Inductively coupled plasma mass spectrometry based platforms for studies involving nanoparticle effects in biological samples

The widespread application of nanoparticles (NPs) in recent times has caused concern because of their effects in biological systems. Although NPs can be produced naturally, industrially synthesized NPs affect the metabolism of a given organism because of their high reactivity. The biotransformation of NPs involves different processes, including aggregation/agglomeration, and reactions with biomolecules that will be reflected in their toxicity. Several analytical techniques, including inductively coupled plasma mass spectrometry (ICP‐MS), have been used for characterizing and quantifying NPs in biological samples. In fact, in addition to providing information regarding the morphology and concentration of NPs, ICP‐MS‐based platforms, such as liquid chromatography/ICP‐MS, single‐particle ICP‐MS, field‐flow fractionation (asymmetrical flow field‐flow fractionation)‐ICP‐MS, and laser ablation‐ICP‐MS, yield elemental information about molecules. Furthermore, such information together with speciation analysis enlarges our understanding of the interaction between NPs and biological organisms. This study reports the contribution of ICP‐MS‐based platforms as a tool for evaluating NPs in distinct biological samples by providing an additional understanding of the behavior of NPs and their toxicity in these organisms.     

Anodic stripping electrochemical analysis of metal nanoparticles

Traditional anodic stripping voltammetry (ASV) involves electrodeposition (reduction) of metal ions from solution over some time scale onto a working electrode followed by stripping (oxidation) of the deposited metal in a second step, where the stripping potential and quantity of charge passed provide information about the metal identity and solution concentration, respectively. ASV has recently been extended to the analysis of metal nanoparticles (NPs), which have grown popular because of their fascinating properties tunable by size, shape, and composition. There is a need for improved methods of NP analysis, and because metal NPs can be oxidized to metal ions, ASV is a logical choice. Early studies involved metal NPs as tags for the detection of biomolecules. More recently, anodic stripping has been used to directly analyze the physical, chemical, and structural properties of metal NPs. This review highlights the stripping analysis of NP assemblies on macroelectrodes, individual NPs in solution during collisions with a microelectrode, and a single NP attached to an electrode. A surprising amount of information can be learned from this very simple, low-cost technique.     

Computer simulation studies on the interactions between nanoparticles and cell membrane

In recent times,nanoparticles(NPs)have received intense attention not only due to their potential applications as a candidate for drug delivery,but also because of their undesirable effects on human health.Although extensive experimental studies have been carried out in literature in order to understand the interaction between NPs and a plasma membrane,much less is known about the molecular details of the interaction mechanisms and pathways.As complimentary tools,coarse grained molecular dynamics(CGMD)and dissipative particle dynamics(DPD)simulations have been extensively used on the interaction mechanism and evolution pathway.In the present review we summarize computer simulation studies on the NP-membrane interaction,which developed over the last few years,and particularly evaluate the results from the DPD technique.Those studies undoubtedly deepen our understanding of the NP-membrane interaction mechanisms and provide a design guideline for new NPs.     

Electrode chemistry yields a nanoparticle-based NMR sensor for calcium

Magnetic nanoparticles (NPs) have been used to obtain NMR-based sensors for analytes ranging from small molecules to viruses by the conjugation of biomolecules (antibodies, proteins, oligonucleotides) to the surface of NPs. In the presence of an analyte, the NPs form clusters that alter the relaxation time of the surrounding water protons. Here, we show that an organic molecule that binds calcium ions of nonbiological origin, rather than a biomolecule, can be employed to modify the surface of a magnetic NP. When calcium ions are added, they induce NP clustering, providing an NMR-based sensor for these ions. Our work suggests that the many chemistries of nonbiological origin, such as those employed for ion-selective electrodes, can be adapted to obtain NMR-based sensors for ions.     

Magnetic soft silicone elastomers with tunable mechanical properties for magnetically actuated devices

Polydimethylsiloxane (PDMS)/iron oxide magnetic nanoparticle (NP) composites with tailored mechanical properties are prepared for use in magnetically actuated soft devices based on their controlled deformation by the application of an external magnetic field. This investigation reports the synthesis and functionalization of iron oxide NPs, the preparation of the PDMS/NP composites, the evaluation of NP dispersion using scanning electron microscopy (SEM) and optical microscopy, and the mechanical characterization of the composite films. Characterization includes rheological measurements as well as stress‐strain curves to obtain the Young modulus and elongation at break. SEM is used to probe individual NP dispersion, whereas optical microscopy provides rapid access to quantitative information about the size and distribution of particle aggregates. Results for nonfunctionalized (nf), oleic acid (OA)‐coated, and stearic acid (SA)‐coated iron oxide NPs and their blends are presented. PDMS elastomers containing both OA‐ and SA‐coated iron oxide NPs are found to have very low Young moduli with substantially higher resistance to failure than neat PDMS. For example, a formulation containing 2.5 wt% OA‐coated NPs and 2.5 wt% SA‐coated iron oxide NPs has a modulus of 0.15 MPa (compared with 0.24 MPa for neat PDMS), while it can withstand an elongation of about 1.5 times its initial length compared with only 0.3 times for neat PDMS. As a comparison, the modulus of the most commonly used commercial PDMS elastomer (Sylgard 184) is an order of magnitude higher than that of the composites prepared here, whereas maximum elongation is similar for the two. The formulations developed in this work could be used in applications where high deformability is required with limited magnetic field strength and/or NP loading.     

Ecotoxicity of, and remediation with, engineered inorganic nanoparticles in the environment

This article presents recent developments on the use of inorganic nanoparticles (NPs) for environmental remediation in polluted soil, water and gas. The number of publications on these topics has grown exponentially in recent years, especially those focused on wastewater treatment. Among these topics, removal of metals has become the most popular, although some works relate to the use of nanomaterials for the elimination of nutrients (e.g., nitrogen and some persistent organic pollutants). However, this growth has not been accompanied by knowledge about the behavior of NPs once used and released into the environment. In this article, we also comment upon the current situation with respect to NP toxicology (nanotoxicology). A remarkable number of different toxicology tests has been applied to NPs, often making it very difficult to interpret or to generalize the results. We analyze in detail the bioluminescence, Daphnia magna and other tests, and give some preliminary results obtained in our work.     

Modeling Heterogeneity in UO2 Nanoparticles Using X-ray Absorption Spectroscopy

EXAFS provides the capability to interrogate nanoparticle (NP) structure in atomistic detail without relying on long-range crystallinity. There is a limitation in that EXAFS provides averaged structural information, making it difficult to separate a small amount of heterogeneous structure from bulk. In this work, models were developed to extract surface-specific information from conventional EXAFS measurements collected on UO₂ NPs of varying size. Specifically, the surface terminating species of UO₂ NPs was determined from comparison of coordination numbers with geometric models while the origin of static disorder was interrogated from user-defined simulations. Results show that the degree of oxygenation on the NP surface does not significantly deviate from bulk surface and that static disorder is highly enhanced in NP surface layers but cannot be attributed to surface relaxation effects alone. The approach described herein has the potential to be adapted to a range of inorganic NP systems to interrogate surface structure.     

Formation and grain analysis of spin-cast magnetic nanoparticle monolayers

Ligand-stabilized magnetic nanoparticles (NPs) with diameters of 4-7 nm were spin-cast into monolayers on electron-transparent silicon nitride (SiN) substrates. SiN membranes facilitate detailed high-resolution characterization of the spin-cast monolayers by transmission electron microscopy (TEM) and approximate spin-casting onto wafers. Suspending the NPs in hexanes and pretreating the substrate with ultraviolet light and ozone (UVO) gives the best results. Computer-aided analysis of the arrays elucidates their grain structures, including identification of the grain boundaries and defects and measurements of the grain orientations and translational correlation lengths. Narrow NP size distributions result in close-packed arrays with minimal defects and large grains containing thousands of NPs. Edge dislocations, interstitials, vacancies, and overlapping NPs were observed. Deviations from close packing occur as the normalized standard deviation of the sample's size distribution increases above approximately 11%. Polydisperse size distributions and deviations from spherical NP shapes frustrate assembly and prevent ordered packing.     

Reactive poly（divinyl benzene-co-maleic anhydride） nanoparticles：Preparation and characterization

Polymeric nanoparticles（NPs）have drawn great interest in the past few years due to their potential applications in the felds of biomedical and optical technologies.However,it is still a challenge to prepare functional polymeric NPs,especially for particle diameters smaller than 50 nm.In this work,we demonstrate a one-pot method to fabricate reactive poly（divinyl benzene-co-maleic anhydride）NPs（PDVBMAH NPs）through a self-stable precipitation polymerization process.The size and morphology of these PDVBMAH NPs were characterized in detail by scanning electronic microscopy,and their chemical structure was determined by IR.The results showed that these NPs were highly cross-linked and their diameter was about 30 nm with narrow distribution.Additionally,the DVB and MAH endow the NPs with reactive surface anhydride and pendant vinyl groups,and these particles could be further functionalized through reaction of these groups.A plausible pathway was proposed for the formation of PDVBMAH NPs.     

Interaction force measurement between E. coli cells and nanoparticles immobilized surfaces by using AFM

To better understand environmental behaviors of nanoparticles (NPs), we used the atomic force microscopy (AFM) to measure interaction forces between E. coli cells and NPs immobilized on surfaces in an aqueous environment. The results showed that adhesion force strength was significantly influenced by particle size for both hematite (α-Fe(2)O(3)) and corundum (α-Al(2)O(3)) NPs whereas the effect on the repulsive force was not observed. The adhesion force decreased from 6.3±0.7nN to 0.8±0.4nN as hematite NPs increased from 26nm to 98nm in diameter. Corundum NPs exhibited a similar dependence of adhesion force on particle size. The Johnson-Kendall-Roberts (JKR) model was employed to estimate the contact area between E. coli cells and NPs, and based on the JKR model a new model that considers local effective contact area was developed. The prediction of the new model matched the size dependence of adhesion force in experimental results. Size effects on adhesion forces may originate from the difference in local effective contact areas as supported by our model. These findings provide fundamental information for interpreting the environmental behaviors and biological interactions of NPs, which barely have been addressed.     

Mass spectrometry for the characterisation of nanoparticles

Mass spectrometry (MS) has gained much importance in recent years as a powerful tool for reliable analytical characterisation of nanoparticles (NPs). The outstanding capabilities of different MS-based techniques including elemental and molecular detection and their coupling with different separation techniques and mechanisms are outlined herein. Examples of highly valuable elemental and molecular information for a more complete characterisation of NPs are given. Some selected applications illustrate the analytical potential of MS for NP sizing and quantitative assessment of the size distribution as well.     

Viable Photocatalysts under Solar‐Spectrum Irradiation: Nonplasmonic Metal Nanoparticles

Supported nanoparticles (NPs) of nonplasmonic transition metals (Pd, Pt, Rh, and Ir) are widely used as thermally activated catalysts for the synthesis of important organic compounds, but little is known about their photocatalytic capabilities. We discovered that irradiation with light can significantly enhance the intrinsic catalytic performance of these metal NPs at ambient temperatures for several types of reactions. These metal NPs strongly absorb the light mainly through interband electronic transitions. The excited electrons interact with the reactant molecules on the particles to accelerate these reactions. The rate of the catalyzed reaction depends on the concentration and energy of the excited electrons, which can be increased by increasing the light intensity or by reducing the irradiation wavelength. The metal NPs can also effectively couple thermal and light energy sources to more efficiently drive chemical transformations.     

Systematic selection of ancestry informative SNPs for differentiating Han,Japanese, Dai,and Kinh populations

Biogeographical origin inferences of different populations can provide valuable clues in the forensic investigation by narrowing down the detection scope. However, much research mainly focuses on forensic ancestral origin analyses of major continental populations, which may provide limited information in forensic practice. To improve the ancestral resolution of East Asian populations, we systematically selected ancestry informative single-nucleotide polymorphisms (AISNPs) for differentiating Han, Dai, Japanese, and Kinh populations. In addition, we evaluated the performance of the selected AISNPs to differentiate these populations via multiple methods. Totally 116 AISNPs were selected from the genome-wide data to infer the population origins of these four populations. Results of principle component analysis and population genetic structure of these populations indicated that the selected 116 AISNPs could achieve ancestral resolution of most individuals. Furthermore, the machine learning model built by 116 AISNPs unveiled that most individuals from these four populations could be assigned to correct population origins. To sum up, the selected 116 SNPs could be available for ancestral origin predictions of Han, Dai, Japanese, and Kinh populations, which could provide valuable information for forensic research and genome-wide association study in East Asian populations to some extent.     

Limitations of Linear Dichroism Spectroscopy for Elucidating Structural Issues of Light-Harvesting Aggregates in Chlorosomes

Linear dichroism (LD) spectroscopy is a widely used technique for studying the mutual orientation of the transition-dipole moments of the electronically excited states of molecular aggregates. Often the method is applied to aggregates where detailed information about the geometrical arrangement of the monomers is lacking. However, for complex molecular assemblies where the monomers are assembled hierarchically in tiers of supramolecular structural elements, the method cannot extract well-founded information about the monomer arrangement. Here we discuss this difficulty on the example of chlorosomes, which are the light-harvesting aggregates of photosynthetic green-(non) sulfur bacteria. Chlorosomes consist of hundreds of thousands of bacteriochlorophyll molecules that self-assemble into secondary structural elements of curved lamellar or cylindrical morphology. We exploit data from polarization-resolved fluorescence-excitation spectroscopy performed on single chlorosomes for reconstructing the corresponding LD spectra. This reveals that LD spectroscopy is not suited for benchmarking structural models in particular for complex hierarchically organized molecular supramolecular assemblies.     

Morphological and thermal behavior of porous biopolymeric nanoparticles

The aim of the present work is to design, develop and characterize biodegradable polymeric nanoparticles having well defined size and porous morphology. Poly(dl-lactide-co-glycolide) (PLGA) and poly(l-lactide) (PLLA) nanoparticles (NPs) were prepared by double emulsion method with subsequent solvent evaporation. NPs were characterized by electron microscopes, dynamic light scattering, XRD and thermal properties by differential scanning calorimetry and thermogravimetry. Finally, the in vitro degradation analysis was also performed. Biodegradable NPs display a spherical surface structure with a homogeneous size distribution, and an average diameter of 180 nm for PLLA and 218 nm for the PLGA. The NP nanoporous structure was analyzed by an innovative thermal method: thermoporosimetry, providing information about nanopore dimensions. In vitro degradation studies demonstrate the gradual surface aggregation and degradation of NPs and the effects on polymer properties. Biopolymeric porous nano-systems may offer promise properties for revolutionary improvements in tissue engineering, diagnosis and targeted drug delivery systems.     

New look inside human breast ducts with Raman imaging. Raman candidates as diagnostic markers for breast cancer prognosis: Mammaglobin,palmitic acid and sphingomyelin

Looking inside the human body fascinated mankind for thousands of years. Current diagnostic and therapy methods are often limited by inadequate sensitivity, specificity and spatial resolution. Raman imaging may bring revolution in monitoring of disease and treatment. The main advantage of Raman imaging is that it gives spatial information about various chemical constituents in defined cellular organelles in contrast to conventional methods (liquid chromatography/mass spectrometry, NMR, HPLC) that rely on bulk or fractionated analyses of extracted components. We demonstrated how Raman imaging can drive the progress on breast cancer just unimaginable a few years ago. We looked inside human breast ducts answering fundamental questions about location and distribution of various biochemical components inside the lumen, epithelial cells of the duct and the stroma around the duct during cancer development. We have identified Raman candidates as diagnostic markers for breast cancer prognosis: carotenoids, mammaglobin, palmitic acid and sphingomyelin as key molecular targets in ductal breast cancer in situ, and propose the molecular mechanisms linking oncogenes with lipid programming.     

Peptide analysis of tooth enamel – A sex estimation tool for archaeological,anthropological, or forensic research

Proteomics has become an attractive method to study human and animal material, biological profile, and origin as an alternative to DNA analysis. It is limited by DNA amplification in ancient samples and its contamination, high cost, and limited preservation of nuclear DNA. Currently, three approaches are available to estimate sex–osteology, genomics, or proteomics, but little is known about the relative reliability of these methods in applied settings. Proteomics provides a new, seemingly simple, and relatively non-expensive way of sex estimation without the risk of contamination. Proteins can be preserved in hard teeth tissue (enamel) for tens of thousands of years. It uses two sexually distinct forms of the protein amelogenin in tooth enamel detectable by liquid chromatography-mass spectrometry; the protein amelogenin Y isoform is present in enamel dental tissue only in males, while amelogenin isoform X can be found in both sexes. From the point of view of archaeological, anthropological, and forensic research and applications, the reduced destruction of the methods used is essential, as well as the minimum requirements for sample size.     

Multifunctional Fe3O4/TaO(x) core/shell nanoparticles for simultaneous magnetic resonance imaging and X-ray computed tomography

Multimodal imaging is highly desirable for accurate diagnosis because it can provide complementary information from each imaging modality. In this study, a sol-gel reaction of tantalum(V) ethoxide in a microemulsion containing Fe(3)O(4) nanoparticles (NPs) was used to synthesize multifunctional Fe(3)O(4)/TaO(x) core/shell NPs, which were biocompatible and exhibited a prolonged circulation time. When the NPs were intravenously injected, the tumor-associated vessel was observed using computed tomography (CT), and magnetic resonance imaging (MRI) revealed the high and low vascular regions of the tumor.