Search results for: nanomaterial

Authors: Anna Piasek, Anna Szymkiewicz, Gabriela Wiktor, Jolanta Pulit-Prociak, Marcin Banach

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Carbon dots (CDs) have great potential for application in many fields of science. They are characterized by fluorescent properties that can be manipulated. The nanomaterial has many advantages in addition to its unique properties. CDs may be obtained easily, and they undergo surface functionalization in a simple way. In addition, there is a wide range of raw materials that can be used for their synthesis. An interesting possibility is the use of numerous waste materials of natural origin. In the research presented here, the synthesis of CDs was carried out according to the principles of Green chemistry. Beet molasses was used as a natural raw material. It has a high sugar content. This makes it an excellent high-carbon precursor for obtaining CDs. To increase the fluorescence effect, we modified the surface of CDs with silver (Ag-CDs) nanoparticles. The process of obtaining CQD was based on the hydrothermal method by applying microwave radiation. Silver nanoparticles were formed via the chemical reduction method. The synthesis plans were performed on the Design of the Experimental method (DoE). Variable process parameters such as concentration of beet molasses, temperature and concentration of nanosilver were used in these syntheses. They affected the obtained properties and particle parameters. The Ag-CDs were analyzed by UV-vis spectroscopy. The fluorescence properties and selection of the appropriate excitation light wavelength were performed by spectrofluorimetry. Particle sizes were checked using the DLS method. The influence of the input parameters on the obtained results was also studied.

Keywords: fluorescence, modification, nanosilver, molasses, Green chemistry, carbon dots

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Authors: Tien S. H. Pham, Peter J. Mahon, Aimin Yu

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The detection of drug molecules by voltammetry has attracted great interest over the past years. However, many drug molecules exhibit poor electrochemical signals at common electrodes which result in low sensitivity in detection. An efficient way to overcome this problem is to modify electrodes with functional materials. Since discovered in 2004, graphene (or reduced graphene oxide) has emerged as one of the most studied two-dimensional carbon materials in condensed matter physics, electrochemistry, and so on due to its exceptional physicochemical properties. Additionally, the continuous development of technology has opened the new window for the successful fabrications of many novel graphene-based nanomaterials to serve in electrochemical analysis. This research aims to synthesize and characterize gold nanoparticle coated beta-cyclodextrin functionalized reduced graphene oxide (Au NP–β-CD–RGO) nanocomposites with highly conductive and strongly electro-catalytic properties as well as excellent supramolecular recognition abilities for the modification of electrodes. The electrochemical responses of ciprofloxacin at the as-prepared nanocomposite modified electrode was effectively amplified was much higher in comparison with that at the bare electrode. The linear concentration range was from 0.01 to 120 µM, with a detection limit of 2.7 nM using differential pulse voltammetry. Thus, Au NP–β-CD–RGO nanocomposite has great potential as an ideal material to construct sensitive sensors for the electrochemical determination of ciprofloxacin or similar antibacterial drugs in the future based on its excellent stability, selectivity, and reproducibility.

Keywords: Au nanoparticles, β-CD, ciprofloxacin, electrochemical determination, graphene based nanomaterials

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Authors: H. Boukhatem, L. Djouadi, H. Khalaf, R. M. Navarro, F. V. Ganzalez

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Synthetic organic dyes are used in various industries, such as textile industry, leather tanning industry, paper production, hair dye production, etc. Wastewaters containing these dyes may be harmful to the environment and living organisms. Therefore, it is very important to remove or degrade these dyes before discharging them into the environment. In addition to standard technologies for the degradation and/or removal of dyes, several new specific technologies, the so-called advanced oxidation processes (AOPs), have been developed to eliminate dangerous compounds from polluted waters. AOPs are all characterized by the same chemical feature: production of radicals (•OH) through a multistep process, although different reaction systems are used. These radicals show little selectivity of attack and are able to oxidize various organic pollutants due to their high oxidative capacity (reduction potential of HO• Eo = 2.8 V). Heterogeneous photocatalysis, as one of the AOPs, could be effective in the oxidation/degradation of organic dyes. A major advantage of using heterogeneous photocatalysis for this purpose is the total mineralization of organic dyes, which results in CO2, H2O and corresponding mineral acids. In this study, nanomaterials based on montmorillonite and CuxCd1-xS with different Cu concentration (0.3 < x < 0.7) were utilized for the degradation of the commercial cationic textile dye Methylene blue (MB), used as a model pollutant. The synthesized nanomaterials were characterized by fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG–DTA). Test results of photocatalysis of methylene blue under UV-Visible irradiation show that the photoactivity of nanomaterials montmorillonite/ CuxCd1-xS increases with the increasing of Cu concentration. The kinetics of the degradation of the MB dye was described with the Langmuir–Hinshelwood (L–H) kinetic model.

Keywords: heterogeneous photocatalysis, methylene blue, montmorillonite, nanomaterial

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Authors: Xi Liu, Fan Yuan

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In the evolving landscape of physics-based machine learning (PBML), particularly within fluid dynamics and its applications in electromechanical engineering, robot vision, and robot learning, achieving precision and alignment with researchers' specific needs presents a formidable challenge. In response, this work proposes a methodology that integrates neural transformation with a modified smoothed particle hydrodynamics model for generating transformed 3D fluid simulations. This approach is useful for nanoscale science, where the unique and complex behaviors of viscoelastic medium demand accurate neurally-transformed simulations for materials understanding and manipulation. In electromechanical engineering, the method enhances the design and functionality of fluid-operated systems, particularly microfluidic devices, contributing to advancements in nanomaterial design, drug delivery systems, and more. The proposed approach also aligns with the principles of PBML, offering advantages such as multi-fluid stylization and consistent particle attribute transfer. This capability is valuable in various fields where the interaction of multiple fluid components is significant. Moreover, the application of neurally-transformed hydrodynamical models extends to manufacturing processes, such as the production of microelectromechanical systems, enhancing efficiency and cost-effectiveness. The system's ability to perform neural transfer on 3D fluid scenes using a deep learning algorithm alongside physical models further adds a layer of flexibility, allowing researchers to tailor simulations to specific needs across scientific and engineering disciplines.

Keywords: physics-based machine learning, robot vision, robot learning, hydrodynamics

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Authors: Devendra Sillu, Shekhar Agnihotri

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The 'nano-biocatalyst' utilizes an ordered assembling of enzyme on to nanomaterial carriers to catalyze desirable biochemical kinetics and substrate selectivity. The current study describes an inter-disciplinary approach for converting agriculture waste, sugarcane bagasse into D-glucose exploiting halloysite nanotubes (HNTs) decorated cellulase enzyme as nano-biocatalytic system. Cellulase was successfully immobilized on HNTs employing polydopamine as an eco-friendly crosslinker while iron oxide nanoparticles were attached to facilitate magnetic recovery of material. The characterization studies (UV-Vis, TEM, SEM, and XRD) displayed the characteristic features of both cellulase and magnetic HNTs in the resulting nanocomposite. Various factors (i.e., working pH, temp., crosslinker conc., enzyme conc.) which may influence the activity of biocatalytic system were investigated. The experimental design was performed using Response Surface Methodology (RSM) for process optimization. Analyses data demonstrated that the nanobiocatalysts retained 80.30% activity even at elevated temperature (55°C) and excellent storage stabilities after 10 days. The repeated usage of system revealed a remarkable consistent relative activity over several cycles. The immobilized cellulase was employed to decompose agro-waste and the maximum decomposition rate of 67.2 % was achieved. Conclusively, magnetic HNTs can serve as a potential support for enzyme immobilization with long term usage, good efficacy, reusability and easy recovery from solution.

Keywords: halloysite nanotubes, enzyme immobilization, cellulase, response surface methodology, magnetic recovery

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Authors: Manasa Perikala, Asha Bhardwaj

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Fluorescent carbon dots (CDs), a young member of Carbon nanomaterial family, has gained a lot of research attention across the globe due to its highly luminescent emission properties, non-toxic behavior, stable emission properties, and zero re-absorption lose. These dots have the potential to replace the use of traditional semiconductor quantum dots in light-emitting devices (LED’s, fiber lasers) and other photonic devices (temperature sensor, UV detector). However, One major drawback of Carbon dots is that, till date, the actual mechanism of photoluminescence (PL) in carbon dots is still an open topic of discussion among various researchers across the globe. PL mechanism of CDs based on wide particle size distribution, the effect of surface groups, hybridization in carbon, and charge transfer mechanisms have been proposed. Although these mechanisms explain PL of CDs to an extent, no universally accepted mechanism to explain complete PL behavior of these dots is put forth. In our work, we report parameters affecting the size and surface of CDs, such as time of the reaction, synthesis temperature and concentration of precursors and their effects on the optical properties of the carbon dots. The effect of auxochromes on the emission properties and re-modification of carbon surface using an external surface functionalizing agent is discussed in detail. All the explanations have been supported by UV-Visible absorption, emission spectroscopies, Fourier transform infrared spectroscopy and Transmission electron microscopy and X-Ray diffraction techniques. Once the origin of PL in CDs is understood, parameters affecting PL centers can be modified to tailor the optical properties of these dots, which can enhance their applications in the fabrication of LED’s and other photonic devices out of these carbon dots.

Keywords: carbon dots, photoluminescence, size effects on emission in CDs, surface modification of carbon dots

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Authors: Y. J. Lin, Y. F. Lin

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CO2 is the primary greenhouse gas which causes global warming in recent years. As the carbon capture and storage (CCS) getting maturing, the reuse of carbon dioxide which made from CCS is the important issue. In this way, the most common method is the synthesis of cyclic carbonate chemicals from the cycloaddition reaction of carbon dioxide and epoxide. The catalyst plays an important role in the CO2/epoxide cycloaddition reactions. The Lewis acid and base sites are both needed on the catalyst surface for the help of epoxide ring opening, leading to the synthesis of cyclic carbonate. Furthermore, the larger specific surface area and more active site of the catalyst are also needed to enhance the efficiency of the CO2/epoxide cycloaddition reactions. Aerogel is a mesoporous nanomaterial (pore size between 2~50 nm) with high specific surface area and porosity (at least 90%) and low density. In this study, the ternary metal oxide aerogels, Mg-doped Al2O3 aerogels, with higher specific surface area and Lewis acid and base sites on the aerogel surface are successfully prepared by using a facile sol-gel reaction. The as-prepared Mg-doped Al2O3 aerogels are also served as heterogenous catalyst for the CO2/propylene- oxide cycloaddition reaction. Compared to the pristine Al2O3 aerogels, the Mg-doped Al2O3 aerogels possessed both Lewis acid and base sites on the surface are able to enhance the efficiency of the CO2/propylene oxide cycloaddition reactions. As a result, the as-prepared Mg-doped Al2O3 aerogels are a promising and novel catalyst for the CO2/epoxide cycloaddition reactions.

Keywords: ternary, metal oxide aerogel, CO2 reuse, cycloaddition, propylene oxide

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Authors: Samaneh Nabavi, Hadi Shirzad, Somayeh Khanjani, Shirin Jalili

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Quantum dots (QDs) are semiconductor nanocrystals that exhibit intrinsic optical and electrical properties that are size dependent due to the quantum confinement effect. Quantum confinement is brought about by the fact that in bulk semiconductor material the electronic structure consists of continuous bands, and that as the size of the semiconductor material decreases its radius becomes less than the Bohr exciton radius (the distance between the electron and electron-hole) and discrete energy levels result. As a result QDs have a broad absorption range and a narrow emission which correlates to the band gap energy (E), and hence QD size. QDs can thus be tuned to give the desired wavelength of fluorescence emission.Due to their unique properties, QDs have attracted considerable attention in different scientific areas. Also, they have been considered for forensic applications in recent years. The ability of QDs to fluoresce up to 20 times brighter than available fluorescent dyes makes them an attractive nanomaterial for enhancing the visualization of latent fingermarks, or poorly developed fingermarks. Furthermore, the potential applications of QDs in the detection of nitroaromatic explosives, such as TNT, based on directive fluorescence quenching of QDs, electron transfer quenching process or fluorescence resonance energy transfer have been paid to attention. DNA analysis is associated tightly with forensic applications in molecular diagnostics. The amount of DNA acquired at a criminal site is inherently limited. This limited amount of human DNA has to be quantified accurately after the process of DNA extraction. Accordingly, highly sensitive detection of human genomic DNA is an essential issue for forensic study. QDs have also a variety of advantages as an emission probe in forensic DNA quantification.

Keywords: forensic science, quantum dots, DNA typing, explosive sensor, fingermark analysis

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Authors: Sharmin Ferdewsi Rakhi, AHM Mohsinul Reza, Brynley Davies, Jianzhong Wang, Youhong Tang, Jian Qin

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Mass production of microalgae has become a focus of research owing to their promising aspects for sustainable food, biofunctional compounds, and biofuel feedstock. However, low lipid content with optimum algal biomass is still a challenge that must be resolved for commercial use. This research aims to determine the effects of light spectral shift and reactive oxygen species (ROS) on growth and lipid biosynthesis in a green microalga, Chlamydomonas reinhardtii. Aggregation Induced Emission (AIE)-based photosensitisers, CN-TPAQ-PF6 ([C₃₂H₂₃N₄]+) with high ROS productivity, was introduced into the algal culture media separately for effective conversion of the green-yellow-light to the red spectra. The intense photon energy and high-photon flux density in the photosystems and ROS supplementation induced photosynthesis and lipid biogenesis. In comparison to the control, maximum algal growth (0.15 g/l) was achieved at 2 µM CN-TPAQ-PF6 exposure. A significant increase in total lipid accumulation (146.87 mg/g dry biomass) with high proportion of 10-Heptadecanoic acid (C17:1) linolenic acid (C18:2), α-linolenic acid (C18:3) was observed. The elevated level of cellular NADP/NADPH triggered the Acetyl-Co-A production in lipid biogenesis cascade. Furthermore, MTT analysis suggested that this nanomaterial is highly biocompatible on HaCat cell lines with 100% cell viability. This study reveals that the AIE-based approach can strongly impact algal biofactory development for sustainable food, healthy lipids and eco-friendly biofuel.

Keywords: microalgae, photosensitiser, lipid, biomass, aggregation-induced-emission, reactive oxygen species

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Authors: Medhat Gad

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Wastewater treatment became a big issue in this decade due to shortage of water resources, growth of population and modern live requirements. Reuse of treated wastewater in industrial and agriculture sectors has a big demand to substitute the shortage of clean water supply as well as to save the eco system from dangerous pollutants in insufficient treated wastewater In last decades, most of wastewater treatment plants are built using primary or secondary biological treatment technology which almost does not provide enough treatment and removal of phosphorus and nitrogen. those plants which built ten to 15 years ago also now suffering from overflow which decrease the treatment efficiency of the plant. Discharging treated wastewater which contains phosphorus and nitrogen to water reservoirs and irrigation canals destroy ecosystem and aquatic life. Using chemical material to enhance treatment efficiency for domestic wastewater but it leads to huge amount of sludge which cost a lot of money. To enhance wastewater treatment, we used INNPT nano material which consists of calcium, aluminum and iron oxides and compounds plus silica, sodium and magnesium. INNPT nano material used with a dose of 100 mg/l to upgrade SBR treatment plant in Cairo Egypt -which has three treatment tanks each with a capacity of 2500 cubic meters per day - to tertiary treatment level by removing Phosphorus, Nitrogen and increase dissolved oxygen in final effluent. The results showed that the treatment retention time decreased from 9 hours in SBR system to one hour using INNPT nano material with improvement in effluent quality while increasing plant capacity to 20 k cubic meters per day. Nitrogen removal efficiency achieved 77%, while phosphorus removal efficiency achieved 90% and COD removal efficiency was 93% which all comply with tertiary treatment limits according to Egyptian law.

Keywords: INNPT technology, nanomaterial, tertiary wastewater treatment, capacity extending

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Authors: Anna Yagodnitsyna, Alexander Kovalev, Artur Bilsky

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The efficiency of certain technological processes in two-phase microfluidics such as emulsion production, nanomaterial synthesis, nitration, extraction processes etc. depends on two-phase flow regimes in microchannels. For practical application in chemistry and biochemistry it is very important to predict the expected flow pattern for a large variety of fluids and channel geometries. In the case of immiscible liquids, the plug flow is a typical and optimal regime for chemical reactions and needs to be predicted by empirical data or correlations. In this work flow patterns of immiscible liquid-liquid flow in a rectangular microchannel with T-junction are investigated. Three liquid-liquid flow systems are considered, viz. kerosene – water, paraffin oil – water and castor oil – paraffin oil. Different flow patterns such as parallel flow, slug flow, plug flow, dispersed (droplet) flow, and rivulet flow are observed for different velocity ratios. New flow pattern of the parallel flow with steady wavy interface (serpentine flow) has been found. It is shown that flow pattern maps based on Weber numbers for different liquid-liquid systems do not match well. Weber number multiplied by Ohnesorge number is proposed as a parameter to generalize flow maps. Flow maps based on this parameter are superposed well for all liquid-liquid systems of this work and other experiments. Plug length and velocity are measured for the plug flow regime. When dispersed liquid wets channel walls plug length cannot be predicted by known empirical correlations. By means of particle tracking velocimetry technique instantaneous velocity fields in a plug flow regime were measured. Flow circulation inside plug was calculated using velocity data that can be useful for mass flux prediction in chemical reactions.

Keywords: flow patterns, hydrodynamics, liquid-liquid flow, microchannel

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Authors: Gaurav Bhanjana, Ganga Ram Chaudhary, Sandeep Kumar, Neeraj Dilbaghi

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Main sources of endocrine disrupting compounds in the ecosystem are hormones, pesticides, phthalates, flame retardants, dioxins, personal-care products, coplanar polychlorinated biphenyls (PCBs), bisphenol A, and parabens. These endocrine disrupting compounds are responsible for learning disabilities, brain development problems, deformations of the body, cancer, reproductive abnormalities in females and decreased sperm count in human males. Although discharge of these chemical compounds into the environment cannot be stopped, yet their amount can be retarded through proper evaluation and detection techniques. The available techniques for determination of these endocrine disrupting compounds mainly include high performance liquid chromatography (HPLC), mass spectroscopy (MS) and gas chromatography-mass spectrometry (GC–MS). These techniques are accurate and reliable but have certain limitations like need of skilled personnel, time consuming, interference and requirement of pretreatment steps. Moreover, these techniques are laboratory bound and sample is required in large amount for analysis. In view of above facts, new methods for detection of endocrine disrupting compounds should be devised that promise high specificity, ultra sensitivity, cost effective, efficient and easy-to-operate procedure. Nowadays, electrochemical sensors/biosensors modified with nanomaterials are gaining high attention among researchers. Bioelement present in this system makes the developed sensors selective towards analyte of interest. Nanomaterials provide large surface area, high electron communication feature, enhanced catalytic activity and possibilities of chemical modifications. In most of the cases, nanomaterials also serve as an electron mediator or electrocatalyst for some analytes.

Keywords: electrochemical, endocrine disruptors, microscopy, nanoparticles, sensors

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Authors: Vrinda P. S. Borker

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Major water pollutants are dyes from effluents of industries. Different methods have been tried to degrade or treat the effluent before it is left to the environment. In order to understand the degradation process and later apply it to effluents, solar degradation study of methylene blue (MB) and methyl red (MR), the model dyes was carried out in the presence of photo-catalysts, the oxides of cobalt oxide Co₃O₄, and copper doped cobalt oxides (Co₀.₉Cu₀.₁)₃O₄ and (Co₀.₉₅Cu₀.₀₅)₃O₄. They were prepared from oxalate complex and hydrazinated oxalate complex of cobalt as well as mix metals, copper, and cobalt. The complexes were synthesized and characterized by FTIR. Complexes were decomposed to form oxides and were characterized by XRD. They were found to be monophasic. Solar degradation of MR and MB was carried out in presence of these oxides in acidic and basic medium. Degradation was faster in alkaline medium in the presence of Co₃O₄ obtained from hydrazinated oxalate. Doping of nanomaterial oxides modifies their characteristics. Doped cobalt oxides are found to photo-decolourise MR in alkaline media efficiently. In the absence of photocatalyst, solar degradation of alkaline MR does not occur. In acidic medium, MR is minimally decolorized even in the presence of photocatalysts. The industrial textile effluent contains chemicals like NaCl and Na₂CO₃ along with the unabsorbed dye. It is reported that these two chemicals hamper the degradation of dye. The chemicals like K₂S₂O₈ and H₂O₂ are reported to enhance degradation. The solar degradation study of MB in presence of photocatalyst (Co₀.₉Cu₀.₁)₃O₄ and these four chemicals reveals that presence of K₂S₂O₈ and H₂O₂ enhances degradation. It proves that H₂O₂ generates hydroxyl ions required for degradation of dye and the sulphate anion radical being strong oxidant attacks dye molecules leading to its fragmentation rapidly. Thus addition of K₂S₂O₈ and H₂O₂ during solar degradation in presence of (Co₀.₉Cu₀.₁)₃O₄ helps to break the organic moiety efficiently.

Keywords: cobalt oxides, Cu-doped cobalt oxides, H₂O₂ in dye degradation, photo-catalyst, solar dye degradation

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Authors: Vadanasundari Vedarethinam, Kun Qian

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The metabolic analysis is more distal over proteomics and genomics engaging in clinics and needs rationally distinct techniques, designed materials, and device for clinical diagnosis. Conventional techniques such as spectroscopic techniques, biochemical analyzers, and electrochemical have been used for metabolic diagnosis. Currently, there are four major challenges including (I) long-term process in sample pretreatment; (II) difficulties in direct metabolic analysis of biosamples due to complexity (III) low molecular weight metabolite detection with accuracy and (IV) construction of diagnostic tools by materials and device-based platforms for real case application in biomedical applications. Development of chips with nanomaterial is promising to address these critical issues. Mass spectroscopy (MS) has displayed high sensitivity and accuracy, throughput, reproducibility, and resolution for molecular analysis. Particularly laser desorption/ ionization mass spectrometry (LDI MS) combined with devices affords desirable speed for mass measurement in seconds and high sensitivity with low cost towards large scale uses. We developed a plasmonic chip for clinical metabolic fingerprinting as a hot carrier in LDI MS by series of chips with gold nanoshells on the surface through controlled particle synthesis, dip-coating, and gold sputtering for mass production. We integrated the optimized chip with microarrays for laboratory automation and nanoscaled experiments, which afforded direct high-performance metabolic fingerprinting by LDI MS using 500 nL of serum, urine, cerebrospinal fluids (CSF) and exosomes. Further, we demonstrated on-chip direct in-vitro metabolic diagnosis of early-stage lung cancer patients using serum and exosomes without any pretreatment or purifications. To our best knowledge, this work initiates a bionanotechnology based platform for advanced metabolic analysis toward large-scale diagnostic use.

Keywords: plasmonic chip, metabolic fingerprinting, LDI MS, in-vitro diagnostics

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Authors: Hanan Fayez Hussein

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‘Due to increasing environmental challenges and security problems in the world such as global warming, storms, and terrorism’, humans have discovered new technologies and new materials in order to program daily life. As providing physical and psychological security is one of the primary functions of architecture, so in order to provide security, building must prevents unauthorized entry and harm to occupant and reduce the threat of attack by making building less attractive targets by new technologies such as; Nanotechnology, which has emerged as a major science and technology focus of the 21st century and will be the next industrial revolution. Nanotechnology is control of the properties of matter, and it deals with structures of the size 100 nanometers or smaller in at least one dimension and has wide application in various fields. The construction and architecture sectors were among the first to be identified as a promising application area for nanotechnology. The advantages of using nanomaterials in construction are enormous, and promises heighten building security by utilizing the strength of building materials to make our buildings more secure and get smart home. Access barriers such as wall and windows could incorporate stronger materials benefiting from nano-reinforcement utilizing nanotubes and nano composites to act as protective cover. Carbon nanotubes, as one of nanotechnology application, can be designed up to 250 times stronger than steel. Nano-enabled devices and materials offer both enhanced and, in some cases, completely new defence systems. In the addition, the small amount of carbon nanoparticles to the construction materials such as; cement, concrete, wood, glass, gypson, and steel can make these materials act as defence elements. This paper highlights the fact that nanotechnology can impact the future global security and how building’s envelop can act as a defensive cover for the building and can be resistance to any threats can attack it. Then focus on its effect on construction materials such as; Concrete can obtain by nanoadditives excellent mechanical, chemical, and physical properties with less material, which can acts as a precautionary shield to the building.

Keywords: nanomaterial, global warming, building security, smart homes

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Authors: Sultan Ben Jaber

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Optical properties of molecules exhibit dramatic changes when adsorbed close to nano-structure metallic surfaces such as gold and silver nanomaterial. This phenomena opened a wide range of research to improve conventional spectroscopies efficiency. A well-known technique that has an intensive focus of study is surface-enhanced Raman spectroscopy (SERS), as since the first observation of SERS phenomena, researchers have published a great number of articles about the potential mechanisms behind this effect as well as developing materials to maximize the enhancement. Infrared and Raman spectroscopy are complementary techniques; thus, surface-enhanced infrared absorption (SEIRA) also shows a noticeable enhancement of molecules in the mid-IR excitation on nonmetallic structure substrates. In the SEIRA, vibrational modes that gave change in dipole moments perpendicular to the nano-metallic substrate enhanced 200 times greater than the free molecule’s modes. SEIRA spectroscopy is promising for the characterization and identification of adsorbed molecules on metallic surfaces, especially at trace levels. IR reflection-absorption spectroscopy (IRAS) is a well-known technique for measuring IR spectra of adsorbed molecules on metallic surfaces. However, SEIRA spectroscopy sensitivity is up to 50 times higher than IRAS. SEIRA enhancement has been observed for a wide range of molecules adsorbed on metallic substrates such as Au, Ag, Pd, Pt, Al, and Ni, but Au and Ag substrates exhibited the highest enhancement among the other mentioned substrates. In this work, trace levels of 3,4-methylenedioxymethamphetamine (MDMA) have been detected using gold nanoparticles (AuNPs) substrates with surface-enhanced infrared absorption (SEIRA). AuNPs were first prepared and washed, then mixed with different concentrations of MDMA samples. The process of fabricating the substrate prior SEIRA measurements included mixing of AuNPs and MDMA samples followed by vigorous stirring. The stirring step is particularly crucial, as stirring allows molecules to be robustly adsorbed on AuNPs. Thus, remarkable SEIRA was observed for MDMA samples even at trace levels, showing the rigidity of our approach to preparing SEIRA substrates.

Keywords: surface-enhanced infrared absorption (SEIRA), gold nanoparticles (AuNPs), amphetamines, methylene dioxy- methamphetamine (MDMA), enhancement factor

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Authors: Erico R. Carmona, Lucas Hernandez-Saravia, Aliro Villacorta, Felipe Carevic

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Tailings and electronic waste (e-waste) are an important source of global contamination. Chile is one of Organisation for Economic Co-operation and Development (OECD) member countries that least recycled this kind of industrial waste, reaching only 3% of the total. Tailings and e-waste recycling offers a valuable tool to minimize the increasing accumulation of waste, supplement the scarcity of some raw materials and to obtain economic benefits through the commercialization of these. It should be noted that this type of industrial waste is an important source of valuable metals, such as copper, which allow generating new business and added value through its transformation into new materials with advanced physical and biological properties. In this sense, the development of nanotechnology has led to the creation of nanomaterials with multiple applications given their unique physicochemical properties. Among others, copper nanoparticles (CuNPs) have gained great interest due to their optical, catalytic, conductive properties, and particularly because of their broad-spectrum antimicrobial activity. There are different synthesis methods of copper nanoparticles; however, green synthesis is one of the most promising methodologies, since it is simple, low-cost, ecological, and generates stable nanoparticles, which makes it a promising methodology for scaling up. Currently, there are few initiatives that involve the development of methods for the recovery and transformation of copper from waste to produce nanoparticles with new properties and better technological benefits. Thus, the objective of this work is to show preliminary data about the develop a sustainable transformation process of tailings and e-waste that allows obtaining a copper-based nanotechnological product with potential antimicrobial applications. For this, samples of tailings and e-waste collected from Tarapacá and Antofagasta region of northern Chile were used to recover copper through efficient, ecological, and low-cost alkaline hydrometallurgical treatments, which to allow obtaining copper with a high degree of purity. On the other hand, the transformation process from recycled copper to a nanomaterial was carried out through a green synthesis approach by using vegetal organic residue extracts that allows obtaining CuNPs following methodologies previously reported by authors. Initial physical characterization with UV-Vis, FTIR, AFM, and TEM methodologies will be reported for CuNPs synthesized.

Keywords: nanomaterials, industrial waste, chile, recycling

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Authors: Arnab Hazra

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Breath analysis is a quick, noninvasive and inexpensive technique for disease diagnosis can be used on people of all ages without any risk. Only a limited number of volatile organic compounds (VOCs) can be associated with the occurrence of specific diseases. These VOCs can be considered as disease markers or breath markers. Selective detection with specific concentration of breath marker in exhaled human breath is required to detect a particular disease. For example, acetone (C₃H₆O), ethanol (C₂H₅OH), ethane (C₂H₆) etc. are the breath markers and abnormal concentrations of these VOCs in exhaled human breath indicates the diseases like diabetes mellitus, renal failure, breast cancer respectively. Nanomaterial-based vapor sensors are inexpensive, small and potential candidate for the detection of breath markers. In practical measurement, selectivity is the most crucial issue where trace detection of breath marker is needed to identify accurately in the presence of several interfering vapors and gases. Current article concerns a novel technique for selective and lower ppb level detection of breath markers at very low temperature based on TiO₂ nanotube array based vapor sensor devices. Highly ordered and oriented TiO₂ nanotube array was synthesized by electrochemical anodization of high purity tatinium (Ti) foil. 0.5 wt% NH₄F, ethylene glycol and 10 vol% H₂O was used as the electrolyte and anodization was carried out for 90 min with 40 V DC potential. Au/TiO₂ Nanotube/Ti, sandwich type sensor device was fabricated for the selective detection of VOCs in low concentration range. Initially, sensor was characterized where resistive and capacitive change of the sensor was recorded within the valid concentration range for individual breath markers (or organic vapors). Sensor resistance was decreased and sensor capacitance was increased with the increase of vapor concentration. Now, the ratio of resistive slope (mR) and capacitive slope (mC) provided a concentration independent constant term (M) for a particular vapor. For the detection of unknown vapor, ratio of resistive change and capacitive change at any concentration was same to the previously calculated constant term (M). After successful identification of the target vapor, concentration was calculated from the straight line behavior of resistance as a function of concentration. Current technique is suitable for the detection of particular vapor from a mixture of other interfering vapors.

Keywords: breath marker, vapor sensors, selective detection, TiO₂ nanotube array

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Authors: Yunha Ryu, Kyoungsik Kim

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Raman spectroscopy is one of the most powerful techniques for chemical detection, but the low sensitivity originated from the extremely small cross-section of the Raman scattering limits the practical use of Raman spectroscopy. To overcome this problem, Surface Enhanced Raman Scattering (SERS) has been intensively studied for several decades. Because the SERS effect is mainly induced from strong electromagnetic near-field enhancement as a result of localized surface plasmon resonance of metallic nanostructures, it is important to design the plasmonic structures with high density of electromagnetic hot spots for SERS substrate. One of the useful fabrication methods is using porous nanomaterial as a template for metallic structure. Internal pores on a scale of tens of nanometers can be strong EM hotspots by confining the incident light. Also, porous structures can capture more target molecules than non-porous structures in a same detection spot thanks to the large surface area. Herein we report the facile fabrication method of porous SERS substrate by integrating solvent-assisted nanoimprint lithography and selective etching of block copolymer. We obtained nanostructures with high porosity via simple selective etching of the one microdomain of the diblock copolymer. Furthermore, we imprinted of the nanocone patterns into the spin-coated flat block copolymer film to make three-dimensional SERS substrate for the high density of SERS hot spots as well as large surface area. We used solvent-assisted nanoimprint lithography (SAIL) to reduce the fabrication time and cost for patterning BCP film by taking advantage of a solvent which dissolves both polystyrenre and poly(methyl methacrylate) domain of the block copolymer, and thus block copolymer film was molded under the low temperature and atmospheric pressure in a short time. After Ag deposition, we measured Raman intensity of dye molecules adsorbed on the fabricated structure. Compared to the Raman signals of Ag coated solid nanocone, porous nanocone showed 10 times higher Raman intensity at 1510 cm(-1) band. In conclusion, we fabricated porous metallic nanocone arrays with high density electromagnetic hotspots by templating nanoimprinted diblock copolymer with selective etching and demonstrated its capability as an effective SERS substrate.

Keywords: block copolymer, porous nanostructure, solvent-assisted nanoimprint, surface-enhanced Raman spectroscopy

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Authors: Ram Mohan, Mahendran Samykano, Shyam Aravamudhan

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Metallic nanowires with sub-micron and hundreds of nanometer diameter have a diversity of applications in nano/micro-electromechanical systems (NEMS/MEMS). Characterizing the mechanical properties of such sub-micron and nano-scale metallic nanowires are tedious; require sophisticated and careful experimentation to be performed within high-powered microscopy systems (scanning electron microscope (SEM), atomic force microscope (AFM)). Also, needed are nanoscale devices for placing the nanowires; loading them with the intended conditions; obtaining the data for load–deflection during the deformation within the high-powered microscopy environment poses significant challenges. Even picking the grown nanowires and placing them correctly within a nanoscale loading device is not an easy task. Mechanical characterizations through experimental methods for such nanowires are still very limited. Various techniques at different levels of fidelity, resolution, and induced errors have been attempted by material science and nanomaterial researchers. The methods for determining the load, deflection within the nanoscale devices also pose a significant problem. The state of the art is thus still at its infancy. All these factors result and is seen in the wide differences in the characterization curves and the reported properties in the current literature. In this paper, we discuss and present our experimental method, results, and discussions of uniaxial tensile loading and the development of subsequent stress–strain characteristics curves for Nickel nanowires. Nickel nanowires in the diameter range of 220–270 nm were obtained in our laboratory via an electrodeposition method, which is a solution based, template method followed in our present work for growing 1-D Nickel nanowires. Process variables such as the presence of magnetic field, its intensity; and varying electrical current density during the electrodeposition process were found to influence the morphological and physical characteristics including crystal orientation, size of the grown nanowires1. To further understand the correlation and influence of electrodeposition process variables, associated formed structural features of our grown Nickel nanowires to their mechanical properties, careful experiments within scanning electron microscope (SEM) were conducted. Details of the uniaxial tensile characterization, testing methodology, nanoscale testing device, load–deflection characteristics, microscopy images of failure progression, and the subsequent stress–strain curves are discussed and presented.

Keywords: uniaxial tensile characterization, nanowires, electrodeposition, stress-strain, nickel

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Authors: Ram V. Mohan, John Rivas-Murillo, Ahmed Mohamed, Wayne D. Hodo

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Cementitious materials, an excellent example of highly complex, heterogeneous material systems, are cement-based systems that include cement paste, mortar, and concrete that are heavily used in civil infrastructure; though commonly used are one of the most complex in terms of the material morphology and structure than most materials, for example, crystalline metals. Processes and features occurring at the nanometer sized morphological structures affect the performance, deformation/failure behavior at larger length scales. In addition, cementitious materials undergo chemical and morphological changes gaining strength during the transient hydration process. Hydration in cement is a very complex process creating complex microstructures and the associated molecular structures that vary with hydration. A fundamental understanding can be gained through multi-scale level modeling for the behavior and properties of cementitious materials starting from the material chemistry level atomistic scale to further explore their role and the manifested effects at larger length and engineering scales. This predictive modeling enables the understanding, and studying the influence of material chemistry level changes and nanomaterial additives on the expected resultant material characteristics and deformation behavior. Atomistic-molecular dynamic level modeling is required to couple material science to engineering mechanics. Starting at the molecular level a comprehensive description of the material’s chemistry is required to understand the fundamental properties that govern behavior occurring across each relevant length scale. Material chemistry level models and molecular dynamics modeling and simulations are employed in our work to describe the molecular-level chemistry features of calcium-silicate-hydrate (CSH), one of the key hydrated constituents of cement paste, their associated deformation and failure. The molecular level atomic structure for CSH can be represented by Jennite mineral structure. Jennite has been widely accepted by researchers and is typically used to represent the molecular structure of the CSH gel formed during the hydration of cement clinkers. This paper will focus on our recent work on the shear and compressive deformation and failure behavior of CSH represented by Jennite mineral structure that has been widely accepted by researchers and is typically used to represent the molecular structure of CSH formed during the hydration of cement clinkers. The deformation and failure behavior under shear and compression loading deformation in traditional hydrated CSH; effect of material chemistry changes on the predicted stress-strain behavior, transition from linear to non-linear behavior and identify the on-set of failure based on material chemistry structures of CSH Jennite and changes in its chemistry structure will be discussed.

Keywords: cementitious materials, deformation, failure, material chemistry modeling

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Authors: Sankha Chakrabortty, Biswajit Ruj, Parimal Pal

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Methanol is one of the most important chemical products and intermediates. It can be used as a solvent, intermediate or raw material for a number of higher valued products, fuels or additives. From the last one decay, the total global demand of methanol has increased drastically which forces the scientists to produce a large amount of methanol from a renewable source to meet the global demand with a sustainable way. Different types of non-renewable based raw materials have been used for the synthesis of methanol on a large scale which makes the process unsustainable. In this circumstances, photocatalytic conversion of CO₂ into methanol under solar/UV excitation becomes a viable approach to give a sustainable production approach which not only meets the environmental crisis by recycling CO₂ to fuels but also reduces CO₂ amount from the atmosphere. Development of such sustainable production approach for CO₂ conversion into methanol still remains a major challenge in the current research comparing with conventional energy expensive processes. In this backdrop, the development of environmentally friendly materials, like photocatalyst has taken a great perspective for methanol synthesis. Scientists in this field are always concerned about finding an improved photocatalyst to enhance the photocatalytic performance. Graphene-based hybrid and composite materials with improved properties could be a better nanomaterial for the selective conversion of CO₂ to methanol under visible light (solar energy) or UV light. The present invention relates to synthesis an improved heterogeneous graphene-based photocatalyst with improved catalytic activity and surface area. Graphene with enhanced surface area is used as coupled material of copper-loaded titanium oxide to improve the electron capture and transport properties which substantially increase the photoinduced charge transfer and extend the lifetime of photogenerated charge carriers. A fast reduction method through H₂ purging has been adopted to synthesis improved graphene whereas ultrasonication based sol-gel method has been applied for the preparation of graphene coupled copper loaded titanium oxide with some enhanced properties. Prepared photocatalysts were exhaustively characterized using different characterization techniques. Effects of catalyst dose, CO₂ flow rate, reaction temperature and stirring time on the efficacy of the system in terms of methanol yield and productivity have been studied in the present study. The study shown that the newly synthesized photocatalyst with an enhanced surface resulting in a sustained productivity and yield of methanol 0.14 g/Lh, and 0.04 g/gcat respectively, after 3 h of illumination under UV (250W) at an optimum catalyst dosage of 10 g/L having 1:2:3 (Graphene: TiO₂: Cu) weight ratio.

Keywords: renewable energy, CO₂ capture, photocatalytic conversion, methanol

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Authors: Qing Zhang, Janak L. Pathak, Macro N. Helder, Richard T. Jaspers, Yin Xiao

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Introduction: Nanomaterial-based bone regeneration is greatly influenced by the immune microenvironment. Tissue-engineered nanomaterials mediate the inflammatory response of macrophages to regulate bone regeneration. Silica nanoparticles have been widely used in tissue engineering-related preclinical studies. However, the effect of topological features on the surface of silica nanoparticles on the immune response of macrophages remains unknown. Purposes: The aims of this research are to compare the influences of normal and pollen-like silica nano-surface topography on macrophage immune responses and to obtain insight into their potential regulatory mechanisms. Method: Macrophages (RAW 264.7 cells) were exposed to mesoporous silica nanoparticles with normal morphology (MSNs) and pollen-like morphology (PMSNs). RNA-seq, RT-qPCR, and LSCM were used to assess the changes in expression levels of immune response-related genes and proteins. SEM and TEM were executed to evaluate the contact and adherence of silica nanoparticles by macrophages. For the assessment of the immunomodulation-mediated osteogenic potential, BMSCs were cultured with conditioned medium (CM) from LPS pre-stimulated macrophage cultures treated with MSNs or PMSNs. Osteoimmunomodulatory potential of MSNs and PMSNs in vivo was tested in a mouse cranial bone osteolysis model. Results: The results of the RNA-seq, RT-qPCR, and LSCM assays showed that PMSNs inhibited the expression of pro-inflammatory genes and proteins in macrophages. SEM images showed distinct macrophage membrane surface binding patterns of MSNs and PMSNs. MSNs were more evenly dispersed across the macrophage cell membrane, while PMSNs were aggregated. PMSNs-induced macrophage anti-inflammatory response was associated with upregulation of the cell surface receptor CD28 and inhibition of ERK phosphorylation. TEM images showed that both MSNs and PMSNs could be phagocytosed by macrophages, and inhibiting nanoparticle phagocytosis did not affect the expression of anti-inflammatory genes and proteins. Moreover, PMSNs-induced conditioned medium from macrophages enhanced BMP-2 expression and osteogenic differentiation mBMSCs. Similarly, PMSNs prevented LPS-induced bone resorption via downregulation of inflammatory reaction. Conclusions: PMSNs can promote bone regeneration by modulating osteoimmunological processes through surface topography. The study offers insights into how surface physical contact cues can modulate the regulation of osteoimmunology and provides a basis for the application of nanoparticles with pollen-like morphology to affect immunomodulation in bone tissue engineering and regeneration.

Keywords: physical contact, osteoimmunology, macrophages, silica nanoparticles, surface morphology, membrane receptor, osteogenesis, inflammation

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Authors: Zhaoyang Liu, Detao Qin, Darren Delai Sun

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The onshore production of oil and gas (for example, shale gas) generates large quantities of wastewater, referred to be ‘produced water’, which contains high contents of oils and salts. The direct discharge of produced water, if not appropriately treated, can be toxic to the environment and human health. Membrane filtration has been deemed as an environmental-friendly and cost-effective technology for treating oily wastewater. However, conventional polymeric membranes have their drawbacks of either low salt rejection rate or high membrane fouling tendency when treating oily wastewater. Recent years, forward osmosis (FO) membrane filtration has emerged as a promising technology with its unique advantages of low operation pressure and less membrane fouling tendency. However, until now there is still no report about FO membranes specially designed and fabricated for treating the oily and salty produced water. In this study, a novel nanocomposite FO membrane was developed specially for treating oil- and salt-polluted produced water. By leveraging the recent advance of nanomaterials and nanotechnology, this nanocomposite FO membrane was designed to be made of double layers: an underwater oleophobic selective layer on top of a nanomaterial infused polymeric support layer. Wherein, graphene oxide (GO) nanosheets were selected to add into the polymeric support layer because adding GO nanosheets can optimize the pore structures of the support layer, thus potentially leading to high water flux for FO membranes. In addition, polyvinyl alcohol (PVA) hydrogel was selected as the selective layer because hydrated and chemically-crosslinked PVA hydrogel is capable of simultaneously rejecting oil and salt. After nanocomposite FO membranes were fabricated, the membrane structures were systematically characterized with the instruments of TEM, FESEM, XRD, ATR-FTIR, surface zeta-potential and Contact angles (CA). The membrane performances for treating produced waters were tested with the instruments of TOC, COD and Ion chromatography. The working mechanism of this new membrane was also analyzed. Very promising experimental results have been obtained. The incorporation of GO nanosheets can reduce internal concentration polarization (ICP) effect in the polymeric support layer. The structural parameter (S value) of the new FO membrane is reduced by 23% from 265 ± 31 μm to 205 ± 23 μm. The membrane tortuosity (τ value) is decreased by 20% from 2.55 ± 0.19 to 2.02 ± 0.13 μm, which contributes to the decrease of S value. Moreover, the highly-hydrophilic and chemically-cross-linked hydrogel selective layer present high antifouling property under saline oil/water emulsions. Compared with commercial FO membrane, this new FO membrane possesses three times higher water flux, higher removal efficiencies for oil (>99.9%) and salts (>99.7% for multivalent ions), and significantly lower membrane fouling tendency (<10%). To our knowledge, this is the first report of a nanocomposite FO membrane with the combined merits of high salt rejection, high oil repellency and high water flux for treating onshore oil/gas produced waters. Due to its outstanding performance and ease of fabrication, this novel nanocomposite FO membrane possesses great application potential in wastewater treatment industry.

Keywords: nanocomposite, membrane, polymer, graphene oxide

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Authors: Katherine Dropiewski, Michael Yakimov, Vadim Tokranov, Allan Minns, Pavel Murat, Serge Oktyabrsky

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InAs Quantum Dots (QDs) in a GaAs matrix is a well-documented luminescent material with high light yield, as well as thermal and ionizing radiation tolerance due to quantum confinement. These benefits can be leveraged for high-efficiency, room temperature scintillation detectors. The proposed scintillator is composed of InAs QDs acting as luminescence centers in a GaAs stopping medium, which also acts as a waveguide. This system has appealing potential properties, including high light yield (~240,000 photons/MeV) and fast capture of photoelectrons (2-5ps), orders of magnitude better than currently used inorganic scintillators, such as LYSO or BaF2. The high refractive index of the GaAs matrix (n=3.4) ensures light emitted by the QDs is waveguided, which can be collected by an integrated photodiode (PD). Scintillation structures were grown using Molecular Beam Epitaxy (MBE) and consist of thick GaAs waveguiding layers with embedded sheets of modulation p-type doped InAs QDs. An AlAs sacrificial layer is grown between the waveguide and the GaAs substrate for epitaxial lift-off to separate the scintillator film and transfer it to a low-index substrate for waveguiding measurements. One consideration when using a low-density material like GaAs (~5.32 g/cm³) as a stopping medium is the matrix thickness in the dimension of radiation collection. Therefore, luminescence properties of very thick (4-20 microns) waveguides with up to 100 QD layers were studied. The optimization of the medium included QD shape, density, doping, and AlGaAs barriers at the waveguide surfaces to prevent non-radiative recombination. To characterize the efficiency of QD luminescence, low temperature photoluminescence (PL) (77-450 K) was measured and fitted using a kinetic model. The PL intensity degrades by only 40% at RT, with an activation energy for electron escape from QDs to the barrier of ~60 meV. Attenuation within the waveguide (WG) is a limiting factor for the lateral size of a scintillation detector, so PL spectroscopy in the waveguiding configuration was studied. Spectra were measured while the laser (630 nm) excitation point was scanned away from the collecting fiber coupled to the edge of the WG. The QD ground state PL peak at 1.04 eV (1190 nm) was inhomogeneously broadened with FWHM of 28 meV (33 nm) and showed a distinct red-shift due to self-absorption in the QDs. Attenuation stabilized after traveling over 1 mm through the WG, at about 3 cm⁻¹. Finally, a scintillator sample was used to test detection and evaluate timing characteristics using 5.5 MeV alpha particles. With a 2D waveguide and a small area of integrated PD, the collected charge averaged 8.4 x10⁴ electrons, corresponding to a collection efficiency of about 7%. The scintillation response had 80 ps noise-limited time resolution and a QD decay time of 0.6 ns. The data confirms unique properties of this scintillation detector which can be potentially much faster than any currently used inorganic scintillator.

Keywords: GaAs, InAs, molecular beam epitaxy, quantum dots, III-V semiconductor

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Authors: Ashish Thakur

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This technical paper was written in view of focusing the biomaterials and its various applications in modern industries. Author tires to elaborate not only the medical, infect plenty of application in other industries. The scope of the research area covers the wide range of physical, biological and chemical sciences that underpin the design of biomaterials and the clinical disciplines in which they are used. A biomaterial is now defined as a substance that has been engineered to take a form which, alone or as part of a complex system, is used to direct, by control of interactions with components of living systems, the course of any therapeutic or diagnostic procedure. Biomaterials are invariably in contact with living tissues. Thus, interactions between the surface of a synthetic material and biological environment must be well understood. This paper reviews the benefits and challenges associated with surface modification of the metals in biomedical applications. The paper also elaborates how the surface characteristics of metallic biomaterials, such as surface chemistry, topography, surface charge, and wettability, influence the protein adsorption and subsequent cell behavior in terms of adhesion, proliferation, and differentiation at the biomaterial–tissue interface. The chapter also highlights various techniques required for surface modification and coating of metallic biomaterials, including physicochemical and biochemical surface treatments and calcium phosphate and oxide coatings. In this review, the attention is focused on the biomaterial-associated infections, from which the need for anti-infective biomaterials originates. Biomaterial-associated infections differ markedly for epidemiology, aetiology and severity, depending mainly on the anatomic site, on the time of biomaterial application, and on the depth of the tissues harbouring the prosthesis. Here, the diversity and complexity of the different scenarios where medical devices are currently utilised are explored, providing an overview of the emblematic applicative fields and of the requirements for anti-infective biomaterials. In addition to this, chapter introduces nanomedicine and the use of both natural and synthetic polymeric biomaterials, focuses on specific current polymeric nanomedicine applications and research, and concludes with the challenges of nanomedicine research. Infection is currently regarded as the most severe and devastating complication associated to the use of biomaterials. Osteoporosis is a worldwide disease with a very high prevalence in humans older than 50. The main clinical consequences are bone fractures, which often lead to patient disability or even death. A number of commercial biomaterials are currently used to treat osteoporotic bone fractures, but most of these have not been specifically designed for that purpose. Many drug- or cell-loaded biomaterials have been proposed in research laboratories, but very few have received approval for commercial use. Polymeric nanomaterial-based therapeutics plays a key role in the field of medicine in treatment areas such as drug delivery, tissue engineering, cancer, diabetes, and neurodegenerative diseases. Advantages in the use of polymers over other materials for nanomedicine include increased functionality, design flexibility, improved processability, and, in some cases, biocompatibility.

Keywords: nanomedicine, tissue, infections, biomaterials

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Authors: E. Locatelli, I. Monaco, R. C. Martin, Y. Li, R. Pini, M. Chiariello, M. Comes Franchini

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Despite the many advantages of application of nanomaterials in the field of nanomedicine, increasing concerns have been expressed on their potential adverse effects on human health. There is urgency for novel green strategies toward novel materials with enhanced biocompatibility using safe reagents. Photothermal ablation therapy, which exploits localized heat increase of a few degrees to kill cancer cells, has appeared recently as a non-invasive and highly efficient therapy against various cancer types; anyway new agents able to generate hyperthermia when irradiated are needed and must have precise biocompatibility in order to avoid damage to healthy tissues and prevent toxicity. Recently, there has been increasing interest in magnesium as a biomaterial: it is the fourth most abundant cation in the human body, and it is essential for human metabolism. However magnesium nanoparticles (Mg NPs) have had limited diffusion due to the high reduction potential of magnesium cations, which makes NPs synthesis challenging. Herein, we report the synthesis of Mg NPs and their surface functionalization for the obtainment of a stable and biocompatible nanomaterial suitable for photothermal ablation therapy against cancer. We synthesized the Mg crystals by reducing MgCl2 with metallic lithium and exploiting naphthalene as an electron carrier: the lithium–naphthalene complex acts as the real reducing agent. Firstly, the nanocrystal particles were coated with the ligand 12-ethoxy ester dodecanehydroxamic acid, and then entrapped into water-dispersible polymeric micelles (PMs) made of the FDA-approved PLGA-b-PEG-COOH copolymer using the oil-in-water emulsion technique. Lately, we developed a more straightforward methodology by introducing chitosan, a highly biocompatible natural product, at the beginning of the process, simultaneously using lithium–naphthalene complex, thus having a one-pot procedure for the formation and surface modification of MgNPs. The obtained MgNPs were purified and fully characterized, showing diameters in the range of 50-300 nm. Notably, when coated with chitosan the particles remained stable as dry powder for more than 10 months. We proved the possibility of generating a temperature rise of a few to several degrees once MgNPs were illuminated using a 810 nm diode laser operating in continuous wave mode: the temperature rise resulted significant (0-15 °C) and concentration dependent. We then investigated potential cytotoxicity of the MgNPs: we used HN13 epithelial cells, derived from a head and neck squamous cell carcinoma and the hepa1-6 cell line, derived from hepatocellular carcinoma and very low toxicity was observed for both nanosystems. Finally, in vivo photothermal therapy was performed on xenograft hepa1-6 tumor bearing mice: the animals were treated with MgNPs coated with chitosan and showed no sign of suffering after the injection. After 12 hours the tumor was exposed to near-infrared laser light. The results clearly showed an extensive damage to tumor tissue after only 2 minutes of laser irradiation at 3Wcm-1, while no damage was reported when the tumor was treated with the laser and saline alone in control group. Despite the lower photothermal efficiency of Mg with respect to Au NPs, we consider MgNPs a promising, safe and green candidate for future clinical translations.

Keywords: chitosan, magnesium nanoparticles, nanomedicine, photothermal therapy

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Authors: Junkal Gutierrez, Hernane S. Barud, Sidney J. L. Ribeiro, Agnieszka Tercjak

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Nowadays the interest on green nanocomposites and on the development of more environmental friendly products has been increased. Bacterial cellulose has been recently investigated as an attractive environmentally friendly material for the preparation of low-cost nanocomposites. The formation of cellulose by laboratory bacterial cultures is an interesting and attractive biomimetic access to obtain pure cellulose with excellent properties. Additionally, properties as molar mass, molar mass distribution, and the supramolecular structure could be control using different bacterial strain, culture mediums and conditions, including the incorporation of different additives. This kind of cellulose is a natural nanomaterial, and therefore, it has a high surface-to-volume ratio which is highly advantageous in composites production. Such property combined with good biocompatibility, high tensile strength, and high crystallinity makes bacterial cellulose a potential material for applications in different fields. The aim of this investigation work was the fabrication of novel hybrid inorganic-organic composites based on bacterial cellulose, cultivated in our laboratory, as a template. This kind of biohybrid nanocomposites gathers together excellent properties of bacterial cellulose with the ones displayed by typical inorganic nanoparticles like optical, magnetic and electrical properties, luminescence, ionic conductivity and selectivity, as well as chemical or biochemical activity. In addition, the functionalization of cellulose with inorganic materials opens new pathways for the fabrication of novel multifunctional hybrid materials with promising properties for a wide range of applications namely electronic paper, flexible displays, solar cells, sensors, among others. In this work, different pathways for fabrication of multifunctional biohybrid nanopapers with tunable properties based on BC modified with amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (EPE) block copolymer, sol-gel synthesized nanoparticles (titanium, vanadium and a mixture of both oxides) and functionalized iron oxide nanoparticles will be presented. In situ (biosynthesized) and ex situ (at post-production level) approaches were successfully used to modify BC membranes. Bacterial cellulose based biocomposites modified with different EPE block copolymer contents were developed by in situ technique. Thus, BC growth conditions were manipulated to fabricate EPE/BC nanocomposite during the biosynthesis. Additionally, hybrid inorganic/organic nanocomposites based on BC membranes and inorganic nanoparticles were designed via ex-situ method, by immersion of never-dried BC membranes into different nanoparticle solutions. On the one hand, sol-gel synthesized nanoparticles (titanium, vanadium and a mixture of both oxides) and on the other hand superparamagnetic iron oxide nanoparticles (SPION), Fe2O3-PEO solution. The morphology of designed novel bionanocomposites hybrid materials was investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). In order to characterized obtained materials from the point of view of future applications different techniques were employed. On the one hand, optical properties were analyzed by UV-vis spectroscopy and spectrofluorimetry and on the other hand electrical properties were studied at nano and macroscale using electric force microscopy (EFM), tunneling atomic force microscopy (TUNA) and Keithley semiconductor analyzer, respectively. Magnetic properties were measured by means of magnetic force microscopy (MFM). Additionally, mechanical properties were also analyzed.

Keywords: bacterial cellulose, block copolymer, advanced characterization techniques, nanoparticles

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Authors: Laura Norfolk, Georgina Zimbitas, Jan Sefcik, Sarah Staniland

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Magnetite nanoparticles (MNP) have been an area of increasing research interest due to their extensive applications in industry, such as in carbon capture, water purification, and crucially, the biomedical industry. The use of MNP in the biomedical industry is rising, with studies on their effect as Magnetic resonance imaging contrast agents, drug delivery systems, and as hyperthermic cancer treatments becoming prevalent in the nanomaterial research community. Particles used for biomedical purposes must meet stringent criteria; the particles must have consistent shape and size between particles. Variation between particle morphology can drastically alter the effective surface area of the material, making it difficult to correctly dose particles that are not homogeneous. Particles of defined shape such as octahedral and cubic have been shown to outperform irregular shaped particles in some applications, leading to the need to synthesize particles of defined shape. In nature, highly homogeneous MNP are found within magnetotactic bacteria, a unique bacteria capable of producing magnetite nanoparticles internally under ambient conditions. Biomineralisation proteins control the properties of the MNPs, enhancing their homogeneity. One of these proteins, Mms6, has been successfully isolated and used in vitro as an additive in room-temperature co-precipitation reactions (RTCP) to produce particles of defined mono-dispersed size & morphology. When considering future industrial scale-up it is crucial to consider the costs and feasibility of an additive, as an additive that is not readily available or easily synthesized at a competitive price will not be sustainable. As such, additives selected for this research are inspired by the functional groups of biomineralisation proteins, but cost-effective, environmentally friendly, and compatible with scale-up. Diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA) have been successfully used in RTCP to modulate the properties of particles synthesized, leading to the formation of octahedral nanoparticles with no use of organic solvents, heating, or toxic precursors. By extending this principle to a fluidic system, ongoing research will reveal whether the amine additives can also exert morphological control in an environment which is suited toward higher particle yield. Two fluidic systems have been employed; a peristaltic turbulent flow mixing system suitable for the rapid production of MNP, and a macrofluidic system for the synthesis of tailored nanomaterials under a laminar flow regime. The presence of the amine additives in the turbulent flow system in initial results appears to offer similar morphological control as observed under RTCP conditions, with higher proportions of octahedral particles formed. This is a proof of concept which may pave the way to green synthesis of tailored MNP on an industrial scale. Mms6 and amine additives have been used in the macrofluidic system, with Mms6 allowing magnetite to be synthesized at unfavourable ferric ratios, but no longer influencing particle size. This suggests this synthetic technique while still benefiting from the addition of additives, may not allow additives to fully influence the particles formed due to the faster timescale of reaction. The amine additives have been tested at various concentrations, the results of which will be discussed in this paper.

Keywords: bioinspired, green synthesis, fluidic, magnetite, morphological control, scale-up

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