A Distinctive Insight into Inorganic Sonosensitizers: Design Principles and Application Domains.

Sonodynamic therapy (SDT) as a promising non-invasive anti-tumor means features the preferable penetration depth, which nevertheless, usually can't work without sonosensitizers. Sonosensitizers produce reactive oxygen species (ROS) in the presence of ultrasound to directly kill tumor cells, and concurrently activate anti-tumor immunity especially after integration with tumor microenvironment (TME)-engineered nanobiotechnologies and combined therapy. Current sonosensitizers are classified into organic and inorganic ones, and current most reviews only cover organic sonosensitizers and highlighted their anti-tumor applications. However, there have few specific reviews that focus on inorganic sonosensitizers including their design principles, microenvironment regulation, etc. In this review, inorganic sonosensitizers are first classified according to their design rationales rather than composition, and the action rationales and underlying chemistry features are highlighted. Afterward, what and how TME is regulated based on the inorganic sonosensitizers-based SDT nanoplatform with an emphasis on the TME targets-engineered nanobiotechnologies are elucidated. Additionally, the combined therapy and their applications in non-cancer diseases are also outlined. Finally, the setbacks and challenges, and proposed the potential solutions and future directions is pointed out. This review provides a comprehensive and detailed horizon on inorganic sonosensitizers, and will arouse more attentions on SDT.

Diagnosis and treatment status of inoperable locally advanced breast cancer and the application value of inorganic nanomaterials.

Locally advanced breast cancer (LABC) is a heterogeneous group of breast cancer that accounts for 10-30% of breast cancer cases. Despite the ongoing development of current treatment methods, LABC remains a severe and complex public health concern around the world, thus prompting the urgent requirement for innovative diagnosis and treatment strategies. The primary treatment challenges are inoperable clinical status and ineffective local control methods. With the rapid advancement of nanotechnology, inorganic nanoparticles (INPs) exhibit a potential application prospect in diagnosing and treating breast cancer. Due to the unique inherent characteristics of INPs, different functions can be performed via appropriate modifications and constructions, thus making them suitable for different imaging technology strategies and treatment schemes. INPs can improve the efficacy of conventional local radiotherapy treatment. In the face of inoperable LABC, INPs have proposed new local therapeutic methods and fostered the evolution of novel strategies such as photothermal and photodynamic therapy, magnetothermal therapy, sonodynamic therapy, and multifunctional inorganic nanoplatform. This article reviews the advances of INPs in local accurate imaging and breast cancer treatment and offers insights to overcome the existing clinical difficulties in LABC management.

Eco-Friendly Inorganic Binders: A Key Alternative for Reducing Harmful Emissions in Molding and Core-Making Technologies.

Many years of foundry practice and much more accurate analytical methods have shown that sands with organic binders, in addition to their many technological advantages, pose risks associated with the emission of many compounds, including harmful ones (e.g., formaldehyde, phenol, benzene, polycyclic aromatic hydrocarbons, and sulfur), arising during the pouring of liquid casting alloys into molds, their cooling, and knock-out. The aim of this research is to demonstrate the potential benefits of adopting inorganic binders in European iron foundries. This will improve the environmental and working conditions by introducing cleaner and more ecological production methods, while also ranking the tested binders studied in terms of their harmful content. The article pays special attention to the analysis of seven innovative inorganic binders and one organic binder, acting as a reference for emissions of gases from the BTEX (benzene, toluene, ethylbenzene, and xylenes) and PAHs (polycyclic aromatic hydrocarbons) groups and other compounds such as phenol, formaldehyde, and isocyanates (MDI and TDI) generated during the mold pouring process with liquid metals. The knowledge gained will, for the first time, enrich the database needed to update the Reference Document on The Best Available Techniques for the Smitheries and Foundries Industry (SF BREF).

Ab Initio Machine Learning in Chemical Compound Space.

Chemical compound space (CCS), the set of all theoretically conceivable combinations of chemical elements and (meta-)stable geometries that make up matter, is colossal. The first-principles based virtual sampling of this space, for example, in search of novel molecules or materials which exhibit desirable properties, is therefore prohibitive for all but the smallest subsets and simplest properties. We review studies aimed at tackling this challenge using modern machine learning techniques based on (i) synthetic data, typically generated using quantum mechanics based methods, and (ii) model architectures inspired by quantum mechanics. Such Quantum mechanics based Machine Learning (QML) approaches combine the numerical efficiency of statistical surrogate models with an ab initio view on matter. They rigorously reflect the underlying physics in order to reach universality and transferability across CCS. While state-of-the-art approximations to quantum problems impose severe computational bottlenecks, recent QML based developments indicate the possibility of substantial acceleration without sacrificing the predictive power of quantum mechanics.

Inorganic Enzyme Mimics.

Enzyme mimics (or artificial enzymes) have emerged as valuable alternatives to natural enzymes since the pioneering work of Ronald Breslow. They have numerous advantages over natural enzymes, such as high stability, low cost, and tailorable activity. Among varieties of materials explored to mimic enzymes, the inorganic ones, including inorganic complexes and nanomaterials, have attracted increasing interest over the last decade and have the potential to address the current challenges in energy, environment, health, etc.

Inorganic oxidizer detection from propellants, pyrotechnics, and homemade explosive powders using gradient elution moving boundary electrophoresis.

Advancement in rapid targeted chemical analysis of homemade and improvised explosive devices is critical for the identification of explosives-based hazards and threats. Gradient elution moving boundary electrophoresis (GEMBE), a robust electrokinetic separation technique, was employed for the separation and detection of common inorganic oxidizers from frequently encountered fuel-oxidizer mixtures. The GEMBE system incorporated sample and run buffer reservoirs, a short capillary (5 cm), an applied electric field, and a pressure-driven counterflow. GEMBE provided a separation format that allowed for continuous injection of sample, selectivity of analytes, and no sample cleanup or filtration prior to analysis. Nitrate, chlorate, and perchlorate oxidizers were successfully detected from low explosive propellants (e.g., black powders and black powder substitutes), pyrotechnics (e.g., flash powder), and tertiary explosive mixtures (e.g., ammonium nitrate- and potassium chlorate-based fuel-oxidizer mixtures). Separation of these mixtures exhibited detection without interference from a plethora of additional organic and inorganic fuels, enabled single particle analysis, and demonstrated semiquantitative capabilities. The bulk counterflow successfully excluded difficult components from fouling the capillary, yielding estimated limits of detection down to approximately 10 µmol/L. Finally, nitrate was separated and detected from postblast debris collected and directly analyzed from two nitrate-based charges.

Flower-Like Superstructures: Structural Features, Applications and Future Perspectives.

Mimicking natural objects such as flowers, is an objective of scientists not only because of their attractive appearance, but also to understand the natural phenomena that underpin real world applications such as drug delivery, enzymatic reactions, electronics, and catalysis, to name few. This article reviews the types, preparation methods, and structural features of flower-like structures along with their key applications in various fields. We discuss the various types of flower-like structures composed of inorganic, organic-inorganic hybrid, inorganic-protein, inorganic-enzyme and organic compositions. We also discuss recent development in flower-like structures prepared by self-assembly approaches. Finally, we conclude our review with the future prospects of flower-like micro-structures in key fields, being biomedicine, sensing and catalysis.

Versatile Types of Organic/Inorganic Nanohybrids: From Strategic Design to Biomedical Applications.

Organic/inorganic nanohybrids have attracted widespread interests due to their favorable properties and promising applications in biomedical areas. Great efforts have been made to design and fabricate versatile nanohybrids. Among different organic components, diverse polymers offer unique avenues for multifunctional systems with collective properties. This review focuses on the design, properties, and biomedical applications of organic/inorganic nanohybrids fabricated from inorganic nanoparticles and polymers. We begin with a brief introduction to a variety of strategies for the fabrication of functional organic/inorganic nanohybrids. Then the properties and functions of nanohybrids are discussed, including properties from organic and inorganic parts, synergistic properties, morphology-dependent properties, and self-assembly of nanohybrids. After that, current situations of nanohybrids applied for imaging, therapy, and imaging-guided therapy are demonstrated. Finally, we discuss the prospect of organic/inorganic nanohybrids and highlight the challenges and opportunities for the future investigations.

Intermediate state representation approach to physical properties of molecular electron-attached states: Theory, implementation, and benchmarking.

Computational schemes for comprehensive studies of molecular electron-attached states and the calculation of electron affinities (EAs) are formulated and implemented employing the intermediate state representation (ISR) formalism and the algebraic-diagrammatic construction approximation for the electron propagator (EA-ADC). These EA-ADC(n)/ISR(m) schemes allow for a consistent treatment of not only electron affinities and pole strengths up to third-order of perturbation theory (n = 3) but also one-electron properties of electron-attached states up to second order (m = 2). The EA-ADC/ISR equations were implemented in the Q-Chem program for Sz-adapted intermediate states, allowing also open-shell systems to be studied using unrestricted Hartree-Fock references. For benchmarking of the EA-(U)ADC/ISR schemes, EAs and dipole moments of various electron-attached states of small closed- and open-shell molecules were computed and compared to full configuration interaction data. As an illustrative example, EA-ADC(3)/ISR(2) has been applied to the thymine-thymine (6-4) DNA photolesion.

Differential effects of inorganic salts on cellulase kinetics in enzymatic saccharification of cellulose and lignocellulosic biomass.

Inorganic salt pretreatment of lignocellulosic biomass has proven to be an efficient way to increase the efficiency of enzymatic saccharification. However, it is not clear that this improvement is the result of modification of the lignocellulosic substrate after pretreatment, or removal of inhibitor, or enhancement of cellulase or a combination of these events. Therefore, this study aimed to analyze the effects of inorganic salts on kinetics of cellulase enzymes (celluclast 1.5L and accellerase 1500). Two substrates rich in cellulose content [carboxymethylcellulose (CMC), avicel (AV)] and lignocellulose substrate [sugarcane bagasse (SB)] were considered. The enzymatic saccharification was carried with and without the addition of inorganic salts (NaCl and KCl) at 0.5 M and 1.0 M concentration. The kinetic parameters, Km and Vm, were determined to mechanically understand the pattern of inhibition and enhancement of inorganic salts on enzymatic saccharification. The kinetics parameters of celluclast 1.5L and accellerase 1500 for hydrolysis of CMC and AV with NaCl showed uncompetitive inhibition. Whereas, influences of KCl on both cellulase were differentiated to function in inhibition or enhancement modes when challenged with different substrates. On the other hand, enzymatic hydrolysis efficiencies of SB using both cellulases were enhanced under addition of NaCl and KCl, by increasing Vm of celluclast 1.5L from 0.303 to 0.635 mg/mL min (0.5 M KCl) and accellerase 1500 from 0.383 to 0.719 mg/mL min (1.0 M NaCl). The details of kinetic analysis in this work revealed the mechanism of inorganic salts on cellulase kinetics to be involved in substrate modification and removal of inhibitor.

Stereospecific interactions between chiral inorganic nanomaterials and biological systems.

Chirality is ubiquitous in nature and plays mysterious and essential roles in maintaining key biological and physiological processes. As biological systems display high selectivity for chiral biomolecules, chiral bio-nanoscience has become a popular research field during the last decade. Homochirality, as an essential attribute of natural compounds (l-amino acids, d-sugars, etc.), inspired the emergence of synthetic chiral nanomaterials, which in turn impacted their biological functions and fates. This review is a comprehensive overview of the interactions between chiral inorganic nanostructures and biosystems. We start with the recent progress in biocompatible chiral nanomaterials and focus on stereospecific biological interactions ranging from enantioselective reactions in applications such as sensing and catalysis to chirality-dependent controllable manipulation of cell behaviours and finally to enantiopure nanoplatforms for improved disease therapy. We also discuss the current challenges and future potential of these chiral nanotechnologies in biomedicine and bioengineering, provide strategies to overcome these barriers and offer a future perspective.

Antimicrobial Resistance and Inorganic Nanoparticles.

Antibiotics are being less effective, which leads to high mortality in patients with infections and a high cost for the recovery of health, and the projections that are had for the future are not very encouraging which has led to consider antimicrobial resistance as a global health problem and to be the object of study by researchers. Although resistance to antibiotics occurs naturally, its appearance and spread have been increasing rapidly due to the inappropriate use of antibiotics in recent decades. A bacterium becomes resistant due to the transfer of genes encoding antibiotic resistance. Bacteria constantly mutate; therefore, their defense mechanisms mutate, as well. Nanotechnology plays a key role in antimicrobial resistance due to materials modified at the nanometer scale, allowing large numbers of molecules to assemble to have a dynamic interface. These nanomaterials act as carriers, and their design is mainly focused on introducing the temporal and spatial release of the payload of antibiotics. In addition, they generate new antimicrobial modalities for the bacteria, which are not capable of protecting themselves. So, nanoparticles are an adjunct mechanism to improve drug potency by reducing overall antibiotic exposure. These nanostructures can overcome cell barriers and deliver antibiotics to the cytoplasm to inhibit bacteria. This work aims to give a general vision between the antibiotics, the nanoparticles used as carriers, bacteria resistance, and the possible mechanisms that occur between them.

Inorganic Elements in Mytilus galloprovincialis Shells: Geographic Traceability by Multivariate Analysis of ICP-MS Data.

The international seafood trade is based on food safety, quality, sustainability, and traceability. Mussels are bio-accumulative sessile organisms that need regular control to guarantee their safe consumption. However, no well-established and validated methods exist to trace mussel origin, even if several attempts have been made over the years. Recently, an inorganic multi-elemental fingerprint coupled to multivariate statistics has increasingly been applied in food quality control. The mussel shell can be an excellent reservoir of foreign inorganic chemical species, allowing recording long-term environmental changes. The present work investigates the multi-elemental composition of mussel shells, including Al, Cu, Cr, Zn, Mn, Cd, Co, U, Ba, Ni, Pb, Mg, Sr, and Ca, determined by inductively-coupled plasma mass-spectrometry in Mytilus galloprovincialis collected along the Central Adriatic Coast (Marche Region, Italy) at 25 different sampling sites (18 farms and 7 natural banks) located in seven areas. The experimental data, coupled with chemometric approaches (principal components analysis and linear discriminant analysis), were used to create a statistical model able to discriminate samples as a function of their production site. The LDA model is suitable for achieving a correct assignment of >90% of individuals sampled to their respective harvesting locations and for being applied to counteract fraud.

Environment-Induced Reversible Modulation of Optical and Electronic Properties of Lead Halide Perovskites and Possible Applications to Sensor Development: A Review.

Lead halide perovskites are currently widely investigated as active materials in photonic and optoelectronic devices. While the lack of long term stability actually limits their application to commercial devices, several experiments demonstrated that beyond the irreversible variation of the material properties due to degradation, several possibilities exist to reversibly modulate the perovskite characteristics by acting on the environmental conditions. These results clear the way to possible applications of lead halide perovskites to resistive and optical sensors. In this review we will describe the current state of the art of the comprehension of the environmental effects on the optical and electronic properties of lead halide perovskites, and of the exploitation of these results for the development of perovskite-based sensors.

Reversible Diels-Alder Reactions with a Fluorescent Dye on the Surface of Magnetite Nanoparticles.

Diels-Alder reactions on the surface of nanoparticles allow a thermoreversible functionalization of the nanosized building blocks. We report the synthesis of well-defined magnetite nanoparticles by thermal decomposition reaction and their functionalization with maleimide groups. Attachment of these dienophiles was realized by the synthesis of organophosphonate coupling agents and a partial ligand exchange of the original carboxylic acid groups. The functionalized iron oxide particles allow a covalent surface attachment of a furfuryl-functionalized rhodamine B dye by a Diels-Alder reaction at 60 °C. The resulting particles showed the typical fluorescence of rhodamine B. The dye can be cleaved off the particle surface by a retro-Diels-Alder reaction. The study showed that organic functions can be thermoreversibly attached onto inorganic nanoparticles.

Physico-Chemical Properties of Inorganic NPs Influence the Absorption Rate of Aquatic Mosses Reducing Cytotoxicity on Intestinal Epithelial Barrier Model.

Noble metals nanoparticles (NPs) and metal oxide NPs are widely used in different fields of application and commercial products, exposing living organisms to their potential adverse effects. Recent evidences suggest their presence in the aquifers water and consequently in drinking water. In this work, we have carefully synthesized four types of NPs, namely, silver and gold NPs (Ag NPs and Au NPs) and silica and titanium dioxide NPs (SiO2 NPs and TiO2 NPs) having a similar size and negatively charged surfaces. The synthesis of Ag NPs and Au NPs was carried out by colloidal route using silver nitrate (AgNO3) and tetrachloroauric (III) acid (HAuCl4) while SiO2 NPs and TiO2 NPs were achieved by ternary microemulsion and sol-gel routes, respectively. Once the characterization of NPs was carried out in order to assess their physico-chemical properties, their impact on living cells was studied. We used the human colorectal adenocarcinoma cells (Caco-2), known as the best representative intestinal epithelial barrier model to understand the effects triggered by NPs through ingestion. Then, we moved to explore how water contamination caused by NPs can be lowered by the ability of three species of aquatic moss, namely, Leptodictyum riparium, Vesicularia ferriei, and Taxiphyllum barbieri, to absorb them. The experiments were conducted using two concentrations of NPs (100 µM and 500 Μm as metal content) and two time points (24 h and 48 h), showing a capture rate dependent on the moss species and NPs type. Then, the selected moss species, able to actively capture NPs, appear as a powerful tool capable to purify water from nanostructured materials, and then, to reduce the toxicity associated to the ingestion of contaminated drinking water.

Materials and Designs for Power Supply Systems in Skin-Interfaced Electronics.

Recent advances in materials chemistry and composite materials design establish the foundations for classes of electronics with physical form factors that bridge the gap between soft biological organisms and rigid microsystems technologies. Skin-interfaced platforms of this type have broad utility in continuous clinical-grade monitoring of physiological status, with the potential to significantly lower the cost and increase the efficacy of modern health care. Development of materials and device designs for power supply systems in this context is critically important, and it represents a rapidly expanding focus of research in the chemical sciences. Reformulating conventional technologies into biocompatible platforms and co-integrating them into skin-interfaced systems demand innovative approaches in materials chemistry and engineering. In terms of physical properties, the resulting devices must offer levels of flexibility, stretchability, thickness, and mass density that approach those of the epidermis itself, while maintaining operational characteristics and mechanical durability for practical use outside of a laboratory or hospital. While nearly all commercially available components for energy storage and harvesting are rigid and planar, recent research provides options in devices that are biocompatible not only at the level of the constituent materials but also in terms of the mechanics and geometrical forms, with resulting capabilities for establishing stable, nonirritating, intimate interfaces to the skin for extended periods of time. This Account highlights the range of materials choices and associated device architectures for skin-interfaced power supply systems. The Account begins with an overview of the main design strategies, ranging from one-, two-, and three-dimensional engineered composite structures to active materials that are intrinsically stretchable. The following sections describe a broad collection of devices based on these concepts, starting with batteries and supercapacitors for storage and then photovoltaic, piezoelectric, triboelectric, and thermoelectric devices for harvesting. Representative examples highlight recent advances, with a focus on the relationship between the materials and the performance during deformation. A final section discusses the challenges and opportunities in this area. Continued efforts in fundamental chemical research will be critically important to progress in this emerging field of technology. For example, understanding the mechanisms by which physical deformations affect the intrinsic materials properties and the system-level performance requires further study. The development of stretchable and biocompatible solid electrolytes with high ionic conductivity is an example of a specific area of interest for energy storage devices. Here and in other storage and harvesting systems advanced materials are needed to provide robust barriers to environmental factors. Work to address these and other interesting challenges will demand multidisciplinary collaborations between chemists, materials scientists, bioengineers, and clinicians, all oriented toward establishing the foundations for technologies that could help to address global grand challenges in human health care.

Impacts of foodborne inorganic nanoparticles on the gut microbiota-immune axis: potential consequences for host health.

BACKGROUND: In food toxicology, there is growing interest in studying the impacts of foodborne nanoparticles (NPs, originating from food additives, food supplements or food packaging) on the intestinal microbiome due to the important and complex physiological roles of these microbial communities in host health. Biocidal activities, as described over recent years for most inorganic and metal NPs, could favour chronic changes in the composition and/or metabolic activities of commensal bacteria (namely, intestinal dysbiosis) with consequences on immune functions. Reciprocally, direct interactions of NPs with the immune system (e.g., inflammatory responses, adjuvant or immunosuppressive properties) may in turn have effects on the gut microbiota. Many chronic diseases in humans are associated with alterations along the microbiota-immune system axis, such as inflammatory bowel diseases (IBD) (Crohn's disease and ulcerative colitis), metabolic disorders (e.g., obesity) or colorectal cancer (CRC). This raises the question of whether chronic dietary exposure to inorganic NPs may be viewed as a risk factor facilitating disease onset and/or progression. Deciphering the variety of effects along the microbiota-immune axis may aid the understanding of how daily exposure to inorganic NPs through various foodstuffs may potentially disturb the intricate dialogue between gut commensals and immunity, hence increasing the vulnerability of the host. In animal studies, dose levels and durations of oral treatment are key factors for mimicking exposure conditions to which humans are or may be exposed through the diet on a daily basis, and are needed for hazard identification and risk assessment of foodborne NPs. This review summarizes relevant studies to support the development of predictive toxicological models that account for the gut microbiota-immune axis. CONCLUSIONS: The literature indicates that, in addition to evoking immune dysfunctions in the gut, inorganic NPs exhibit a moderate to extensive impact on intestinal microbiota composition and activity, highlighting a recurrent signature that favours colonization of the intestine by pathobionts at the expense of beneficial bacterial strains, as observed in IBD, CRC and obesity. Considering the long-term exposure via food, the effects of NPs on the gut microbiome should be considered in human health risk assessment, especially when a nanomaterial exhibits antimicrobial properties.

Application of micro-dried droplets for quantitative analysis of particulate inorganic samples with LA-ICP-MS demonstrated on surface-modified nanoparticle TiO2 catalyst materials.

A quick, flexible and reliable method was developed, based on laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), for accurate assessment of nanomaterial composition with sample amounts in the picogram to nanogram range. We demonstrate its capabilities for the analysis of surface-modified TiO2 nanoparticulate (NP) catalyst materials. For sampling, suspensions of NP were deposited on a substrate material, ablated with a pulsed laser and then analysed using quadrupole ICP-MS. The calibration and quantification approach is based on the use of so-called micro-dried droplets (µDD) as the standard material. To overcome some of the major drawbacks of conventional dried droplet approaches, self-aliquoting wells were used in this work. By mimicking the ablation conditions for the sample and standard, it was possible to create a pseudo-matrix-matched calibration, not only for this specific NP composition but also for a larger variety of samples. A commercially available reference material (AUROlite™, Strem Chemicals) was used to compare the method against established methods such as slurry analysis and microwave-assisted digestion in combination with subsequent liquid sample measurement. The results obtained with the proposed procedure (0.74%wt ± 0.13%wt) are in good agreement to a certified value (0.8%wt) and added an additional layer of information. Due to the significantly reduced sampling size in comparison with the investigated liquid measurement approaches, it was possible to obtain information about the homogeneity of the catalyst material. The results indicate that the AUROlite™ reference material has a heterogeneous loading which requires more than 300 pg of material to be used to cancel out. This was not observed for the custom materials discussed in this work. Graphical abstract.

Cargo-Compatible Encapsulation in Virus-Based Nanoparticles.

Molecule encapsulation in virus-based nanoparticles (VNPs) is an emerging bioinspired way to design novel functional nanostructures and devices. Here, we report a general cargo-compatible approach to encapsulate guest materials based on the apparent critical assembly concentration (CACapp) of VNPs. Different from the conventional buffer-exchange method, the new method drives the reassembly of VNPs to encapsulate cargoes by simply concentrating an adequately diluted mixture of VNP building blocks and cargoes to a concentration above the CACapp. This method has been proved to work well on different types of cargoes (including inorganic nanoparticles and proteins) and VNPs. The major advantage of this method is that it can maximally preserve cargo stability and activity by providing the freedom to choose cargo-friendly buffer conditions throughout the encapsulation process. This method would benefit the realization of the potentials of VNPs and other protein nanocages as nanomaterials in diverse fields of nanotechnology.