Soft Corona Research Articles

Size and surface functionalization of iron oxide nanoparticles influence the composition and dynamic nature of their protein corona.

Nanoparticles (NPs) adsorb proteins when in the biological matrix, and the resulted protein corona could affect NP-cell interactions. The corona has a dynamic nature with the adsorbed proteins constantly exchanging with the free proteins in the matrix at various rates. The rapidly exchanging proteins compose the soft corona, which responds more dynamically to environment changes than the hard corona established by the ones with slow exchange rates. In the present study, the corona formed on the superparamagnetic iron oxide NPs (SPIONs) in human serum was studied by flow field-flow fractionation and ultracentrifugation, which rapidly differentiated the corona proteins based on their exchange rates. By varying the surface hydrophobicity of the SPIONs with a core size around 10 nm, we found out that, the more hydrophobic surface ligand attracted proteins with higher surface hydrophobicity and formed a more dynamic corona with a larger portion of the involved proteins with fast exchange rates. Increasing the core diameter of the SPIONs but keeping the surface ligand the same could also result in a more dynamic corona. A brief investigation of the effect on the cellular uptake of SPIONs using one selected corona protein, transferrin, was conducted. The result showed that, only the stably bound transferrin could significantly enhance cellular uptake, while transferrin bound in a dynamic nature had negligible impact. Our study has led to a better understanding of the relationship between the particle properties and the dynamic nature of the corona, which can help with design of nanomaterials with higher biocompatibility and higher efficacy in biosystems for biomedical applications.

Safety concerns towards the biomedical application of PbS nanoparticles: An approach through protein-PbS interaction and corona formation

Semiconductor nanoparticles (NPs) with near-infrared (NIR) fluorescence has achieved great interest for early detection of colon tumors/cancer. We have synthesized lead sulphide (PbS) NPs (5–7 nm) having emission in NIR region and investigated its interaction with bovine serum albumin (BSA) to determine the bio-safety of PbS NPs. The interaction of PbS NPs with BSA occurs through formation of “hard” and “soft” protein NPs corona and follows exponential association. The hard corona represents that the core PbS NPs are fully covered by BSA with shell thickness of ∼8 nm, i.e., the dimension of BSA monomer. A large number of PbS NPs with hard corona of BSA forms “colony” with diameters in the range of 200–400 nm. The soft corona grows surrounding this colony. The quenching of fluorescence BSA in the presence of PbS NPs follows dynamic quenching process with tryptophan as major binding sites. Nearest to human body temperature, positive cooperative association between PbS NPs and BSA are found, and affinity of BSA to the PbS NPs gradually increases in superlinear fashion. The electrostatic interaction is the key force in binding of PbS NPs with BSA, and hydrophobic interaction between PbS NPs and BSA is responsible for conformational change of BSA.

Spatial Mapping and Quantification of Soft and Hard Protein Coronas at Silver Nanocubes

Protein coronas around silver nanocubes were quantified in serum-containing media using localized surface plasmon resonances. Both soft and hard coronas showed exposure-time and concentration-dependent changes in protein surface density with time-dependent hardening. We observed spatially dependent kinetics of the corona-formation at cube edges/corners versus facets at short incubation times, where the polymer stabilization agent delayed corona hardening. The soft corona contained more protein than the hard corona at all time-points (8-fold difference with 10% serum conditions).

Optimizing the Properties of the Protein Corona Surrounding Nanoparticles for Tuning Payload Release

We manipulate the passive release rates of DNA payloads on protein coronas formed around nanoparticles (NPs) by varying the corona composition. The coronas are prepared using a mixture of hard and soft corona proteins. We form coronas around gold nanorods (NRs), nanobones (NBs), and carbon nanotubes (CNTs) from human serum (HS) and find that tuning the amount of human serum albumin (HSA) in the NR-coronas (NR-HS-DNA) changes the payload release profile. The effect of buffer strength, HS concentration, and concentration of the cetyltrimethylammonium bromide (CTAB) passivating the NP surfaces on passive release is explored. We find that corona properties play an important role in passive release, and concentrations of CTAB, HS, and phosphate buffer used in corona formation can tune payload release profiles. These advances in understanding protein corona properties bring us closer toward developing a set of basic design rules that enable their manipulation and optimization for particular biological applications.

Study of Wild-Type α-Synuclein Binding and Orientation on Gold Nanoparticles

The disruption of α-synuclein (α-syn) homeostasis in neurons is a potential cause of Parkinson's disease, which is manifested pathologically by the appearance of α-syn aggregates, or Lewy bodies. Treatments for neurological diseases are extremely limited. To study the potential use of gold nanoparticles (Au NPs) to limit α-syn misfolding, the binding and orientation of α-syn on Au NPs were investigated. α-Syn was determined to interact with 20 and 90 nm Au NPs via multilayered adsorption: a strong electrostatic interaction between α-syn and Au NPs in the hard corona and a weaker noncovalent protein-protein interaction in the soft corona. Spectroscopic and light-scattering titrations led to the determinations of binding constants for the Au NP α-syn coronas: for the hard corona on 20 nm Au NPs, the equilibrium association constant was 2.9 ± 1.1 × 10(9) M(-1) (for 360 ± 70 α-syn/NP), and on 90 nm Au NPs, the hard corona association constant was 9.5 ± 0.8 × 10(10) M(-1) (for 5300 ± 700 α-syn/NP). The binding of the soft corona was thermodynamically unfavorable and kinetically driven and was in constant exchange with "free" α-syn in solution. A protease digestion method was used to deduce the α-syn orientation and structure on Au NPs, revealing that α-syn absorbs onto negatively charged Au NPs via its N-terminus while apparently retaining its natively unstructured conformation. These results suggest that Au NPs could be used to sequester and regulate α-syn homeostasis.

Protein corona formation for nanomaterials and proteins of a similar size: hard or soft corona?

Nanoparticles (NPs) entering a biological fluid undergo surface modification due to dynamic, physicochemical interactions with biological components, especially proteins. In this work we used complementary bio-physico-chemical approaches to characterize the effects of interactions between CeO(2) NPs, immunoglobulins (IgGs) and bovine serum albumin (BSA) of a similar size on protein structural evolution as well as formation of (hetero-) aggregates. Using circular dichroism we showed that IgGs and BSA underwent significant structural changes after interaction with NPs. The NPs and protein-NPs were observed after size exclusion chromatography, highlighting the fact that few aggregates were stable enough to pass this mild separation step. X-ray absorption spectroscopy suggested that the surface chemistry of NPs was not affected by these proteins, also implying weak interactions. Competitive experiments revealed that, while the serum was more concentrated for BSA, IgG-NP aggregates were more stable. Altogether, our results indicate that, under our experimental conditions, the formation of a "protein corona" is an unstable and reversible mechanism. This indicates that, when NPs and proteins are similar in size, the adsorption concept (i.e. protein corona concept) cannot be applied to model the NP-protein interaction, and a heteroaggregation model is more appropriate.

Comparison of solar activity during last two minima on turn of Activity Cycles 22/23 and 23/24

AbstractThe subject of our work is the review and comparison of solar activity during the last two solar minima that occurred between recent activity cycles. We use the soft X-ray global solar corona observations covering the two nine-months long time intervals in 1997/98 and 2009. Data from RF15-I multichannel photometer are used for the penultimate minimum. For the last unusually deep and prolonged solar activity minimum in 2009 the data from SphinX spectrophotometer are used. Comparison of measurements from both minima takes place in the overlapping energy range 2–15 keV. We focus on the active region formation, evolution and flaring productivity during respective minima.

Reversible versus Irreversible Binding of Transferrin to Polystyrene Nanoparticles: Soft and Hard Corona

Protein adsorption to nanoparticles (NPs) is a key prerequisite to understand NP-cell interactions. While the layer thickness of the protein corona has been well characterized in many cases, the absolute number of bound proteins and their exchange dynamics in body fluids is difficult to assess. Here we measure the number of molecules adsorbed to sulfonate (PSOSO(3)H) and carboxyl-(PSCOOH) polystyrene NPs using fluorescence correlation spectroscopy. We find that the fraction of molecules bound to NPs falls onto a single, universal adsorption curve, if plotted as a function of molar protein-to-NP ratio. The adsorption curve shows the build-up of a strongly bound monolayer up to the point of monolayer saturation (at a geometrically defined protein-to-NP ratio), beyond which a secondary, weakly bound layer is formed. While the first layer is irreversibly bound (hard corona), the secondary layer (soft corona) exhibits dynamic exchange, if competing unlabeled is added. In the presence of plasma proteins, the hard corona is stable, while the soft corona is almost completely removed. The existence of two distinct time scales in the protein off-kinetics, for both NP types studied here, indicates the possibility of an exposure memory effect in the NP corona.

Soft Interactions at Nanoparticles Alter Protein Function and Conformation in a Size Dependent Manner

Weak protein-nanoparticle (NP) interactions are studied in a low binding regime as a model for the soft protein corona around nanoparticles in complex biological fluids. Noncovalent, reversible interactions between Subtilisin Carlsberg (SC) and silica NPs shows significant alteration in conformation and enzymatic activity in a NP-size dependent manner. Very weak interactions between SC and silica NPs were revealed by centrifugation-based separations and further supported by small-angle X-ray scattering, while bovine serum albumin was used as a strongly interacting reference. Secondary and tertiary structure changes of SC were studied via circular dichroism and correlated to enzymatic activity where the enzyme kinetics showed a critical role for nanoparticle size.

Differential rotation measurement of soft X-ray corona

The aim of this paper is to study the latitudinal variation in the solar rotation in soft X-ray corona. The time series bins are formed on different latitude regions of the solar full disc (SFD) images that extend from 80°S to 80°N. These SFD images are obtained with the soft X-ray telescope (SXT) on board the Yohkoh solar observatory. The autocorrelation analyses are performed with the time series that track the SXR flux modulations in the solar corona. Then for each year, extending from 1992 to 2001, we obtain the coronal sidereal rotation rate as a function of the latitude. The present analysis from SXR radiation reveals that: (i) the equatorial rotation rate of the corona is comparable to the rotation rate of the photosphere and the chromosphere, (ii) the differential profile with respect to the latitude varies throughout the period of the study; it was more in the year 1999 and least in 1994, and (iii) the equatorial rotation period varies systematically with sunspot numbers and indicates its dependence on the phases of the solar activity cycle.

Fluorescence Emission of Disperse Red 1 in PS-b-P4VP Micelles Controlled by a Toluene/Ethanol Solvent Mixture

The effects of Disperse Red 1 (DR1) in the poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) micelle on micellar morphology and fluorescence emission were studied using small-angle X-ray scattering (SAXS), generalized indirect Fourier transform (GIFT), Fourier transform infrared (FT-IR), transmission electron microscopy (TEM), and photoluminescence (PL). PS-b-P4VP was coupled with DR1 in 10 mg/mL toluene/ethanol mixture solutions where ethanol and toluene were P4VP and PS selective, respectively. Hydrogen bonds were formed between the -OH group of DR1 and the pyridine ring in PS-b-P4VP. DR1 (which was coupled with P4VP) was confined in the core or corona of the micelle depending on the location of P4VP. The micellar structure was strongly dependent on varphi (weight percentage of toluene in a toluene/ethanol mixture). The PS-b-P4VP-DR1 complex in the mixture solutions showed the spherical micelle with the cores of P4VP and PS in ethanol-rich and toluene-rich solvents, respectively. The quenching phenomenon was observed for DR1 in the corona of PS-b-P4VP micelles [at varphi = 0 (ethanol)], while the fluorescence quantum yield decreased. However, significant increases in the fluorescence quantum yields at varphi = 100 were observed when DR1 was confined in the core of the PS-b-P4VP micelles. The confinement of DR1 in the hard core was more effective in fluorescence emission than that in the soft corona due to the slow trans-to-cis transition of DR1.

The Cycles of Alpha Centauri

AbstractThe main AB pair of the nearby Alpha Centauri triple system has one of the most extensive X-ray records of any cosmic object, stretching over three decades. The primary, α Cen A (G2V), is a near twin of the Sun, with a similarly soft (1–2 MK) corona. The secondary, α Cen B (K1V), is more active than the Sun, with a generally harder coronal spectrum. Here, spatially resolved measurements of the pair by Chandra's High Resolution Camera are compared, on a common basis, with previous pointings from ROSAT and XMM-Newton.

THE CYCLES OF α CENTAURI

The main AB pair of the nearby α Centauri triple system has one of the most extensive X-ray records of any cosmic object, stretching over 30 years. The primary, α Cen A (G2 V), is a near twin of the Sun, with a similarly soft (1-2 MK) corona. The secondary, α Cen B (K1 V), is more active than the Sun, with a generally harder coronal spectrum. Here, more than a decade of spatially resolved measurements from ROSAT, XMM-Newton, and Chandra are compared on a common basis, with careful attention to conversion factors that translate count rates of the different instruments into absolute energy fluxes. For the latter purpose, two epochs of Chandra transmission grating spectra, which fully resolve the binary, were modeled using a differential emission measure formalism. The aggregate time series suggests that α Cen B was near X-ray maximum in the mid-1990s, minimum in the late-1990s, then peaked again in 2004-2005, and more recently has been declining toward another minimum. Meanwhile, α Cen A showed minimal variability 1995-2000, and like the secondary presently is mired in an activity lull (in fact, as seen by XMM-Newton, the primary fainted from view in the 2005 time frame). Comparisons between X-ray luminosities in the 0.2-2 keV (6-60 A) ROSAT WGACAT band and a softer counterpart 0.06-1.2 keV (10-200 A) reinforce the idea that cycle depth is strongly dependent on the energy span of the measurement, and that much of the coronal luminosity of cool-corona objects like the Sun falls at longer wavelengths than are recorded efficiently by contemporary instruments. Consequently, one must be careful in discussing X-ray cycles, their amplitudes, and coronal heating requirements unless one can demonstrate good control over the out-of-band component.

Supramolecular Organization of Heteroxylan-Dehydrogenation Polymers (Synthetic Lignin) Nanoparticles

The supramolecular organization of particles composed of heteroxylans (HX) and synthetic lignin (dehydrogenation polymer, DHPs) was studied by light scattering (LS), atomic force microscopy (AFM), and fluorescent probes. Results from static and quasi-elastic light scattering indicate a dense core surrounded by a soft corona. Such organization is also supported by AFM images of the particles that display Gaussian height profiles when a low tapping force is applied, whereas the shape of the profile obtained at a higher mechanical solicitation is irregular and sharp due to deformation of the particles resulting from the tip indentation. This suggests a difference in mechanical behavior between the inner and outer parts of the particles. The formation of local chemical heterogeneities was demonstrated by use of two fluorescent polarity probes (pyrene and methyl-amino-pyrene) to be induced by the core-corona organization.

Surface-functionalized nanoparticles with liquid-like behavior: The role of the constituent components

Ionically modified silica nanoparticles with large counter anions (sulfonate, isostearate) at two silica volume fractions (13 and 27%) form a viscous fluid and a glass but not crystalline solids. Dielectric spectroscopy, Brillouin scattering and shear rheometry were employed to investigate these new nanoparticle-based fluids. The glass transition temperature and hence the local dynamics are governed by the large counter anions, whereas the flow properties can be controlled by the spatial correlation between the nanoparticles, e.g. by tuning the volume fraction of hard cores and local interactions between segments in the soft corona. Liquid-like ordering of the cores was revealed by X-ray scattering and found to influence significantly the macroscopic flow properties of these salts.

Stripe patterns in two-dimensional systems with core-corona molecular architecture.

The behavior of a two-dimensional system of particles interacting through a potential consisting of a hard core surrounded by a soft repulsive corona is investigated at several densities and temperatures. We find that the competition between hard and soft repulsions gives origin to the spontaneous formation of spatial patterns resembling stripe textures. The effect of varying the hard and soft core radii ratio as well as that of adding an attractive component to the interparticle interaction is studied. The model investigated is relevant for macromolecular topologies possessing two intrinsic length scales.

The Advanced Technology Solar Spectroscopic Imager—a novel experiment employing a transition-edge sensor to probe the soft X-ray solar corona

The Advanced Technology Solar Spectroscopic Imager (ATSSI) is a sounding rocket-borne experiment that will employ a Transition-Edge Sensor (TES) placed at the focus of a Wolter-I mirror to study large active region loops in the solar corona. The TES instrument will operate in the ∼500–1500eV EUV/soft X-ray bandpass, obtaining ∼3eV energy-resolved spectra at ∼6.25arcsec image resolution with a count rate of ∼1000photons/sec/pixel. Over a typical observation period of ∼360sec, we will raster scan over a 0.6×0.6 arcmin field of view to obtain a 6×6 pixel image containing true EUV/soft X-ray spectroheliograms of a solar active region. Using these observations, we can directly determine composition, electron density and thermal differential emission measure of large active region loops in order to constrain models of heating mechanisms and accurately measure the thermal morphology of these structures. In the current analysis, we present an initial instrument concept and discuss some of the mission science goals.

Stripe phases from isotropic repulsive interactions.

One of the most striking signatures of self-organization is spontaneous pattern formation. Among the morphologies observed, stripes are intrinsically fascinating and have potential for technological applications including nanolithography and nanoelectricity. Examples of materials featuring stripe patterns include Langmuir monolayers, magnetic films, lipid monolayers, liquid crystals and polymer films. Stripe formation is generally attributed to the competition between short-range attractive forces and long-range repulsion arising from dipole interactions. Here we show that stripe phases may result from a different mechanism based on a purely repulsive isotropic short-range pair potential with two characteristic length scales. We consider a two-dimensional (2D) assembly of particles consisting of a hard core surrounded by a soft corona and find that at densities where the hard-and-soft core radii compete with each other, decreasing the temperature induces a transition from a disordered state to an orientationally ordered phase characterized by stripe patterns.

The magnetic topology of a sigmoid

Recent surveys of solar features have linked the “sigmoid-to-arcade” scenario observed in the soft X-ray corona to coronal mass ejection (CME) onset (Geophys. Res. Lett. 26 (1999) 627, Geophys. Res. Lett. 14 (1998) 2481). Further to these observations, incorporation of extreme-ultraviolet, white light and H-alpha data into such a survey (Geophys. Res. Lett. 27 (2000) 2161) has illustrated the need for a quantitative definition of the term “sigmoid” and further understanding of such features if they are to be used as a means by which to predict CME onset. We analyse two sample active regions in detail, each appearing both sigmoidal and eruptive in Yohkoh soft X-ray telescope (SXT) full-disk data. Both regions were observed during October 1997 and each produced a flare displaying eruptive characteristics. In each case, formation of a flare-arcade was observed by both SXT and the extreme ultraviolet imaging telescope (EIT) following the event. EUV dimming and coronal EIT waves were also observed in each case. We have studied each active region both before and after eruption using soft X-ray, EUV and H-alpha data. A linear force-free field extrapolation has also been applied as a means by which to determine the active region field deviation from potential in each case. Each active region was observed to erupt by means of a different mechanism and while both events show signatures of eruption and consequently, mass ejection, only one produced a CME large enough to be observed by the SoHO large angle spectroscopic coronagraph. The implications of these observations in terms of CME prediction are discussed.

Characterization of Polyisoprene-b-Poly(methyl methacrylate) Diblock Copolymer Micelles in Acetonitrile

In acetonitrile, polyisoprene-b-poly(methyl methacrylate) (PI−PMMA) diblock copolymers form starlike micelles with a dense core of the insoluble PI blocks and a soft solvent-swollen corona of the soluble PMMA blocks. Static and dynamic light scattering experiments in combination with viscosity measurements show that these micelles behave hydrodynamically as hard spheres. The block copolymers are labeled at the block junction, with a single fluorescent dye, either a donor chromophore (phenanthrene) or an acceptor chromophore (anthracene). These dyes are confined to the interface during self-assembly. Fluorescence energy-transfer experiments on molecularly mixed micelles of donor- and acceptor-labeled copolymers provide a core radius of 7.6 ± 0.8 nm and a number-average aggregation number ( ) of 98 ± 22 under the assumption that the energy transfer takes place on a surface of a sphere. Simulations in terms of a Helfand−Tagami junction distribution profile confirm that the core−corona interface of the PI−PMMA micelles is thin (ca. 0.9 nm) and that almost all of the energy transfer occurs within a narrow interfacial region. From the static light scattering measurements of the mixed micelles a weight-average aggregation number ( ) of 127 ± 6 is obtained. The ratio / = 1.3 agrees with size polydispersity of the micelles obtained from the analysis of dynamic light scattering data. The experimental corona thicknesses are in good agreement with those calculated from expressions describing starlike block copolymer micelles. (Less)