Micelles from HOOC-PnBA- b -PAA-C12_{12} H15_{15} Diblock Amphiphilic Polyelectrolytes as Protein Nanocarriers

We investigate the potential of self-assembled nanostructures of the PnBA-b-PAA amphiphilic diblock polyelectrolyte as candidates for protein nanocarriers. Three PnBA-b-PAA copolymers with different molecular weights and PnBA/PAA weight ratios are tested. The system with the most well-defined core–shell micellar structure is chosen for complexation with lysozyme. Its solutions are found to contain well-defined core–shell micelles that are stable upon increase in solution salt content to physiological levels. Upon mixing with lysozyme we find that the protein globules accumulate preferably at the outer parts of the hydrated corona of the micelles. Increasing the protein concentration, intermicellar aggregation is enhanced in a controllable way. At high salt content the number of proteins per micelle is lower compared with the low salt content, which points to an interaction of predominantly electrostatic nature. While light scattering is very sensitive to complexation, small-angle neutron scattering is able to distinguish between the contributions from individual micelles and aggregates. This work demonstrates the use of scattering techniques to characterize protein–polymer interactions in multiple hierarchical levels

Characterization of Industrial Coolant Fluids and Continuous Ageing Monitoring by Wireless Node-Enabled Fiber Optic Sensors

Environmentally robust chemical sensors for monitoring industrial processes or infrastructures are lately becoming important devices in industry. Low complexity and wireless enabled characteristics can offer the required flexibility for sensor deployment in adaptable sensing networks for continuous monitoring and management of industrial assets. Here are presented the design, development and operation of a class of low cost photonic sensors for monitoring the ageing process and the operational characteristics of coolant fluids used in an industrial heavy machinery infrastructure. The chemical, physical and spectroscopic characteristics of specific industrial-grade coolant fluids were analyzed along their entire life cycle range, and proper parameters for their efficient monitoring were identified. Based on multimode polymer or silica optical fibers, wide range (3–11) pH sensors were developed by employing sol-gel derived pH sensitive coatings. The performances of the developed sensors were characterized and compared, towards their coolants’ ageing monitoring capability, proving their efficiency in such a demanding application scenario and harsh industrial environment. The operating characteristics of this type of sensors allowed their integration in an autonomous wireless sensing node, thus enabling the future use of the demonstrated platform in wireless sensor networks for a variety of industrial and environmental monitoring applications

Development of hybrid photonic materials as devices for optical sensors

In the present study the synthesis of hybrid materials consisting of metal nanoparticles incorporated into organic and inorganic matrices is presented. The synthesized materials can be divided into two categories; the first one consists of Au and Ag nanoparticles incorporated into polymeric matrices, while the second one consists of Au, Ag and NiCl2 nanoparticles incorporated into inorganic matrices. The thesis was focused on the synthesis and the spectroscopic study of these materials. Meanwhile, the optical and photonic properties of these materials were exploited. Moreover, the biological applications of the synthesized hybrid materials were investigated. In more detail, the larger part of this work focuses on the in situ synthesis of Au and Ag nanoparticles either inside the core or on the corona of di- and triblock copolymers and random copolymers. More specifically, the synthesis protocol requires three steps. First, the proper solvent must be chosen, which should be selective for one of the blocks of the amphiphilic copolymer, in order for micelles to be formed, consisting of a dense core and a solubilized corona. Then the metal precursor is added, which is preferentially dissolved into the core or is coordinated on the periphery of the corona block, depending on the chemical affinity that each block displays toward the metal compound. Finally, the metal ions are reduced in metal nanoparticles either by the addition of a reducing agent or by the coordinating block of the copolymer. The second category of the materials involves the synthesis of Au, Ag and NiCl2 nanoparticles inside inorganic matrices such as SiO2 and TiO2. Solutions containing SiO2 and TiO2 precursors were mixed with metal salts and the standard sol-gel methods were followed for the in situ synthesis of the hybrid materials. Thermal treatment and ageing were the two main parameters that influenced the size and the degree of aggregation of the metal nanoparticles, as well as the porosity of the final material. The non-linear optical properties of the synthesized hybrid materials were studied using the OKE and Z-scan techniques. All the materials studied displayed nonlinear refraction which was proportional to the ratio between the metal vii nanoparticles and the polymer. The composition of the block copolymer itself played also an important role. The hybrid nano materials were also evaluated as active components in potential photonic sensors. In the presence of methanol and ammonia, morphological changes on the surface of the materials were noticed. These changes were recorded as a signal modulation in respect to the reference signal. Finally, some of the synthesized hybrid materials displayed biocompatibility and their ability to coordinate with proteins and DNA molecules was examined, toward their utilization in bioanalytical devicesΣτην παρούσα εργασία παρουσιάζεται η σύνθεση και η μελέτη υβριδικών υλικών, τα οποία αποτελούνται από νανοσωματίδια εγκλωβισμένα σε οργανικές και ανόργανες μήτρες. Τα υλικά που συντέθηκαν μπορούν να χωριστούν σε δύο κατηγορίες. Η πρώτη περιλαμβάνει μεταλλικά νανοσωματίδια Au και Ag εγκλωβισμένα σε πολυμερικές μήτρες, ενώ η δεύτερη κατηγορία περιλαμβάνει νανοσωματίδια Au, Ag και NiCl2 σε ανόργανες μήτρες. Η εργασία επικεντρώθηκε στην σύνθεση και την φασματοσκοπική μελέτη των υλικών χρησιμοποιώντας όλες τις διαθέσιμες τεχνικές δομικού χαρακτηρισμού των υλικών. Παράλληλα, πραγματοποιήθηκε μελέτη των οπτικών ιδιοτήτων και της χημειο-οπτικής ενεργότητας των υλικών. Επίσης, μελετήθηκε η βιοσυμβατότητα των υλικών στις περιπτώσεις που αυτό ήταν δυνατό. Αναλυτικότερα, στο μεγαλύτερο κομμάτι της εργασίας αυτής περιγράφεται η in situ σύνθεση μεταλλικών νανοσωματιδίων Au και Ag στον πυρήνα και στην κορώνα δισυσταδικών συμπολυμερών καθώς και τυχαίων συμπολυμερών. Το πρωτόκολλο που ακολουθήθηκε περιλαμβάνει τα παρακάτω βήματα: αρχικά για την διαλυτοποίηση του αμφίφιλου συμπολυμερούς επιλέγεται εκλεκτικός διαλύτης ως προς την μία συστάδα του, ώστε να σχηματιστούν μικκήλια αποτελούμενα από ένα συμπαγή πυρήνα και μια διαλυτή κορώνα. Στην συνέχεια, προστίθεται το άλας του μετάλλου στο διάλυμα του συμπολυμερούς με αποτέλεσμα είτε την εισροή του στον πυρήνα, είτε την συναρμογή του μεταλλικού ιόντος με την κορώνα ανάλογα με την χημική συνάφεια που φέρει η κάθε συστάδα ως προς το μέταλλο. Τέλος, ακολουθεί η αναγωγή του μεταλλικών ιόντων σε μεταλλικά νανοσωματίδια είτε προσθέτοντας κάποιο αναγωγικό μέσο, είτε από το ίδιο το συμπολυμερές που περιβάλλει τα μεταλλικά ιόντα. Η δεύτερη κατηγορία υλικών αφορά στην σύνθεση νανοσωματιδίων Au, Ag και NiCl2 σε ανόργανες μήτρες. Σε αυτή την περίπτωση επιλέχθηκαν πρόδρομες ενώσεις SiO2 και TiO2, οι οποίες αναμίχθηκαν με το άλας των μετάλλων ακολουθώντας την μέθοδο sol-gel ώστε να σχηματιστούν νανοσωματίδια. Μελετήθηκε η επίδραση των πειραματικών παραμέτρων, όπως η θέρμανση και η γήρανση, στο μέγεθος και τον βαθμό συσσωμάτωσης των μεταλλικών νανοσωματιδίων καθώς επίσης και στο πορώδες του τελικού υλικού. Από τα v διαλύματα που προέκυψαν, σχηματίστηκαν λεπτά υμένια με την μέθοδο του spincoating, τα οποία στην συνέχεια θερμάνθηκαν σε υψηλές θερμοκρασίες ώστε να απομακρυνθούν οι οργανικές ομάδες και να σταθεροποιηθεί το τελικό υλικό. Μέρος των υβριδικών υλικών που συντέθηκαν μελετήθηκαν ως προς την μη-γραμμική τους απόκριση χρησιμοποιώντας τις τεχνικές OKE και Z-scan. Όπως προέκυψε από τις μετρήσεις τα υλικά αυτά παρουσιάζουν μη-γραμμικότητα, η οποία εξαρτάται άμεσα τόσο από την αναλογία μετάλλου ως προς το συμπολυμερές αλλά και από την σύσταση του ίδιου του συμπολυμερούς. Τα νανοσύνθετα υλικά που συντέθηκαν αξιολογήθηκαν επίσης ως ενεργά υλικά σε πιθανούς φωτονικούς αισθητήρες

Micelles from HOOC-PnBA‑<i>b</i>‑PAA‑C₁₂H₁₅ Diblock Amphiphilic Polyelectrolytes as Protein Nanocarriers

We investigate the potential of self-assembled nanostructures of the PnBA-<i>b</i>-PAA amphiphilic diblock polyelectrolyte as candidates for protein nanocarriers. Three PnBA-<i>b</i>-PAA copolymers with different molecular weights and PnBA/PAA weight ratios are tested. The system with the most well-defined core–shell micellar structure is chosen for complexation with lysozyme. Its solutions are found to contain well-defined core–shell micelles that are stable upon increase in solution salt content to physiological levels. Upon mixing with lysozyme we find that the protein globules accumulate preferably at the outer parts of the hydrated corona of the micelles. Increasing the protein concentration, intermicellar aggregation is enhanced in a controllable way. At high salt content the number of proteins per micelle is lower compared with the low salt content, which points to an interaction of predominantly electrostatic nature. While light scattering is very sensitive to complexation, small-angle neutron scattering is able to distinguish between the contributions from individual micelles and aggregates. This work demonstrates the use of scattering techniques to characterize protein–polymer interactions in multiple hierarchical levels

Characterization of industrial coolant fluids and continuous ageing monitoring by wireless node-enabled fiber optic sensors

Altres ajuts: This work was funded by COST Action TD1001 "Novel and Reliable Optical Fibre Sensor Systems for Future Security and Safety Applications"Environmentally robust chemical sensors for monitoring industrial processes or infrastructures are lately becoming important devices in industry. Low complexity and wireless enabled characteristics can offer the required flexibility for sensor deployment in adaptable sensing networks for continuous monitoring and management of industrial assets. Here are presented the design, development and operation of a class of low cost photonic sensors for monitoring the ageing process and the operational characteristics of coolant fluids used in an industrial heavy machinery infrastructure. The chemical, physical and spectroscopic characteristics of specific industrial-grade coolant fluids were analyzed along their entire life cycle range, and proper parameters for their efficient monitoring were identified. Based on multimode polymer or silica optical fibers, wide range (3-11) pH sensors were developed by employing sol-gel derived pH sensitive coatings. The performances of the developed sensors were characterized and compared, towards their coolants' ageing monitoring capability, proving their efficiency in such a demanding application scenario and harsh industrial environment. The operating characteristics of this type of sensors allowed their integration in an autonomous wireless sensing node, thus enabling the future use of the demonstrated platform in wireless sensor networks for a variety of industrial and environmental monitoring applications

Modulation of the singlet-singlet through-space energy transfer rates in cofacial bisporphyrin and porphyrin-corrole dyads

International audienc

Thermoresponsive behavior of poly(N-isopropylacrylamide)s with dodecyl and carboxyl terminal groups in aqueous solution: pH-dependent cloud point temperature

It was recently reported that poly(N-isopropyl acrylamide) (PNIPAm) polymers synthesized by RAFT polymerization using S-1-dodecyl-S′-(α,α′-dimethyl-α′′-acetic acid)trithiocarbonate as a chain transfer agent form micelles in aqueous solutions with the core of hydrophobic terminal dodecyl groups and the corona of PNIPAm chains with carboxylic groups at the periphery, the ionization of which prevents the micelles from phase separation above the lower critical solution temperature of PNIPAm in water (Langmuir 30:7986–7992). In this paper, we study the pH- and ionic strength-dependence of the aggregation behavior of two HOOC-PNIPAm-C12 polymers, differing in the degree of polymerization, in aqueous solutions. We show that the cloud point temperature (CPT) of HOOC-PNIPAm-C12 can be shifted up to several tens of K by changing pH of the solution. The aggregation of the PNIPAms above the CPT can be efficiently accelerated by screening electrostatic repulsion between PNIPAm micelles by changing ionic strength of the solution