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Macromolecules 55(19), 8757 - 8765 (2022). doi:10.1021/acs.macromol.2c01326, Dynamics of nanoparticles (NPs) in microscopic networks, in particular, localization and transport, play a key role in designing new functional nanocomposites and drug delivery systems. To this aim, it is crucial to understand the interplay between the network structure and dynamics on the microscopic scale which determines NP diffusion. Here, we study the localization and transport of spherical NPs in photorheological wormlike micellar nanocomposites where the mobility of the NPs is controlled by the network mesh size and the micelle length, which can be tuned by UV-illumination. The macroscopic viscoelastic properties are measured by classical rheology, while X-ray photon correlation spectroscopy and nanorheology provide information on the microscopic NP dynamics on length scales on the order of the network mesh size. On long time scales, the data reveal that transport through the network is determined by the ratio between the NP size and the network mesh size, while upon UV illumination, the NP mobility is drastically enhanced. On shorter time scales, the influence of the dynamical and structural micelle properties on the NP dynamics under confinement is explored and indicates an anomalous speed-up of the dynamics, which is discussed in the context of changes in the local structure and non-linear phenomena such as strain stiffening and hopping motion., Published by Soc., Washington, DC

The pandemic emergency determined by the spreading worldwide of the SARS-CoV-2 virus has focused the scientific and economic efforts of the pharmaceutical industry and governments on the possibility to fight the virus by genetic immunization. The genetic material must be delivered inside the cells by means of vectors. Due to the risk of adverse or immunogenic reaction or replication connected with the more efficient viral vectors, non-viral vectors are in many cases considered as a preferred strategy for gene delivery into eukaryotic cells. This paper is devoted to the evaluation of the gene delivery ability of new synthesized gemini bis-pyridinium surfactants with six methylene spacers, both hydrogenated and fluorinated, in comparison with compounds with spacers of different lengths, previously studied. Results from MTT proliferation assay, electrophoresis mobility shift assay (EMSA), transient transfection assay tests and atomic force microscopy (AFM) imaging confirm that pyridinium gemini surfactants could be a valuable tool for gene delivery purposes, but their performance is highly dependent on the spacer length and strictly related to their structure in solution. All the fluorinated compounds are unable to transfect RD-4 cells, if used alone, but they are all able to deliver a plasmid carrying an enhanced green fluorescent protein (EGFP) expression cassette, when co-formulated with 1,2-dioleyl-sn-glycero-3-phosphoethanolamine (DOPE) in a 1:2 ratio. The fluorinated compounds with spacers formed by six (FGP6) and eight carbon atoms (FGP8) give rise to a very interesting gene delivery activity, greater to that of the commercial reagent, when formulated with DOPE. The hydrogenated compound GP16_6 is unable to sufficiently compact the DNA, as shown by AFM images.

There are huge demands on multifunctional nanocarriers to be used in nanomedicine. Herein, we present a simple and efficient method for the preparation of multifunctional magnetically responsive polymeric-based nanocarriers optimized for biomedical applications. The hybrid delivery system is composed of drug-loaded polymer nanoparticles (poly(caprolactone), PCL) coated with a multilayer shell of polyglutamic acid (PGA) and superparamagnetic iron oxide nanoparticles (SPIONs), which are known as bio-acceptable components. The PCL nanocarriers with a model anticancer drug (Paclitaxel, PTX) were formed by the spontaneous emulsification solvent evaporation (SESE) method, while the magnetically responsive multilayer shell was formed via the layer-by-layer (LbL) method. As a result, we obtained magnetically responsive polycaprolactone nanocarriers (MN-PCL NCs) with an average size of about 120 nm. Using the 9.4 T preclinical magnetic resonance imaging (MRI) scanner we confirmed, that obtained MN-PCL NCs can be successfully used as a MRI-detectable drug delivery system. The magnetic hyperthermia effect of the MN-PCL NCs was demonstrated by applying a 25 mT radio-frequency (f = 429 kHz) alternating magnetic field. We found a Specific Absorption Rate (SAR) of 55 W g−1. The conducted research fulfills the first step of investigation for biomedical application, which is mandatory for the planning of any in vitro and in vivo studies.

The ability to detect early damage is of great significance in load bearing composite materials used for high performance applications. Microdamages if left unchecked can grow under subsequent stress, leading to catastrophic structural failure. The sensing of early stage damage via nondestructive methods is therefore critically important for the safe use of these materials. Herein a supramolecular approach to self-diagnosis of early stage damage in a carbon fiber epoxy composite material, via the incorporation of a CB[8] based ternary complex as an additive is reported. The complex comprising a fluorescent probe and a quencher encapsulated by the CB[8] is introduced into the epoxy resin of the composite as a supramolecular cross-linking agent, whose stress-induced dissociation results in the turn on of fluorescence of the probe. In this way, detection of irreversible mechanical strain and fatigue at an early stage is attainable, enabling the assessment of microdamage in the material.

This paper reports on the setting up and calibration of a portable NIR fluorimeter specifically developed for quantitative direct detection of the highly reactive singlet oxygen (1O2) chemical specie, of great importance in Photodynamic therapies. This quantification relies on the measurement of fluorescence emission of 1O2, which is peaked in the near-infrared (NIR) at λ = 1270 n m . In recent years, several nanostructures capable of generating reactive oxygen species (ROS) when activated by penetrating radiation (X-rays, NIR light) have been developed to apply Photodynamic Therapy (PDT) to tumours in deep tissue, where visible light cannot penetrate. A bottleneck in the characterization of these nanostructures is the lack of a fast and reliable technique to quantitatively assess their performances in generating ROS, and in particular 1O2. For instance, the widely used PDT “Singlet Oxygen Sensor Green” kit suffers from self-activation under X-ray irradiation. To solve this difficulty, we propose here direct detection of 1O2 by spectroscopic means, using an apparatus developed by us around a recent thermoelectrically-cooled InGaAs single photon avalanche photodiode (SPAD). The SPAD is coupled to a custom-made integrating sphere designed for use under irradiation with high-energy X-ray beams from clinical Radiotherapy sources. We determine the detection threshold for our apparatus, which turns to be ∼ 9 · 10 8 1O2 in realistic experimental condition and for measurements extending to 1 min of integration. After calibrations on standard photosensitizers, we demonstrate the potentiality of this instrument characterizing some photosensitizing nanostructures developed by us.

The use of metal nanoparticles is an established paradigm for the synthesis of semiconducting one-dimensional nanostructures. In this work we study their effect on the synthesis of two-dimensional semiconducting materials, by using gold nanoparticles for chemical vapor deposition growth of two-dimensional molybdenum disulfide (MoS2). In comparison with the standard method, the employment of gold nanoparticles allows us to obtain large monolayer MoS2 flakes, up to 20 μm in lateral size, even if they are affected by the localized overgrowth of MoS2 bilayer and trilayer islands. Important modifications of the optical and electronic properties of MoS2 triangular domains are reported, where the photoluminescence intensity of the A exciton is strongly quenched and a shift to a positive threshold voltage in back-gated field effect transistors is observed. These results indicate that the use of gold nanoparticles influences the flake growth and properties, indicating a method for possible localized synthesis of two-dimensional materials, improving the lateral size of monolayers and modifying their properties.

BGaAs/GaAs epilayers and BInGaAs/GaAs quantum well (QW) have been prepared using metal-organic chemical vapor deposition under different growth conditions, and their physical and structural properties have been examined. SEM-EDS investigation showed a dependence of surface properties of the ternary compound on the growth conditions. High-resolution X-ray diffraction evidenced a tensile strain for the ternary alloys whatever the growth condition, while the quaternary QW always shows a compressive strain state. Room temperature optical absorption allowed to follow the variation of the bandgap with boron incorporation. Photoluminescence measurements confirmed the carrier-localization phenomenon and its dependence with the growth conditions. Deposition temperature and diborane (B2H6) flow rate are with particularly significant effects on the optical properties: lower diborane flow rate and high growth temperature enhance the radiative emission. Computer simulation using localized state ensemble model quantitatively relates the lattice inhomogeneity to the optical properties and suggests a way to engineer the localization phenomenon and avoid clustering effects. Electrical investigations by current-voltage, capacitance and conductance methods have been performed for the first time on selected BGaAs samples. The ideality factor of Schottky barriers has been determined, while their height and film doping level could only be approximately estimated. Such physical properties make boron-based alloys very promising for applications in multijunction solar cells.

We report on the sharpness of the magnetostructural transition in a Ni-Co-Mn-Ga-In Heusler alloy, which has a key role in defining the magnetocaloric effect exploitable in efficient and environmentally friendly magnetic refrigerators. Magnetic and calorimetric analysis together with optical microscopy in phase-imaging mode are compared to correlate the transition broadening with microscopic features of the sample. The three techniques give the same temperature behavior of the martensitic transition. Microscopy analysis of different sample areas and during cycles in temperature reveals the spatial homogeneity of the transition width and its reproducibility in subsequent transformations.

Physical review letters 125(5), 055701 (2020). doi:10.1103/PhysRevLett.125.055701, We present a detailed investigation of the wave-vector dependence of collective atomic motion in Au$_{49}$Cu$_{26.9}$Si$_{16.3}$Ag$_{5.5}$Pd$_{2.3}$ and Pd$_{42.5}$Cu$_{27}$Ni$_{9.5}$P$_{21}$ supercooled liquids close to the glass transition temperature. Using x-ray photon correlation spectroscopy in a previously uncovered spatial range of only a few interatomic distances, we show that the microscopic structural relaxation process mimics the structure and presents a marked slowing down at the main average interparticle distance. This behavior is accompanied by dramatic changes in the shape of the intermediate scattering functions, which suggest the presence of large dynamical heterogeneities at length scales corresponding to a few particle diameters. A ballisticlike mechanism of particle motion seems to govern the structural relaxation of the two systems in the highly viscous phase, likely associated with hopping of caged particles in agreement with theoretical studies., Published by APS, College Park, Md.

Objectives To describe clinical characteristics, management and outcome of individuals with coronavirus disease 2019 (COVID-19); and to evaluate risk factors for all-cause in-hospital mortality. Methods This retrospective study from a University tertiary care hospital in northern Italy, included hospitalized adult patients with a diagnosis of COVID-19 between 25 February 2020 and 25 March 2020. Results Overall, 317 individuals were enrolled. Their median age was 71 years and 67.2% were male (213/317). The most common underlying diseases were hypertension (149/317; 47.0%), cardiovascular disease (63/317; 19.9%) and diabetes (49/317; 15.5%). Common symptoms at the time of COVID-19 diagnosis included fever (285/317; 89.9%), shortness of breath (167/317; 52.7%) and dry cough (156/317; 49.2%). An ‘atypical' presentation including at least one among mental confusion, diarrhoea or nausea and vomiting was observed in 53/317 patients (16.7%). Hypokalaemia occurred in 25.8% (78/302) and 18.5% (56/303) had acute kidney injury. During hospitalization, 111/317 patients (35.0%) received non-invasive respiratory support, 65/317 (20.5%) were admitted to the intensive care unit (ICU) and 60/317 (18.5%) required invasive mechanical ventilation. All-cause in-hospital mortality, assessed in 275 patients, was 43.6% (120/275). On multivariable analysis, age (per-year increase OR 1.07; 95% CI 1.04–1.10; p Conclusions COVID-19 mainly affected elderly patients with predisposing conditions and caused severe illness, frequently requiring non-invasive respiratory support or ICU admission. Despite supportive care, COVID-19 remains associated with a substantial risk of all-cause in-hospital mortality.

X-ray induced Photodynamic Therapy (XPDT) is a proposed therapy for deep tumours. The idea is to use the X-ray beam of a standard radiotherapy facility to excite a scintillator which is coupled with a photosensitizing agent which in turn generates reactive oxygen species (ROS) which induce local oxidative stress. Alike in standard Photodynamic Therapy, this oxidative stress may be used to treat tumours. Preliminary results [F. Rossi et al. Sci. Rep. 5 (2015) 7606] demonstrated that can XPDT enhance the efficacy of standard radiotherapy, while reducing its unwanted side effects. This work reports the rationale development of a nanostructure incorporating nanoparticles (NP) for XPDT around a silica core by means of electrostatic adsorption. To this aim, scintillator CeF3 and photosensitizer ZnO, both in form of nanoparticles, have been adsorbed into a polyelectrolyte Layer-by-Layer (LbL) multilayer grown around a SiO2 core. This structure, in a future work, could be a platform for drug delivery. We optimized the growth of the structure basing on results from adsorption on planar substrates, as a function of incubation time, of particle concentration, and of the composition of the outer polyelectrolyte layer, having also in mind the need to avoid the formation of micrometric aggregates. This drove the rationale synthesis of the nanocapsules. The resulting structures are studied by Scanning Electron Microscopy, X-ray Microanalysis, Dynamic Light Scattering, and ζ-potential analysis.

We report here an overview of current trends and a selection of recent results regarding the characterization of emulsions by Diffusing Wave Spectroscopy (DWS). We provide a synopsis of the state of the art of the DWS technique, and a critical discussion of experiments performed on samples in which Brownian and ballistic dynamics coexist. A novel analysis scheme is introduced for DWS experiments on creaming or sedimenting emulsions, allowing to extract not only average values for drop size and drop dynamics - as usual in DWS - but also properties related to the width of the distributions governing these quantities. This analysis scheme starts from a realistic Monte Carlo simulation of light diffusing in the volume of the sample and reaching the detector. This simulation is more accurate than the analytical expressions available for the idealized geometries normally used in DWS interpretation. By disentangling Brownian and ballistic motions we directly access the variance of velocity distribution, σv. In relatively unstable emulsions σv governs the frequency of drop-drop collisions and subsequent coalescence events. Furthermore, when gravity dominates dynamics, as in emulsions subject to sedimentation or creaming, σv is strongly related to the 2nd and 4th moments of drop size distribution. This novel analysis scheme is exemplified investigating freshly formed model emulsions. Results are validated by comparison with microscopy imaging. This analysis is then extended to emulsions with a much broader drop size distribution, resembling those that are planned to be investigated in microgravity by the Soft Matter Dynamics facility onboard the International Space Station (ISS). This review is concluded by sketching some promising directions, and suggesting useful complementarities between DWS and other techniques, for the characterization of transient regimes in emulsions, and of destabilization processes of great practical importance.

Diffusing Wave Spectroscopy (DWS) is a technique used to characterize microscopic structure and rheological properties of turbid samples. This is achieved by analyzing the time evolution of coherence speckles of light that has been multiply scattered within the sample. One attractive feature of DWS is that it is non-invasive, and robust. For this reason, DWS has been selected as a diagnostic tool for an experiment module uploaded onboard the International Space Station (ISS) and devoted to the study of soft matter dynamics –related phenomena, among which, the basic mechanisms responsible for emulsions and foams aging. Moreover, the sensitivity of DWS to tiny motions and to fast time scales allows to extend measurements beyond the limits of usual rheological techniques, of micro-imaging and related techniques. However, the accuracy obtainable by DWS measurements is often limited. Here we revise different experimental approaches to the characterization of emulsions by DWS. We provide quantification of the accuracy of the correlation functions and we discuss how this affects the determination of the mechanical moduli, providing an objective criterion to establish the time window over which DWS results are reliable. These concepts are applied to discuss a laboratory prototype and to address the design of the DWS diagnostics suitable for the emulsion studies to be performed onboard the ISS.

We employ Diffusing Wave Spectroscopy (DWS) to characterize microscopic structure, internal dynamics and rheological properties of a paradigmatic emulsion formed by water and dodecane stabilized by the anionic surfactant Sodium Dodecyl Sulfate (SDS). We focus on ageing and stability in the regime of low surfactant concentration, well below the Critical Micellar Concentration (CMC). In the long-time ageing regimes differentiate in stable and unstable, depending on surfactant concentration. For the stable case, ageing affects the dynamics following a power law with an exponent independent on surfactant concentration, presumably related to the late stages of the water drainage process. On the contrary, at constant ageing, the dependence of the dynamics from surfactant concentration shows a slowdown, corresponding to a maximum in the bulk shear mechanical modulus, around [ S D S ] = 2 m M which is reminiscent of a similar maximum found by drop tensiometry in the dilational modulus of the single interface. This suggests a consistent picture of the mechanisms (de)stabilizing the emulsion, explained in terms of elementary process at the interface. These results show furthermore that DWS can be a reliable diagnostic for the study of the aging and of the mechanical properties of concentrate emulsions. This might be relevant to control stability of emulsions when a low concentration of surfactant is desired, e.g. for economical or environment reasons.

To synthesize and characterize the performances of a new all-inorganic nanocomposite (NC) for self-lighted photodynamic therapy against cancer. This NC could allow radiotherapy doses to be reduced, as it enhances the effects of x-rays, generating cytotoxic reactive oxygen species as singlet oxygen.The proposed NC combines CeFNC blocks A549's cell cycle before mitosis in the dark. Upon low-dose x-ray irradiation (2 Gy), reactive oxygen species/singlet oxygen are generated, further blocking cell cycle and reducing viability by 18% with respect to the sum of x-ray irradiation and NC dark activity.These novel NCs promise to reduce doses in radiotherapy, helping to reduce unwanted side effects.

Complex interfaces, such as vesicles and biological membranes, and interface-dominated systems, such as foams and emulsions, are central to a vast range of naturally occurring and synthetic materials. In order to characterize their dynamics, it is necessary to cover a wide range of length and time scales. This can only be done by a combination of different techniques. We review here recent results and discuss new trends focusing on two class of techniques: correlation spectroscopies and microscopies, highlighting some examples of their combined use.

The control of the behavior of oil in water emulsions requires deeper investigations on the adsorption properties of the emulsion stabilizers at the interfaces, which are fundamental to explain the (de)stabilization mechanisms. In this work, we present an extensive study on oil-in-water emulsions stabilized by sodium dodecyl sulfate (SDS) below its critical micellar concentration. Dynamic tensiometry, dilational rheology, and electrical conductivity measurements are used to investigate the adsorption properties at the droplet interface, whereas the aging of the respective emulsions was investigated by monitoring the macroscopic thickness of the emulsion layer, by microimaging and dynamic light scattering (DLS) analysis, to get information on the drop size distribution. In addition, the droplet coalescence is investigated by a microscopy setup. The results of this multitechnique study allow deriving a coherent scenario where the adsorption properties of this ionic surfactant relate to those of the emulsion, such as, for example, the prevention of droplet coalescence and the presence of other mechanisms, such as Ostwald ripening, responsible for the emulsion aging.

In the debate about Michael Oakeshott’s philosophy there is very little agreement on the theoretical and historical meaning of his skepticism. Starting from the assumption that skepticism is not a fixed theory but a tradition of ideas, this article draws on both published texts and archival materials to contend that Oakeshott developed his thought by confronting himself with, and even merging, different strands of skepticism: the ancient, the modern, as represented by Hobbes and Montaigne, and the idealist, as conceived by F. H. Bradley. The article firstly shows Oakeshott’s awareness of ancient skepticism, even though its impact on his thought is contested and controversial. With regard to modern skepticism, it looks at how Oakeshott defines Hobbes’s skepticism in his “Introduction to Leviathan.” It also examines the relevance of Montaigne to Oakeshott’s image of conversation, his idea of human agency and conception of politics. Finally, the article illustrates the influence of Bradley’s skeptici...

Aim: To synthesize and characterize the performances of a new all-inorganic nanocomposite (NC) for self-lighted photodynamic therapy against cancer. This NC could allow radiotherapy doses to be reduced, as it enhances the effects of x-rays, generating cytotoxic reactive oxygen species as singlet oxygen. Materials & methods: The proposed NC combines CeF3 and ZnO; CeF3 absorbs 6-MeV x-rays and activates the photosensitizer ZnO. Characterization is performed by transmission electron microscopy (TEM), scanning-TEM, energy dispersive x-ray spectrometry and fluorescence spectroscopies. Efficiency on human adenocarcinoma cells (A549) was tested by fluorescence spectroscopy, cytofluorimetry, viability assays, clonogenic assays, cell cycle progression assays. Results: NC blocks A549's cell cycle before mitosis in the dark. Upon low-dose x-ray irradiation (2 Gy), reactive oxygen species/singlet oxygen are generated, further blocking cell cycle and reducing viability by 18% with respect to the sum of x-ray irradiation and NC dark activity. Conclusion: These novel NCs promise to reduce doses in radiotherapy, helping to reduce unwanted side effects.

In this work, we report on the direct measurement of the magnetic field induced temperature change in a series of micrometric thick ribbons of Ni-Mn-In-Sn Heusler alloys, performed with an innovative experimental technique based on the thermo-optical “Mirage Effect.” The technique combines very fast measurement time, 1 T pulsed magnetic field in the millisecond range, and contactless temperature detection. These features make the technique ideal for the characterization of thin samples with a thickness down to a few micrometers. In this work, we demonstrate this by directly measuring the magnetocaloric effect (MCE) of micrometric-thick ribbons of Heusler alloys at the Curie transition, which was tuned on a wide temperature range by varying the Sn to In ratio. The direct test of the MCE in thin samples is fundamental for the development of refrigerant elements with a large heat-transfer coefficient and for the design of solid state micro devices for cooling and energy harvesting.

This paper examines Michael Oakeshott's ideas on the relation between political philosophy and normative thought. To this end, some of the most controversial concepts of his thought are considered in the context of the philosophical debates that developed after the success of analytic philosophy and, in particular, of Ayer's Language, Truth, and Logic. First, the paper argues that, in contrast to analytic and ordinary language thinkers, Oakeshott defends the legitimacy and the rationality of normative thinking. To this end, the importance of the Oakeshottian concepts of tradition and moral practice is stressed, and the controversial notion of ‘pursuit of intimations’ is considered. Through a discussion of Oakeshott's unpublished notes, the relevance of Aristotle for the development of his thought is also highlighted. Second, the paper contends that Oakeshott sees political philosophy as a critical activity aiming at universal concepts. At the same time, the paper stresses the Oakeshottian distinction betw...

The spectral analysis of thermal fluctuations, or flickering, is a simple and non-invasive method widely used to determine the mechanical properties of artificial and biological lipid membranes. In its most common implementation, the position of the edge of a cell or vesicle is tracked from optical microscopy videos. However, a systematic disagreement with X-ray scattering and micromechanical manipulation data has brought into question the validity of the method. We present an improved analysis protocol that resolves these discrepancies by accounting for the finite vertical resolution of the optics used to image fluctuations.

We report here a detailed characterization of the steps leading to the formation of a bidimensional gel at the air/water interface. The 2D geometry is peculiar in that it allows a continuous and controlled variation of the density of the system over a wide range. The evolution of the statistical properties of the structured network, as a function of the externally controlled density, is related to the corresponding evolution of the mechanical properties. We identified three steps in the gel formation: a first step occurs in the incubation time, in which the individual nm-sized gold nanoparticle aggregate to form quasi 1D structures of typical length of a few microns. The second step occurs in the first stages of the compression, with the growth of the branched structure, finally yielding to the onset of the infinite percolative cluster, which is related to the building of the mechanical elastic modulus. The final step identifies with the homogenization and regularization of the distribution of holes sizes, which relates to the further increase of the elastic modulus upon compression. We speculate that this study should help in the formulation of gels with desired characteristics, such as increased mechanical strength, or increased mobility. (C) 2013 Elsevier B.V. All rights reserved.

Controlled phase separation in a polymer film, with subsequent morphology rearrangement on the micro-scale, provides novel perspectives in smart materials. Based on our experience on supramolecularly compatibilised polymer blends consisting of polystyrene and poly(butyl methacrylate), we demonstrate here physical segregation of the blend in the solid state by the application of an electrochemical stimulus. The thereby occurring changes in film morphology, namely the appearance of voids and grains, have been characterised by atomic force microscopy in spin coated and in Langmuir-Schaefer deposited films.

Silica nanoparticles (SiNP) can be incorporated in phospholipid layers to form hybrid organic-inorganic bidimensional mesostructures. Controlling the dynamics in these mesostructures paves the way to high-performance drug-delivery systems. Depending on the different hydrophobicity/hydrophilicity of SiNP, recent X-ray reflectivity experiments have demonstrated opposite structural effects. While these are reasonably well understood, less is known about the effects on the dynamics, which in turn determine molecular diffusivity and the possibility of drug release. In this work we characterize the dynamics of a mixed Langmuir layer made of phospholipid and hydrophobic SiNP. We combine X-ray photon correlation spectroscopy and epifluorescence discrete Fourier microscopy to cover more than 2 decades of Q-range (0.3-80 μm(-1)). We obtain evidence for the onset of an arrested state characterized by intermittent stress-relaxation rearrangement events, corresponding to a gel dominated by attractive interactions. We compare this with our previous results from phospholipid/hydrophilic SiNP films, which show an arrested glassy phase of repulsive disks.

International audience; We report X-ray Photon Correlation Spectroscopy (XPCS) measurements of microscale dynamics in Langmuir-Schaeffer deposited multilayers of a photosensitive azopolymer with a low concentration of gold nanoparticles embedded. Correlation functions were measured as a function of exchanged momentum and illumination conditions (dark and UV light) and fitted with the Kohlrausch-Williams-Watts (KWW) exponential form. The microscopic dynamic of the nanoparticles was quantified, evidencing a non-Brownian superdiffusive behavior with relaxation times tau ≈ q^-1, a result analogous to what previously had been observed in the pure azopolymer [D. Orsi et al., submitted to Phys. Rev. E (2010)]. Such behavior has been related to intermittent rearrangements [L. Cipelletti et al., Phys. Rev. Lett. 84, 2275-2278 (2000)] or random dipolar interactions within an elastic medium [J.-P. Bouchaud and E. Pitard, Eur. Phys. J. E 6, 231-236 (2001)]. Photoperturbation with UV light makes the dynamics faster, in accordance with the reduction of the viscosity of the polymer found by shear rheology, but the KWW form of the correlation functions persists. At constant temperature, the dynamics of the nanoparticles embedded in the polymeric matrix is sensibly faster than the slow microscopic dynamic of the polymer. At the same time, the Vogel-Fulcher-Tammann (VFT) law for the relaxation times indicates a less pronounced temperature dependence than for the pure polymer, resulting in a slightly lower activation temperature T_A.

This chapter firstly contends that in Oakeshott’s political philosophy there are considerations pertaining to the evolution of the international order based on the theory of civil association. In particular, these observations concern war, colonialism, and the evolution of international society. Secondly, the chapter explores and defends the notion of practical association as first presented by Terry Nardin. In particular, it contends that international society may be considered as an association between states constituted by a set of non-instrumental rules that reflect shared moral values, values that represent the shared premises of institutional moral reasoning. Finally, the chapter shows that this approach illuminates the normative nature of customary international law and its relations with international morality.

We report on the synthesis and characterization of a composite nanostructure based on the coupling of cerium fluoride (CeF3) and zinc oxide (ZnO) for applications in self-lighted photodynamic therapy. Self-lighted photodynamic therapy is a novel approach for the treatment of deep cancers by low doses of X-rays. CeF3 is an efficient scintillator: when illuminated by X-rays it emits UV light by fluorescence at 325 nm. In this work, we simulate this effect by exciting directly CeF3 fluorescence by UV radiation. ZnO is photo-activated in cascade, to produce reactive oxygen species. This effect was recently demonstrated in a physical mixture of distinct nanoparticles of CeF3 and ZnO [Radiat. Meas. (2013) 59:139-143]. Oxide surface provides a platform for rational functionalization, e.g., by targeting molecules for specific tumors. Our composite nanostructure is stable in aqueous media with excellent optical coupling between the two components; we characterize its uptake and its good cell viability, with very low intrinsic cytotoxicity in dark.

This chapter shows that Oakeshott’s philosophy is relevant to debates in international theory. It demonstrates that the critique of rationalism in politics is linked to the second Great Debate between classical and scientific approaches that was developed in the second half of the twentieth century. It shows that in Oakeshott’s texts there are references to Morgenthau’s critique of scientific politics, and that Hedley Bull’s argument against the scientific approach resembles Oakeshott’s one against rationalism. The chapter also highlights some of the differences between Oakeshott’s conception of history and those defended by the English School. The relevance of Oakeshott’s philosophy for the development of the so-called normative turn in International Relations is demonstrated. Finally, the chapter highlights some of the similarities between Oakeshott’s epistemology and recent constructivist literature.

This chapter examines Oakeshott’s thought in the light of its idealist sources and shows that he presents a consistent conception of philosophical activity and knowledge. It emerges that Oakeshott maintains a sense of the distinctness and autonomy of modes of experience. Philosophy is a critical activity that identifies the presuppositions of various ideas and forms of understanding, assesses their limited validity, and aims at universal concepts. Oakeshott’s theory of “conversation of mankind” may be regarded as an original interpretation of the idealist conception of dialectic and the ground for Oakeshott’s critique of rationalism. It is on this basis that the broader problem of the relation between philosophy and practice is considered.

This chapter considers the idea of an international civil association, constituted by a set of non-instrumental rules, in the light of realist, universalist, and constitutive theories of International Relations. It highlights the similarities between Oakeshott and realism by exploring Oakeshott’s arguments against theories of universal moral order, as well as his defence of a phronetic conception of political activity. However, on the basis of textual evidence from Oakeshott’s essay “The Rule of Law,” the chapter ultimately argues that, in Oakeshott’s theory, law reflects evolving moral practices, and that this illuminates the source of international legal obligation. As such, the chapter contributes to debates in constructivist literature on the source of international authority and on the relation between moral values and international law.

Despite the considerable impact of Oakeshott’s theory of tradition on English School writers, the relevance of Oakeshott’s philosophy to the theorizing of international practices has been neglected. This chapter shows the contribution of Oakeshott’s philosophy to our understanding of international practices. The chapter starts explaining the impact that Oakeshott’s notion of tradition has had on English School writers, and then demonstrates that the notions of tradition and “pursuit of intimation” delineate a model of practical reasoning conceived as based on shared premises. With this discussion as a background, it then compares Oakeshott’s position to critical theory and shows its contribution to the recent practice turn and normative international theory.

We investigate the interfacial dynamics of a 2D self-organized mixed layer made of silica nanoparticles interacting with phospholipid (DPPC) monolayers at the air/water interface. This system has biological relevance, allowing investigation of toxicological effects of nanoparticles on model membranes and lung surfactants. It might also provide bio-inspired technological solutions, exploiting the self-organization of DPPC to produce a non-trivial 2D structuration of nanoparticles. The characterization of interfacial dynamics yields information on the effects of NPs on the mechanical properties, important to improve performances of systems such as colloidosomes, foams, creams. For this, we combine micro-tracking in real-space with measurement in momentum-space via x-ray photon-correlation spectroscopy and Digital Fourier Microscopy. Using these complementary techniques, we extend the spatial range of investigation beyond the limits of each one. We find a dynamical transition from Brownian diffusion to an arrested state driven by compression, characterized by intermittent rearrangements, compatible with a repulsive glass phase. The rearrangement and relaxation of the monolayer structure results dramatically hindered by the presence of NPs, which is relevant to explain some the mechanical features observed for the dynamic surface pressure response of these systems and which can be relevant for the respiratory physiology and for future drug-delivery composite systems.

Multivalent interactions between deformable mesoscopic units are ubiquitous in biology, where membrane macromolecules mediate the interactions between neighbouring living cells and between cells and solid substrates. Lately, analogous artificial materials have been synthesised by functionalising the outer surface of compliant Brownian units, for example emulsion droplets and lipid vesicles, with selective linkers, in particular short DNA sequences. This development extended the range of applicability of DNA as a selective glue, originally applied to solid nano and colloidal particles. On very deformable lipid vesicles, the coupling between statistical effects of multivalent interactions and mechanical deformation of the membranes gives rise to complex emergent behaviours, as we recently contributed to demonstrate [Parolini et al., Nature Communications, 2015, 6, 5948]. Several aspects of the complex phenomenology observed in these systems still lack a quantitative experimental characterisation and fundamental understanding. Here we focus on the DNA-mediated multivalent interactions of a single liposome adhering to a flat supported bilayer. This simplified geometry enables the estimate of the membrane tension induced by the DNA-mediated adhesive forces acting on the liposome. Our experimental investigation is completed by morphological measurements and the characterisation of the DNA-melting transition, probed by in-situ F\"{o}rster Resonant Energy Transfer spectroscopy. Experimental results are compared with the predictions of an analytical theory that couples the deformation of the vesicle to a full description of the statistical mechanics of mobile linkers. With at most one fitting parameter, our theory is capable of semi-quantitatively matching experimental data, confirming the quality of the underlying assumptions., Comment: 16 pages, 7 figures

In this work, we demonstrate – in two different settings – the potential of the recognition motif made by tetraphosphonate cavitand/N-methyl ammonium salt for the development of supramolecular polymer chemistry. In the first part a novel pH sensitive supramolecular homopolymer was assembled by proper design of the corresponding monomer, and monitoring the self-assembling process by several analytical tools, including NMR spectroscopy and light scattering techniques. These measurements provided the evidence for the formation of the homopolymer and its pH responsiveness. In the second study, the two recognition groups – tetraphosphonate cavitand (Host) and sarcosine hydrochloride (Sarc) – introduced in polystyrene (PS–Host) and poly(butyl methacrylate) (PBMA–Sarc) respectively, led to the mixing of the two otherwise immiscible polymers thanks to the energetically favourable host–guest interactions between the polymer chains. The polymer blending was verified by the presence of a single glass transition temperature (Tg) and showed its homogeneous morphology by atomic force microscopy (AFM).

A new approach is proposed for measuring structural dynamics in materials from multi-speckle scattering patterns obtained with partially coherent X-rays. Coherent X-ray scattering is already widely used at high-brightness synchrotron lightsources to measure dynamics using X-ray photon correlation spectroscopy, but in many situations this experimental approach based on recording long series of images (i.e.movies) is either not adequate or not practical. Following the development of visible-light speckle visibility spectroscopy, the dynamic information is obtained instead by analyzing the photon statistics and calculating the speckle contrast in single scattering patterns. This quantity, also referred to as the speckle visibility, is determined by the properties of the partially coherent beam and other experimental parameters, as well as the internal motions in the sample (dynamics). As a case study, Brownian dynamics in a low-density colloidal suspension is measured and an excellent agreement is found between correlation functions measured by X-ray photon correlation spectroscopy and the decay in speckle visibility with integration time obtained from the analysis presented here.