges have been addressed by the integration of nanotechnological and biotechnological approaches resulting in nano-enabled biogenic fertilizers (NBF), which have revolutionized agriculture sector and food production. This review critically details the state-of-the-art NBF production, types, and mechanism involved in cultivating crop productivity/quality with insights into genetic, physiological, morphological, microbiological, and physiochemical attributes. Besides, it explores the associated challenges and future routes to promote the adoption of NBF for intelligent and sustainable agriculture. Furthermore, diverse applications of nanotechnology in precision agriculture including plant biosensors and its impact on agribusiness and environmental management are discussed.

Agro-waste to sustainable energy: A green strategy of converting agricultural waste to nano-enabled energy applications.

The rising demands of the growing population have raised two significant global challenges viz. energy crisis and solid-waste management, ultimately leading to environmental deterioration. Agricultural waste (agro-waste) contributes to a large amount of globally produced solid waste, contaminating the environment, and raising human-health issues on improper management. It is essential for a circular economy to meet sustainable development goals and to design strategies to convert agro-waste into energy using nanotechnology-based processing strategies, by addressing the two significant challenges. This review illustrates the nano-strategic aspects of state-of-the-art agro-waste applications for energy harvesting and storage. It details the fundamentals related to converting agro-waste into energy resources in the form of green nanomaterials, biofuels, biogas, thermal energy, solar energy, triboelectricity, green hydrogen, and energy storage modules in supercapacitors and batteries. Besides, it highlights the challenges associated with agro-waste-to-green energy modules with their possible alternate solutions and advanced prospects. This comprehensive review will serve as a fundamental structure to guide future research on smart agro-waste management and nanotechnological innovations dedicated to its utilization for green energy applications without harming the environment. The nanomaterials assisted generation and storage of energy from agro-waste is touted to be the near-future of smart solid-waste management strategy for green and circular economy.

Effect of Imidazolium Nitrate Ionic Liquids on Conformational Changes of Poly(N-vinylcaprolactam).

Detailed information about molecular interactions and conformational changes of polymeric components in the presence of ionic liquids (ILs) is essential for designing novel polymeric ionic liquid-based biomaterials. In biomaterials science and technology, thermoresponsive polymers (TRPs) are widely viewed as potential candidates for the fabrication of biorelated medical devices. Here, we synthesized thermoresponsive poly(N-vinyl-caprolactam) (PVCL) polymer and investigated the effects of imidazolium-based ILs (1-ethyl-3-methyl imidazolium nitrate and 1-butyl-3-methylimidazolium nitrate) with common anion and different cations on the phase transition behavior of PVCL aqueous solution. The impact of ILs on the phase transition behavior of PVCL was monitored by using UV-visible absorption spectra, steady-state fluorescence spectroscopy, thermal fluorescence spectroscopy, and temperature dependent dynamic light scattering. Results showed significant changes in the absorbance, molecular interactions, agglomeration, and coil to globule transition behaviors of PVCL in the presence of two ILs. PVCL aqueous solution showed significant conformational changes after the addition of ILs.

How do biological stimuli modulate conformational changes of biomedical thermoresponsive polymer?

Continuing efforts to develop stimuli-responsive polymers (SRPs) as novel smart materials/biomaterials are anticipated to upgrade the quality life of humans. The details of the molecular, physico chemical and biophysical interactions between SRPs and proteins are not fully understood. Indeed, protein - polymer interactions play a major role in a wide range of biomedical/biomaterial applications. In this regard, we have demonstrated the influence of proteins (ß-lactoglobulin (BLG) and stem bromelain (BM) as biological stimuli) on the phase transition behavior of biomedical thermoresponsive poly(N-isopropylacrylamide) (PNIPAM). In order to predict these, we have used a set of biophysical techniques to unveil the influence of biological stimuli on the phase transition behavior of PNIPAM. Absorption spectroscopy, steady-state fluorescence spectroscopy, Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM) were operated at room temperature to examine the changes in absorbance, fluorescence intensity, molecular interactions and surface morphologies, respectively. Furthermore, temperature dependent fluorescence spectroscopy and dynamic light scattering (DLS) studies were also performed to analyze conformational changes, agglomeration behavior, particle size, coil to globule transition and phase behavior. The significant variations obtained in the phase transition temperature values, conformational changes and agglomeration behavior clearly reflects the different molecular interplay induced in presence of biological stimuli. The results demonstrated that the added proteins act as biological stimuli via preferential interactions between the amide group of the polymer and water molecules. The present study can be useful for the design and development of the next generation smart responsive materials/biomaterials.

Influence of biological stimuli on the phase behaviour of a biomedical thermoresponsive polymer: A comparative investigation of hemeproteins.

HYPOTHESIS: Thorough knowledge of the biomolecular interactions between thermoresponsive polymers (TRPs) and proteins are necessary to fabricate potential materials for various bio-related science and technology applications. Although over the past four decades have evidenced that tremendous growth in the utilization of TRPs in the addition of various stimuli systems, a underlying molecular origins of the role of biological stimuli on TRPs phase transition is still missing. EXPERIMENTS: We demonstrated the comparative effect of heme proteins (biological stimuli) such as cytochrome c (Cyt c) and myoglobin (Mb) on the phase behaviour of poly(N-isopropylacrylamide) (PNIPAM) aqueous solution. The sophisticated multiple techniques have confirmed that the structural integrity of the proteins is found to play a vital role in altering the phase transition temperature of PNIPAM to different extents with increasing the concentration of proteins. FINDINGS: With the addition of Cyt c, the lower critical solution temperature (LCST) of PNIPAM (33.0 °C) increased towards higher temperature (35.7 °C) in contrast to this with the addition of Mb the LCST of PNIPAM decreased towards lower temperature (30.7 °C). This discrepancy is due to the difference in contrast structural arrangements of both proteins on the LCST of PNIPAM. On the basis of these results, the variation in the structures of both heme proteins, hydration and dehydration between the heme proteins are compared. These results demonstrated that depending on the type of smart polymers used for bio-related applications, it is necessary to take into account the effect of biological stimuli while designing polymers. We hope that the present study can stimulate more novel concepts and dramatic changes in smart polymer and protein interactions.