Nanoparticle formation of chitosan induced by 4-sulfonatocalixarenes: utilization for alkaloid encapsulation

Spontaneous formation of positively charged nanoparticles was observed upon mixing more than stoichiometric amount of chitosan with 4-sulfonatocalix[8]arene (SCX8) in acidic solution. The particle size did not change with SCX8 concentration, polymer chain length, and the degree of deacetylation at 0.002 ≤ SCX8/chitosan ≤0.043 molar ratios in 0.01 M HCl. However, larger aggregates were produced when chitosan concentration was increased. The most stable nanoparticles with 160 nm diameter and narrow size distribution were obtained at pH 4 using low molecular weight chitosan. These particles encapsulated coralyne with more than 90 % entrapment efficiency and 15 % loading capacity. A loading ratio of [coralyne]/[SCX8] = 1.7 was achieved without any stability loss. 4-Sulfonatocalix[4]arene induced the formation of slightly smaller nanoparticles than its homologs comprising 6 or 8 phenol units. © 2016, Springer-Verlag Berlin Heidelberg

Effect of host–guest complex formation on the fluorescence of 6-methoxy-1-methyl-quinolinium cation with 4-sulfonatocalix[4]arene: utilization as a fluorescent probe for the study of difenzoquat binding

The complexation of the highly fluorescent 6-methoxy-1-methyl-quinolinium (C1MQ) and the widely used herbicide, difenzoquat (DFQ), with 4-sulfonatocalix[4]arene (SCX4) macrocycle was studied by isothermal titration calorimetry, fluorescence and NMR spectroscopy in aqueous solutions at 298 K. Both guests produced 1:1 complexes with SCX4, but the binding affinity of C1MQ was more than one order of magnitude larger than that of DFQ in neutral medium. The higher stability of C1MQSCX4 complex originated from the significant enthalpy gain upon its formation. The encapsulation of C1MQ in SCX4 in the ground state resulted in an efficient fluorescence quenching due to electron transfer from the host to the excited guest. The marked difference in the fluorescence quantum yields for free and bound C1MQ was used to detect the competitive complexation of DFQ in SCX4

Effect of Macrocycle Size on the Self-Assembly of Methylimidazolium Surfactant with Sulfonatocalix[n]arenes

The effect of macrocycle size on the association of supramolecular amphiphiles composed of 4-sulfonatocalix[n]arene and 1-methyl-3-tetradecylimidazolium (C14mim+) was studied in aqueous solutions at pH 7. When the cavitand contained four sulfonatophenol units (SCX4), spherical nanoparticle (NP) formation was observed. In contrast, both supramolecular micelle (SM) and NP formation could be attained in the presence of NaCl when the larger, more flexible 4-sulfonatocalix[8]arene (SCX8) served as host compound. The SCX8-promoted self-assembly into SM was enthalpically more favorable than NP production but the molar heat capacity changes in the two processes barely differed. Addition of 50 mM NaCl significantly increased the enthalpy of C14mim+−SCX8 NP formation making thereby the self-organization into SM more favorable. The transformation of SM into NP at high temperature was due to the substantial entropic contribution to the driving force of NP formation. The critical micelle concentration and the local polarity in the headgroup domain were considerably lower for SM compared to those of C14mim+Br conventional micelle

Effect of Headgroup Variation on the Self-Assembly of Cationic Surfactants with Sulfonatocalix[6]arene

The effect of headgroup variation on the association of supramolecular amphiphiles composed of 4-sulfonatocalix[6]arene (SCX6) and cationic surfactant possessing tetradecyl substituent was studied in aqueous solutions at pH 7. When the surfactant contained hydrophilic trimethylammonium, pyridinium, or 1-methylimidazolium headgroup, highly reversible temperature-responsive nanoparticle-supramolecular micelle transformation could be attained at appropriately chosen component mixing ratios and NaCl concentrations. In these cases, the substantial negative molar heat capacity change (ΔCp) rendered nanoparticle formation strongly endothermic at low temperature, whereas the assembly to supramolecular micelle was always accompanied by enthalpy gain. The ΔCp values became less negative when the charge density and the hydrophilic character of the surfactant headgroup diminished. The association of the more hydrophobic 6-methoxyquinolinium and quinolinium surfactants with SCX6 did not lead to supramolecular micelle formation because the self-assembly into nanoparticles was highly exothermic

Analysis of end-to-end multi-domain management and orchestration frameworks for software defined infrastructures: An architectural survey

Over the last couple of years, industry operators' associations issued requirements towards an end-to-end management and orchestration plane for 5G networks. Consequently, standard organisations started their activities in this domain. This article provides an analysis and an architectural survey of these initiatives and of the main requirements, proposes descriptions for the key concepts of domain, resource and service slicing, end-to-end orchestration and a reference architecture for the end-to-end orchestration plane. Then, a set of currently available or under development domain orchestration frameworks are mapped to this reference architecture. These frameworks, meant to provide coordination and automated management of cloud and networking resources, network functions and services, fulfil multi-domain (i.e. multi-technology and multi-operator) orchestration requirements, thus enabling the realisation of an end-to-end orchestration plane. Finally, based on the analysis of existing single-domain and multi-domain orchestration components and requirements, this paper presents a functional architecture for the end-to-end management and orchestration plane, paving the way to its full realisatio

Analysis of end-to-end multi-domain management and orchestration frameworks for software defined infrastructures: An architectural survey

Over the last couple of years, industry operators' associations issued requirements towards an end-to-end management and orchestration plane for 5G networks. Consequently, standard organisations started their activities in this domain. This article provides an analysis and an architectural survey of these initiatives and of the main requirements, proposes descriptions for the key concepts of domain, resource and service slicing, end-to-end orchestration and a reference architecture for the end-to-end orchestration plane. Then, a set of currently available or under development domain orchestration frameworks are mapped to this reference architecture. These frameworks, meant to provide coordination and automated management of cloud and networking resources, network functions and services, fulfil multi-domain (i.e. multi-technology and multi-operator) orchestration requirements, thus enabling the realisation of an end-to-end orchestration plane. Finally, based on the analysis of existing single-domain and multi-domain orchestration components and requirements, this paper presents a functional architecture for the end-to-end management and orchestration plane, paving the way to its full realisation

On non-cooperative genomic privacy

Over the last few years, the vast progress in genome sequencing has highly increased the availability of genomic data. Today, individuals can obtain their digital genomic sequences at reasonable prices from many online service providers. Individuals can store their data on personal devices, reveal it on public online databases, or share it with third parties. Yet, it has been shown that genomic data is very privacysensitive and highly correlated between relatives. Therefore, individuals’ decisions about how to manage and secure their genomic data are crucial. People of the same family might have very different opinions about (i) how to protect and (ii) whether or not to reveal their genome. We study this tension by using a game-theoretic approach. First, we model the interplay between two purely-selfish family members. We also analyze how the game evolves when relatives behave altruistically. We define closed-form Nash equilibria in different settings. We then extend the game to N players by means of multi-agent influence diagrams that enable us to efficiently compute Nash equilibria. Our results notably demonstrate that altruism does not always lead to a more efficient outcome in genomic-privacy games. They also show that, if the discrepancy between the genome-sharing benefits that players perceive is too high, they will follow opposite sharing strategies, which has a negative impact on the familial utility. © International Financial Cryptography Association 2015

Reversible Nanoparticle–Micelle Transformation of Ionic Liquid–Sulfonatocalix[6]arene Aggregates

The effect of temperature and NaCl concentration variations on the self-assembly of 1-methyl-3- tetradecylimidazolium (C14mim+) and 4-sulfonatocalix[6]- arene (SCX6) was studied by dynamic light scattering and isothermal calorimetric methods at pH 7. Inclusion complex formation promoted the self-assembly to spherical nanoparticles (NP), which transformed to supramolecular micelles (SM) in the presence of NaCl. Highly reversible, temperature-responsive behavior was observed, and the conditions of the NP−SM transition could be tuned by the alteration of C14mim+:SCX6 mixing ratio and NaCl concentration. The association to SM was always exothermic with enthalpy independent of the amount of NaCl. In contrast, NPs were produced in endothermic process at low temperature, and the enthalpy change became less favorable upon increase in NaCl concentration. The NP formation was accompanied by negative molar heat capacity change, which further diminished when NaCl concentration was raised