Inorganic-based Materials Research Articles

Amino-Acid-Substituted Perylene Diimide as the Organic Cathode Materials for Lithium-Ion Batteries.

One of the most effective cost reduction and green engineering projects is to introduce organic compounds to electrode materials instead of expensive inorganic-based materials. In this work, derivatives of perylene diimide substituted with amino acids (PDI_AAs) showed the characteristics of redox-active organic compounds and were, therefore, used as cathode materials of lithium-ion batteries (LIBs). Among the as-synthesized PDI_AAs, the L-alanine-substituted PDI (PDI_A) showed the most improved cycling performances of 86 mAhg-1 over 150 cycles with retention of 95% at 50 mAg-1. Furthermore, at a high current density of 500 mAg-1, PDI_A exhibited a long-term cycling performance of 47 mAhg-1 (retention to 98%) over 5000 cycles. In addition, ex situ attenuated total reflection Fourier-transform infrared spectroscopy (ATR FT-IR) analysis of electrodes at various charging states showed the mechanism of the charge-discharge process of PDI_A.

MoS2 nanoflower-decorated lignin nanoparticles for superior lubricant properties.

Lignin has been, for a long time, treated as a low-value waste product. To change this scenario, high-value applications have been recently pursued, e.g., the preparation of hybrid materials with inorganic components. Although hybrid inorganic-based materials can benefit from the reactive lignin phenolic groups at the interface, often responsible for optimizing specific properties, this is still an underexplored field. Here, we present a novel and green material based on the combination of hydroxymethylated lignin nanoparticles (HLNPs) with molybdenum disulfide (MoS2) nanoflowers grown via a hydrothermal route. By bringing together the lubricant performance of MoS2 and the structural stability of biomass-based nanoparticles, a MoS2-HLNPs hybrid is presented as a bio-derived additive for superior tribological performances. While FT-IR analysis confirmed the structural stability of lignin after the hydrothermal growth of MoS2, TEM and SEM micrographs revealed a homogeneous distribution of MoS2 nanoflowers (average size of 400 nm) on the HLNPs (average size of 100 nm). Regarding the tribological tests, considering a pure oil as reference, only HLNPs as bio-derived additives led to a reduction in the wear volume of 18%. However, the hybrid of MoS2-HLNPs led to a considerably higher reduction (71%), pointing out its superior performance. These results open a new window of opportunity for a versatile and yet underexplored field that can pave the way for a new class of biobased lubricants.

Organic- or Inorganic-based Nanomaterials: Opportunities and Challenges in the Selection for Biomedicines.

Since the inception of nanotechnology, several efforts have been dedicated to fabricating diverse nanodevices with exceptional performance. These innovative constructs have been applied in medicine due to their tailorable physicochemical properties (chemical composition, optical activity, spectra, and charge) and morphological attributes (size, shape, and surface area). Moreover, these versatile nanomedicines could promisingly offer better performance over the conventional therapeutic strategies. Broadly speaking, in terms of chemical composition, nanobiomaterials are classified into two predominant categories of organic and inorganic- based components. Despite their success and enormous versatile advancements in the past two decades, the significant progress towards clinical translation has been hampered by their corresponding intrinsic limitations. In this perspective, we give a brief overview of these organic- and inorganic-based materials, highlighting opportunities and challenges towards their utilization in medicine. Finally, we provide an interesting outlook on the lessons learned and look forward to further developing these materials, emphasizing their potential in clinical translation.

Nanoimprint Lithography Processing of Inorganic-Based Materials

We review past and recent progress in Nano-Imprint Lithography (NIL) methods to (nano-) structure inorganic materials from sol-gel liquid formulations and colloidal suspensions onto a surface. This technique, first inspired by embossing techniques, was developed for soft polymer processing, as final or intermediate materials, but is today fully adapted to hard inorganic materials with high dielectric constant, such as metal oxides, with countless chemical compositions provided by the sol-gel chemistry. Consequently, NIL has become a versatile, high throughput, and highly precise microfabrication method that is mature for lab developments and scaling up. We first describe the state-of-the-art in nanofabrication methods and the plethora of approaches developed in the last decades to imprint metal oxides from inorganic solutions. These are discussed and compared in terms of performances, issues, and ease of implementation. The final part is devoted to relevant applications in domains of interest.

Inorganic-based adsorbent materials for the removal of gaseous pollutants

Inorganic-based adsorbent materials for the removal of gaseous pollutants

Stable and Highly Soluble Anolyte for Non-Aqueous Redox Flow Batteries

Redox flow batteries (RFBs), in which electric charge is stored in redox-active materials (redoxmer) dissolved in liquid electrolytes, show significant potential for grid-scale energy storage applications. Because of the liquid nature, RFBs feature remarkable flexibilities, including decoupled energy and power that is highly desired for adapting various scales of energy storage requirements. Aprotic organic solvents are extensively studied as they can significantly extend the electrochemical window, leading to higher cell voltage and energy density of RFBs. To that end, developing redoxmers with high solubility and stability in non-aqueous solvents are actively pursed in order to realize the full potentials. Inorganic-based redoxmer materials showed good cyclability in aqueous redox flow batteries. Designing non-aqueous compatible redoxmers based on traditional inorganic-based materials encounter critical technical and economic limitations such as low solubility, inferior electrochemical activity, and high cost. In this presentation, a ferrate(III) based low potential redoxmer (anolyte) will be discussed. The synthesized redoxmer showed high solubility in acetonitrile (>2 M) with redox potential of ~-1.36 V (vs Ag/Ag+) and deliver very stable cycling performance evidenced by the symmetric H-cell cycling. The design approach for non-aqueous compatible redoxmers based on traditional inorganic-based materials may represent a promising strategy for constructing high energy dense and stable RFBs.

Inorganic Biomaterials for Regenerative Medicine.

Regenerative medicine leverages the innate potential of the human body to efficiently repair and regenerate damaged tissues using engineered biomaterials. By designing responsive biomaterials with the appropriate biophysical and biochemical characteristics, cellular response can be modulated to direct tissue healing. Recently, inorganic biomaterials have been shown to regulate cellular responses including cell-cell and cell-matrix interactions. Moreover, ions released from these mineral-based biomaterials play a vital role in defining cell identity, as well as driving tissue-specific functions. The intrinsic properties of inorganic biomaterials, such as the release of bioactive ions (e.g., Ca, Mg, Sr, Si, B, Fe, Cu, Zn, Cr, Co, Mo, Mn, Au, Ag, V, Eu, and La), can be leveraged to induce phenotypic changes in cells or modulate the immune microenvironment to direct tissue healing and regeneration. Biophysical characteristics of biomaterials, such as topography, charge, size, electrostatic interactions, and stiffness can be modulated by addition of inorganic micro- and nanoparticles to polymeric networks have also been shown to play an important role in their biological response. In this Review, we discuss the recent emergence of inorganic biomaterials to harness the innate regenerative potential of the body. Specifically, we will discuss various biophysical or biochemical effects of inorganic-based materials in directing cellular response for regenerative medicine applications.

From Green Remediation to Polymer Hybrid Fabrication with Improved Optical Band Gaps.

The present work proposed a novel approach for transferring high-risk heavy metals tometal complexes via green chemistry remediation. The method of remediation of heavy metals developed in the present work is a great challenge for global environmental sciences and engineering because it is a totally environmentally friendly procedure in which black tea extract solution is used. The FTIR study indicates that black tea contains enough functional groups (OH and NH), polyphenols and conjugated double bonds. The synthesis of copper complex was confirmed by the UV-vis, XRD and FTIR spectroscopic studies. The XRD and FTIR analysis reveals the formation of complexation between Cu metal complexes and Poly (Vinyl Alcohol) (PVA) host matrix. The study of optical parameters indicates that PVA-based hybrids exhibit a small optical band gap, which is close to inorganic-based materials. It was noted that the absorption edge shifted to lower photon energy. When Cu metal complexes were added to PVA polymer, the refractive index was significantly tuned. The band gap shifts from 6.2 eV to 1.4 eV for PVA incorporated with 45 mL of Cu metal complexes. The nature of the electronic transition in hybrid materials was examined based on the Taucs model, while a close inspection of the optical dielectric loss was also performed in order to estimate the optical band gap. The obtained band gaps of the present work reveal that polymer hybrids with sufficient film-forming capability could be useful to overcome the drawbacks associated with conjugated polymers. Based on the XRD results and band gap values, the structure-property relationships were discussed in detail.

Materials and Systems for Organic Redox Flow Batteries: Status and Challenges

Redox flow batteries (RFBs) are propitious stationary energy storage technologies with exceptional scalability and flexibility to improve the stability, efficiency, and sustainability of our power grid. The redox-active materials are the key component for RFBs with which to achieve high energy density and good cyclability. Traditional inorganic-based materials encounter critical technical and economic limitations such as low solubility, inferior electrochemical activity, and high cost. Redox-active organic materials (ROMs) are promising alternative “green” candidates to push the boundaries of energy storage because of the significant advantages of molecular diversity, structural tailorability, and natural abundance. Here, the recent development of a variety of ROMs and associated battery designs in both aqueous and nonaqueous electrolytes are reviewed. The critical challenges and potential research opportunities for developing practically relevant organic flow batteries are discussed.

From Nano to Micro: using nanotechnology to combat microorganisms and their multidrug resistance.

The spread of antibiotic resistance and increasing prevalence of biofilm-associated infections is driving demand for new means to treat bacterial infection. Nanotechnology provides an innovative platform for addressing this challenge, with potential to manage even infections involving multidrug-resistant (MDR) bacteria. The current review summarizes recent progress over the last 2 years in the field of antibacterial nanodrugs, and describes their unique properties, mode of action and activity against MDR bacteria and biofilms. Biocompatibility and commercialization are also discussed. As opposed to the more common division of nanoparticles (NPs) into organic- and inorganic-based materials, this review classifies NPs into two functional categories. The first includes NPs exhibiting intrinsic antibacterial properties and the second is devoted to NPs serving as a cargo for delivering antibacterial agents. Antibacterial nanomaterials used to decorate medical devices and implants are reviewed here as well.

Zeolitic Imidazole Framework (ZIF) Nanospheres for Easy Encapsulation and Controlled Release of an Anticancer Drug Doxorubicin under Different External Stimuli: A Way toward Smart Drug Delivery System.

The conventional drug delivery systems made from organic- or inorganic-based materials suffer from some problems associated with uncontrolled drug release, biocompatibility, cytotoxicity, and so forth. To overcome these problems, zeolitic imidazole framework (ZIF) hybrid materials can be one of the solutions. Here, we report a very easy and successful encapsulation of an anticancer drug doxorubicin inside two ZIFs, namely, ZIF-7 and ZIF-8, which are little explored as drug delivery systems, and we studied the controlled release of the drug from these two ZIFs under external stimuli such as change in pH and upon contact with biomimetic systems. Experimental results demonstrate that ZIF-7 remains intact when the pH changes from physiological condition to acidic condition, whereas ZIF-8 successfully releases drug under acidic condition. Interestingly, both the ZIFs are excellent for drug release when they come in contact with micelles or liposomes. In the case of ZIF-8, the drug delivery can be controlled for 3 h, whereas its analogue ZIF-7 delivers the drug for a time span of 10 h. We explained the reluctance of ZIF-7 toward drug release in terms of rigidity. This study highlights that by using different ZIFs and liposomes, the drug release rate can be easily modulated, which implies ample possibility for ZIFs as a good drug delivery system. The study shows a novel strategy for easy drug encapsulation and its release in a controlled manner, which will help future development of the drug delivery system.

Crosslinked Electroactive Polymers Containing Naphthalene-Bisimide Redox Centers for Energy Storage

Electroactive polymers represent an attractive alternative to the current inorganic-based materials for electrochemical energy storage systems as they allow eliminating the need for expensive transition and rare-earth metals. This is particularly relevant for all polymers that can be obtained by direct oxidative polymerization of the corresponding monomer. We investigate the energy storage properties of electroactive polymers based around the concept of attaching a redox-active core to a highly electronically conductive backbone. In this paper we describe the synthesis and characterization of physical and electrochemical properties of the naphthalene-bisimide (NPbIm) core coupled with Poly(3,4-ethylenedioxythiophene) (PEDOT). We find that the composite polymer shows two distinct monoelectronic redox peaks attributed to the reduction of naphthalene-bisimide to radical anion and dianion near 2.5 V vs. Li+/Li, as well as the standard PEDOT electrochemistry. The polymer shows excellent charge retention capabilities with more than 90% capacity maintained after 1000 cycles as an electropolymerized film. Composite electrodes prepared with 73 wt% of powders of active material exhibit good high rate capabilities by retaining more than 70% of the original capacity measured at C/10 when cycled at 1C rate. To the best of our knowledge this is one of the highest performances so far reported for organic materials.

Organic nanocrystals of the resorcinarene hexamer via sonochemistry: evidence of reversed crystal growth involving hollow morphologies.

Nano- and micrometer-scale crystals of a self-assembled hexamer have been synthesized via sonochemistry. The application of ultrasonic irradiation afforded hollow rhombic-dodecahedral crystals of the C-methylcalix[4]resorcinarene hexamer. The formation of the hollow crystals is attributed to a reversed crystal growth mechanism heretofore described only in the synthesis of inorganic-based materials.

Breakthrough and future: nanoscale controls of compositions, morphologies, and mesochannel orientations toward advanced mesoporous materials

Currently, ordered mesoporous materials prepared through the self-assembly of surfactants have attracted growing interests owing to their special properties, including uniform mesopores and a high specific surface area. Here we focus on fine controls of compositions, morphologies, mesochannel orientations which are important factors for design of mesoporous materials with new functionalities. This Review describes our recent progress toward advanced mesoporous materials. Mesoporous materials now include a variety of inorganic-based materials, for example, transition-metal oxides, carbons, inorganic-organic hybrid materials, polymers, and even metals. Mesoporous metals with metallic frameworks can be produced by using surfactant-based synthesis with electrochemical methods. Owing to their metallic frameworks, mesoporous metals with high electroconductivity and high surface areas hold promise for a wide range of potential applications, such as electronic devices, magnetic recording media, and metal catalysts. Fabrication of mesoporous materials with controllable morphologies is also one of the main subjects in this rapidly developing research field. Mesoporous materials in the form of films, spheres, fibers, and tubes have been obtained by various synthetic processes such as evaporation-mediated direct templating (EDIT), spray-dried techniques, and collaboration with hard-templates such as porous anodic alumina and polymer membranes. Furthermore, we have developed several approaches for orientation controls of 1D mesochannels. The macroscopic-scale controls of mesochannels are important for innovative applications such as molecular-scale devices and electrodes with enhanced diffusions of guest species.

Oriented Nanostructures for Energy Conversion and Storage

Recently, the role of nanostructured materials in addressing the challenges in energy and natural resources has attracted wide attention. In particular, oriented nanostructures demonstrate promising properties for energy harvesting, conversion, and storage. In this Review, we highlight the synthesis and application of oriented nanostructures in a few key areas of energy technologies, namely photovoltaics, batteries, supercapacitors, and thermoelectrics. Although the applications differ from field to field, a common fundamental challenge is to improve the generation and transport of electrons and ions. We highlight the role of high surface area to maximize the surface activity and discuss the importance of optimum dimension and architecture, controlled pore channels, and alignment of the nanocrystalline phase to optimize the transport of electrons and ions. Finally, we discuss the challenges in attaining integrated architectures to achieve the desired performance. Brief background information is provided for the relevant technologies, but the emphasis is focused mainly on the nanoscale effects of mostly inorganic-based materials and devices.

Expected and Unexpected Effects of Amino Acid Substitutions on Polypeptide-Directed Crystal Growth

Nature's use of biomineralization polypeptides to control and modulate the growth of biogenic minerals is an important process that, if properly understood, could have significant implications for designing and creating new inorganic-based materials. Although the sequences for a number of biomineralization proteins exist, very little is known about the participation of specific amino acids in the mineral modulation process. In this letter, we investigate the impact of global Asp --> Asn and Glu --> Gln substitutions on two mollusk shell nacre polypeptides, AP7N and n16N. We find that these global substitutions, which remove all anionic Ca(II) binding sites, abolish the expected in vitro mineralization activities associated with each native polypeptide. In addition, the ability of substituted peptides to form complexes with both Ca(II) and Ca(II) metal ion analogs is also abolished. However, some unexpected effects were noted. First, the Asp --> Asn, Glu --> Gln substituted n16N polypeptide is observed to self-assemble and form biofilms or coatings that appear to mineralize in vitro. Second, both polypeptides are structurally affected by these substitutions, with Asp --> Asn substituted AP7N transforming to an alpha helix and Asp --> Asn, Glu --> Gln substituted n16N transforming to a more unfolded random-coil-like structure. We find that the participation of Asp and Glu residues is crucial to the inherent mineralization activities and conformations of AP7N and n16N polypeptides. Surprisingly, we find that the replacement of anionic residues within biomineralization polypeptides such as n16N still permits mineral modulation, but in a different form that now involves peptide self-association and biofilm formation.

Extraction of 106Ru from simulated liquid nuclear wastes using inorganic phases with covalently-bound sulphur ligands and inorganic sulphides

Inorganic-based materials with pendant dithiocarbamate groups have acceptable affinities for 106Ru and the loaded materials have some resistance to radiolysis even at high dosages; inorganic sulphides are also capable of extracting ruthenium.