The ability of the soluble fibre (1->3)(1->4)-β-D-glucan to attenuate postprandial glycemic responses depends on its viscosity which, in turn, depends on molecular weight (MW) and dose. However, the effect of altering viscosity by changing solution volume is unknown. Furthermore, β-glucan solutions may form hard gels when left to age, but the effect of these gels on glycemic responses is unknown. Therefore, the effects of varying the MW and volume of β-glucan solutions and hard gels, on glycemic responses were determined. The results showed that glycemic responses were reduced by increasing viscosity by increasing MW but not by reducing solution volume. Although β-glucan gels reduced the rate of glucose diffusion in vitro, they had no effect on glycemic responses in vivo. Thus, changing solution viscosity through changes in volume does not alter the effect of β-glucan on glycemic response, and β-glucan gels are ineffective at attenuating in vivo glycemic responses.

The ability of the soluble fibre (1->3)(1->4)-β-D-glucan to attenuate postprandial glycemic responses depends on its viscosity which, in turn, depends on molecular weight (MW) and dose. However, the effect of altering viscosity by changing solution volume is unknown. Furthermore, β-glucan solutions may form hard gels when left to age, but the effect of these gels on glycemic responses is unknown. Therefore, the effects of varying the MW and volume of β-glucan solutions and hard gels, on glycemic responses were determined. The results showed that glycemic responses were reduced by increasing viscosity by increasing MW but not by reducing solution volume. Although β-glucan gels reduced the rate of glucose diffusion in vitro, they had no effect on glycemic responses in vivo. Thus, changing solution viscosity through changes in volume does not alter the effect of β-glucan on glycemic response, and β-glucan gels are ineffective at attenuating in vivo glycemic responses.

Nous avons mené une étude prospective randomisée dans le but de comparer l'effet de l'irrigation du cathéter de type PICC avec deux types d'anticoagulants: Héparine standard et Tinzaparine, une héparine de faible poids moléculaire. Notre étude s'adresse aux patients de la clinique externe d'oncologie de l'hôpital Maisonneuve-Rosemont. Entre début Mai 2005 et Mars 2008, nous avons recruté 131 patients dont 70 ont été randomisés. Parmi les 61 patients exclus, 23 n'ont pas rencontré les critères d'inclusion, 30 ont refusé de participer et 8 ne sont pas inclus pour d'autres raisons. Sur les 70, 36 sujets sont randomisés dans le groupe Héparine standard et 34 dans le groupe Tinzaparine. La population en intention de traiter comprend 65 sujets dont 32 dans le groupe Héparine standard et 33 dans le groupe Tinzaparine. Le médicament a été administré pendant un mombre maximal de 30 jours et les sujets ont été suivis pendant 90 jours. La thrombose veineuse associée au cathéter (TVAC) a été objectivée par une phlébographie ou une échographie-Doppler à la fin de la période de 30 jours suivant l'installation du cathéter. L'incidence de la TVAC sur 30 jours est de 14,39 par 1000 cathéter-jours (IC à 95%:[9,0;19,79]/1000 cathéter-jours ou 41,5% (27/65). L'incidence de la thrombose veineuse profonde (TVP) symptômatique du membre supérieur sur la période de suivi de 90 jours est de 0,41 par 1000 cathéter-jours (IC à 95%:[0,08;0,81]/1000 cathéter-jours ou 3% (2/65). Nous n'avons observé aucune différence entre les deux groupes par rapport à la fréquence de la TVAC ni de la TVP. Nous ne pouvons conclure à une différence dans l'efficacité de la Tinzaparine par rapport à l'Héparine standard dans la prévention de la TVAC. / Our prospective, randomized study aims at comparing the effectiveness of two types of heparin used for the instillation of peripherally inserted central catheter (PICC): Standard heparin and Tinzaparin, a low molecular weight heparin. We recruited patients from the ambulatory center of Maisonneuve-Rosemont hospital. Between the beginning of May 2005 and March 2008, 131 patients were enrolled. Of 61 patients excluded, 23 did not satisfy the inclusion criteria, 30 refused to participate and 8 were not enrolled for other reasons. Seventy patients were randomized into two groups, 36 in the Standard heparin group and 34 in the Tinzaparin group. Our population intent-to-treat included 65/70 patients, 32 of these received Standard heparin and 33 received Tinzaparin. The experimental intervention was administered for a maximum of 30 days and all the subjects were followed up for 90 days. The events were documented objectively with a venogram or Doppler ultrasonography by the end of the 30 days following the catheter installation. The incidence of catheter-related venous thrombosis (CRVT) during 30 days of instillation is 14,39/1000 catheter-days (CI 95%:[9,0;19,79]/1000 catheter-days or 41.5% (27/65). The incidence of symptomatic upper extremity deep venous thrombosis (DVT) during the observation period of 90 days is 0,41/1000 catheter-days (CI 95%:[0,08;0,81]/1000 catheter-days or 3% (2/65). We did not observe any difference in the frequency of CRVT or DVT between the two groups. We can not conclude that either Standard heparin or Tinzaparin is more effective in the prevention of CRVT in our population.

La thérapie génique représente l'un des défis de la médecine des prochaines décennies dont la réussite dépend de la capacité d'acheminer l'ADN thérapeutique jusqu'à sa cible. Des structures non virales ont été envisagées, dont le chitosane, polymère cationique qui se combine facilement à l’ADN. Une fois le complexe formé, l’ADN est protégé des nucléases qui le dégradent. Le premier objectif de l'étude est de synthétiser et ensuite évaluer différentes nanoparticules de chitosane et choisir la mieux adaptée pour une efficacité de transfection sélective in vitro dans les cellules carcinomes épidermoïdes (KB). Le deuxième objectif de l'étude est d'examiner in vivo les effets protecteurs du gène de l'IL-1Ra (bloqueur naturel de la cytokine inflammatoire, l’Interleukine-1β) complexé aux nanoparticules de chitosane sélectionnées dans un modèle d'arthrite induite par un adjuvant (AIA) chez le rat. Les nanoparticules varient par le poids moléculaire du chitosane (5, 25 et 50 kDa), et la présence ou l’absence de l’acide folique (FA). Des mesures macroscopiques de l’inflammation seront évaluées ainsi que des mesures de concentrations de l’Interleukine-1β, Prostaglandine E2 et IL-1Ra humaine secrétés dans le sérum. Les nanoparticules Chitosane-ADN en présence de l’acide folique et avec du chitosane de poids moléculaire de 25 kDa, permettent une meilleure transfection in vitro. Les effets protecteurs des nanoparticules contenant le gène thérapeutique étaient évidents suite à la détection de l’IL-1Ra dans le sérum, la baisse d'expressions des facteurs inflammatoires, l’Interleukine-1 et la Prostaglandine-E2 ainsi que la diminution macroscopique de l’inflammation. Le but de cette étude est de développer notre méthode de thérapie génique non virale pour des applications cliniques pour traiter l’arthrite rhumatoïde et d’autres maladies humaines. / Considered to be one of the medical challenges of the coming decade, the success of gene therapy depends on the ability to deliver therapeutic DNA to target cells. Non-viral polymers, such as chitosan (Ch), a cationic polymer, can be easily combined with DNA. Once a complex is formed, DNA is protected from degradation by nucleases. The first objective of this study was to define the characteristics of the best-suited Ch nanoparticle for maximum selective transfection in human epidermoid carcinoma (KB) cells in vitro. Nanoparticles varied by the presence or absence of folic acid (FA) and Ch’s molecular weight (MW 5, 25 and 50 kDa). They were then selected and combined with interleukin-1 receptor antagonist (IL-1Ra) gene, a natural blocker of the inflammatory cytokine interleukin-1beta (IL-1β). The second objective was to inject these carriers by the hydrodynamic method in a rat model of adjuvant-induced arthritis and to evaluate the inhibitory effects of IL-1Ra against inflammation in vivo. Ch-DNA nanoparticles with FA and Ch25 demonstrated selective transfection and significantly increased it in KB cells in vitro. The inhibitory effects of IL-1Ra gene therapy in vivo were evident from lower expression levels of inflammatory factors (IL-1 and prostaglandin E2) and decreased macroscopic limb inflammation. The results also revealed the presence of human recombinant IL-1Ra protein in rat sera. Non-viral gene therapy with Ch-PEG-FA-DNA nanoparticles containing the IL-1Ra gene appears to significantly decrease inflammation in this experimental model of arthritis.

Here, we report on a new temperature responsive polymer brush system with a terminal “click” functionality. Bifunctionalized poly(N-isopropylacrylamide) (PNiPAAm) with distinct functional end groups was synthesized by atom transfer radical polymerization (ATRP) and grafted to a modified silicon substrate. The presence of the active terminal alkyne functionality is validated using an azide-modified rhodamine B (N3-RhB) via copper(I) catalyzed alkyne–azide cycloaddition (CuAAC). The optical properties and swelling dynamics of an N3-RhB modified PNiPAAm brush are analyzed in dry state and in situ by VIS-spectroscopic ellipsometry (SE). The best-fit results are obtained using a Gaussian oscillator model and are confirmed by UV/VIS-spectroscopy. We observed evidence of interactions between the aromatic residues of the dye and the PNiPAAm amide groups, which significantly affect the swelling behavior of the modified polymer brush. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Soil P fractionation was used to examine changes in soil inorganic and organic P under grazed irrigated pasture in a long-term field trial at Winchmore in Mid-Canterbury. The soil P fractionation scheme used involved sequential extractions of soil with O.5M NaHCO₃ @ pH 8.5 (NaHCO₃ P), 0.1M NaOH (NaOH I P), 1M HCl (HCl P) and 0.1M NaOH (NaOH II P). The Winchmore trial comprised 5 treatments: control (no P since 1952), 376R (376 kg superphosphate ha⁻¹ yr⁻¹ 1952-1957, none since), 564R (564 kg superphosphate ha⁻¹ yr⁻¹ 1952-1957, none since) 188PA (188 kg superphosphate ha⁻¹ yr⁻¹ since 1952) and 376PA (376 kg superphosphate ha⁻¹ yr⁻¹ since 1952: Topsoil (0-7.5cm) samples taken from the different treatments in 1958, 1961, 1965, 1968, 1971, 1974 and 1977 were used in this study. Changes in soil P with time showed that significant increases in soil inorganic P occurred in the annually fertilised treatments (l88PA, 376PA). As expected, the overall increase in total soil inorganic P between 1958 and 1977 was greater in the 376PA treatment (159 µg P g⁻¹) than that in the 188PA treatment (37 µg P g⁻¹). However, the chemical forms of inorganic P which accumulated in the annually fertilised treatments changed with time. Between 1958 and 1971 most of the increases in soil inorganic P in these treatments occurred in the NaHCO₃ and NaOH I P fractions. On the other hand, increases in soil inorganic P in the annually fertilised treatments between 1971 and 1977 were found mainly in the HCl and NaOH II P fractions. These changes in soil P forms were attributed to the combined effects of lime addition in 1972 and increased amounts of sparingly soluble apatite P and iron-aluminium P in the single superphosphate applied during the 1970's. In the residual fertiliser treatments (376R, 564R) significant decreases in all of the soil inorganic P fractions (i.e. NaHCO₃ P, NaOH I P, HCl P, NaOH II p) occurred between 1958 and 1977 following the cessation of P fertiliser inputs in 1957. This was attributed to continued plant uptake of P accumulated in the soil from earlier P fertiliser additions. However, levels of inorganic P in the different soil P fractions in the residual fertiliser treatments did not decline to those in the control which indicated that some of the inorganic P accumulated in the soil from P fertiliser applied between 1952 and 1957 was present in very stable forms. In all treatments, significant increases in soil organic P occurred between 1958 and 1971. The overall increases in total soil organic P were greater in the annually fertilised treatments (70-86 µg P g⁻¹) than those in the residual fertiliser (55-64 µg P g⁻¹) and control (34 µg P g⁻¹) treatments which reflected the respective levels of pasture production in the different treatments. These increases in soil organic P were attributed to the biological conversion of native and fertiliser inorganic P to organic P in the soil via plant, animal and microbial residues. The results also showed that annual rates of soil organic P accumulation between 1958 and 1971 decreased with time which indicated that steady-state conditions with regard to net 'organic P accumulation were being reached. In the residual fertiliser treatments, soil organic P continued to increase between 1958 and 1971 while levels of soil inorganic P and pasture production declined. This indicated that organic P which accumulated in soil from P fertiliser additions was more stable and less available to plants than inorganic forms of soil P. Between 1971 and 1974 small (10-38 µg P g⁻¹) but significant decreases in total soil organic P occurred in all treatments. This was attributed to increased mineralisation of soil organic P as a result of lime (4 t ha⁻¹) applied to the trial in 1972 and also to the observed cessation of further net soil organic P accumulation after 1971. Liming also appeared to affect the chemical nature of soil organic P as shown by the large decreases in NaOH I organic P(78-88 µg P g⁻¹) and concomitant smaller increases in NaOH II organic P (53-65 µg P g⁻¹) which occurred in all treatments between 1971 and 1974. The chemical nature of soil organic P in the Winchmore long-term trial was also investigated using 31p nuclear magnetic resonance (NMR) spectroscopy and gel filtration chromatography. This involved quantitative extraction of organic P from the soil by sequential extraction with 0.1M NaOH, 0.2M aqueous acetylacetone (pH 8.3) and 0.5M NaOH following which the extracts were concentrated by ultrafiltration. Soils (0-7.5cm) taken from the control and 376PA annually fertilised treatments in 1958, 1971 and 1983 were used in this study. 31p NMR analysis showed that most (88-94%) of the organic P in the Winchmore soils was present as orthophosphate monoester P while the remainder was found as orthophosphate diester and pyrophosphate P. Orthophosphate monoester P also made up almost all of the soil organic P which accumulated in the 376PA treatment between 1958 and 1971. This indicated that soil organic P in the 376PA and control treatments was very stable. The gel filtration studies using Sephadex G-100 showed that most (61-83%) of the soil organic P in the control and 376PA treatments was present in the low molecular weight forms (<100,000 MW), although the proportion of soil organic P in high molecular weight forms (>100,000 MW) increased from 17-19% in 1958 to 38-39% in 1983. The latter was attributed to the microbial humification of organic P and indicated a shift toward more complex and possibly more stable forms of organic P in the soil with time. Assuming that the difference in soil organic P between the control and 376PA soils sampled in 1971 and 1983 represented the organic P derived from P fertiliser additions, results showed that this soil organic P was evenly distributed between the high and low molecular weight fractions. An exhaustive pot trial was used to examine the relative availability to plants of different forms of soil inorganic and organic P in long-term fertilised pasture soils. This involved growing 3 successive crops of perennial ryegrass (Lolium perenne) in 3 Lismore silt loam (Udic Ustochrept) soils which had received different amounts of P fertiliser for many years. Two of the soils were taken from the annually fertilised treatments in the Winchmore long term trial (188PA, 376PA) and the third (Fairton) was taken from a pasture which had been irrigated with meatworks effluent for over 80 years (65 kg P ha⁻¹ yr⁻¹). Each soil was subjected to 3 treatments, namely control (no nutrients added), N100 and N200. The latter treatments involved adding complete nutrient solutions with different quantities of N at rates of 100kg N ha⁻¹ (N100) and 200kg N ha⁻¹ (N200) on an area basis. The soil P fractionation scheme used was the same as that used in the Winchmore long-term trial study (i.e. NaHCO₃ P, NaOH I P, HCl P, NaOH II p). Results obtained showed that the availability to plants of different extracted inorganic P fractions, as measured by decreases in P fractions before and after 3 successive crops, followed the order: NaHCO₃ P > NaOH I P > HCl P = NaOH II P. Overall decreases in the NaHCO₃ and NaOH I inorganic P fractions were 34% and 16% respectively, while corresponding decreases in the HCl and NaOH II inorganic P fractions were small «10%) and not significant. However, a significant decrease in HCl P (16%) was observed in one soil (Fairton-N200 treatment) which was attributed to the significant decrease in soil pH (from 6.2 to 5.1) which occurred after successive cropping. Successive cropping had little or no effect on the levels of P in the different soil organic P fractions. This indicated that net soil organic P mineralisation did not contribute significantly to plant P uptake over the short-term. A short-term field experiment was also conducted to examine the effects of different soil management practices on the availability of different forms of P to plants in the long-term fertilised pasture soils. The trial was sited on selected plots of the existing annually fertilised treatments in the Winchmore long-term trial (188PA, 376PA) and comprised 5 treatments: control, 2 rates of lime (2 and 4 t ha⁻¹ ) , urea fertiliser (400kg N ha⁻¹ ) and mechanical cultivation. The above ground herbage in the uncultivated treatments was harvested on 11 occasions over a 2 year period and at each harvest topsoil (0-7.5 cm) samples were taken from all of the treatments for P analysis. The soil P fractionation scheme used in this particular trial involved sequential extractions with 0.5M NaHCO₃ @ pH 8.5 (NaHCO₃ P), 0.1M NaOH (NaOH P), ultrasonification with 0.1M NaOH (sonicate-NaOH p) and 1M HCl (HCl P). In addition, amounts of microbial P in the soils were determined. The results showed that liming resulted in small (10-21 µg P g⁻¹) though significant decreases in the NaOH soil organic P fraction in the 188PA and 376PA plots. Levels of soil microbial P were also found to be greater in the limed treatments compared with those in the controls. These results indicated that liming increased the microbial mineralisation of soil organic P in the Winchmore soils. However, pasture dry matter yields and P uptake were not significantly affected. Although urea significantly increased dry matter yields and P uptake, it did not appear to significantly affect amounts of P in the different soil P fractions. Mechanical cultivation and the subsequent fallow period (18 months) resulted in significant increases in amounts of P in the NaHCO₃ and NaOH inorganic P fractions. This was attributed to P released from the microbial decomposition of plant residues, although the absence of plants significantly reduced levels of microbial P in the cultivated soils. Practical implications of the results obtained in the present study were presented and discussed.

Τα πεπτίδια, είτε ως πρωτεϊνικά θραύσματα είτε ως φυσικές οντότητες, χαρακτηρίζονται από την ακολουθία τους και από τα λειτουργικά τους χαρακτηριστικά. Ο σκοπός αυτής της Διδακτορικής Διατριβής είναι η ανάπτυξη μιας μεθοδολογίας εξόρυξης δεδομένων για μοναδικά tags και πεπτιδικά/πρωτεϊνικά χαρακτηριστικά του ανθρώπινου πρωτεώματος καθώς επίσης η ανάλυση και η εφαρμογή αυτών των βιολογικών δεδομένων σε πρωτεϊνες που σχετίζονται με τον καρκίνο. Δημιουργήθηκε μια αποθήκη αρχείων η οποία περιέχει μοριακά βάρη με ακρίβεια 0.01 Da που συνδέονται με τις αντίστοιχες πεπτιδικές ακολουθίες ανθρώπινων πρωτεϊνών της Swiss-Prot βάσης. Αυτές οι πρωτεϊνες διασπάστηκαν εξαντλητικά παρέχοντας ανεξαρτησία στις πεπτιδικές ακολουθίες από άλλες μεθόδους που βασίζονται στην ενζυματική διάσπαση. Από αυτήν την αποθήκη δεδομένων, διαχωρίστηκαν τα μοριακά βάρη που είναι μοναδικά και φτάνουν μέχρι τα 10 kDa καθώς και οι μοναδικές πεπτιδικές ακολουθίες (μέχρι 10 kDa). Στα πλαίσια της αξιοποίησης των δεδομένων εξόρυξης για την ταυτοποίηση των πρωτεϊνών, αναπτύχθηκε μια ευρέως διαθέσιμη διαδικτυακή εφαρμογή όπου γίνεται η αντιστοίχιση των μοριακών βαρών υψηλής ανάλυσης με πεπτίδια και πρωτεϊνες. Μια ακόμη διαδικτυακή εφαρμογή αναπτύχθηκε για να προσφέρει την πληροφορία της μοναδικότητας των μοριακών βαρών και των πεπτιδικών ακολουθιών στο ανθρώπινο πρωτέωμα. Η εφαρμογή μπορεί να αναζητήσει μοναδικά πρωτεϊνικά θραύσματα που προκύπτουν από την εζυματική διάσπαση πρωτεϊνών και να προσφέρει την πληροφορία για όλα τα μοναδικά μοριακά βάρη και τις μοναδικές πεπτιδικές ακολουθίες που περιέχονται σε μια πρωτεϊνη. Πολλές φορές χρειάζεται η μαζική διαχείριση των πεπτιδίων από λίστες. Για το σκοπό αυτό, αναπτύχθηκε ένας web server ο οποίος διαχειρίζεται τις πεπτιδικές λίστες, αναλύοντας τα χαρακτηριστικά των πεπτιδίων και ομαδοποιώντας τα πεπτίδια σύμφωνα μα αυτά τα χαρακτηριστικά, ενώ οπτικοποιείται η ομαδοποίηση με την χρήση ενός java applet. Το PepServe είναι ένα χρήσιμο εργαλείο για την κατανόηση της κατανομής των πεπτιδικών χαρακτηριστικών για ένα σύνολο πεπτιδίων. Τέλος, αναλύθηκαν σύνολα πρωτεϊνών που σχετίζονται με διάφορες περιπτώσεις καρκίνων, για πεπτιδικά χαρακτηριστικά. Αυτή η ανάλυση έχει σκοπό την εύρεση πιθανών προτιμήσεων σε χαρακτηριστικά και την εύρεση μοναδικών tags των πρωτεϊνών που σχετίζονται με καρκίνους. Τα μοναδικά tags μπορούν να χρησιμοποιηθούν στην ανακάλυψη βιοδεικτών και την ανάπτυξη νεων φαρμάκων για την πιο αποτελεσματική διάγνωση και θεραπεία. / Peptides, either as protein fragments or as naturally occurring entities are characterized by their sequence and function features. The purpose of the present Ph.D. thesis is to develop a datamining method for unique tags and peptide/protein characteristics in the human proteome and to analyze and apply the derived biological data in cancer-related proteins. A file repository has been created, containing indexed information that relates molecular masses with an accuracy of 0.01 Da to the corresponding peptides existing in human proteins. These proteins have been deposited in a completely digested protein database (Swiss-Prot) providing independence from any specific enzyme/digestion method. From this repository, the unique molecular masses, ranging from 1 to 10 kDa, and the unique peptide sequences from all the possible sequence fragments (up to 10 kDa) have been mined. A publicly available web application has been developed which facilitates a high resolution mapping of measured molecular masses to peptides and proteins, irrespectively of the enzyme/digestion method used. Μulti-filtering may be applied in terms of measured mass tolerance, molecular mass and isoelectric point range as well as pattern matching to refine the results In addition, another publicly available web application has been developed that offers information concerning the uniqueness of molecular masses and peptide sequences in the human proteome. The application is able to search for unique protein fragments derived computationally from enzymatic digestion driven by certain enzymes. Furthermore, the application can list all the unique masses and peptides of a given protein. Through this application, researchers are able to find unique tags, either on a molecular mass level or on a sequence level. A web server has beed developed that manages peptide lists in terms of feature analysis as well as interactive clustering and visualization of the given peptides. PepServe is a useful tool towards understanding peptide feature distribution among a group of peptides. Finally, cancer-related proteins have been analyzed producing peptide features and peptide feature’s sequence uniqueness resulting in some feature preferences and peptide unique tags. These unique tags can be used in biomarker discovery, and novel drug development for an efficient diagnosis and treatment.

This study investigated characteristics of algal organic matter (AOM) derived from four species (cyanobacteria Microcystis aeruginosa and Merismopedia tenuissima, diatom Fragilaria crotonensis and green alga Chlamydomonas geitleri) dominating phytoplanktonic populations in the reservoirs supplying drinking water treatment plants - the water reservoirs Švihov (the Želivka water treatment plant) and Josefův Důl (the Jizerské Mountains), Czech Republic. The four mentioned microorganisms were cultivated under laboratory conditions and the algal growth was quantified by a number of cells, chrorophyll-a and optical density. Production of AOM was evaluated by dissolved organic carbon concentration measurements, by specific UV absorbance, the amount of peptide/protein and non-peptide (carbohydrate) contents, water affinity and molecular weight (MW). AOM of all considered microorganisms are formed predominantly by hydrophilic substances with low values of specific UV absorbance (< 2 L/(m.mg)). Considerable portions of both types of AOM, i.e. extracellular and cellular organic matters are represented by substances with MW < 1 kDa or with MW > 100 kDa. However, the total amount and composition of AOM significantly depend on algal species and their growth. The obtained results imply that the knowledge of AOM...

Depuis 1973, l’un des objectifs principaux de la France est la diminution de la consommation des énergies de chauffage des bâtiments du résidentiel et du tertiaire qui représentent plus de 40% de la consommation énergétique totale du pays. Le développement des isolants thermiques a été par conséquent un sujet de recherche qui a abouti à de nouveaux matériaux : les super-isolants thermiques de conductivité thermique inférieure à 25 mW.m-1.K-1. Les aérogels organiques de faible densité de Z-Phe-NH-Napht étudiés au LCPM présentent une structure fibrillaire qui leur confère des propriétés thermiques intéressantes malgré une résistance mécanique faible. Une étude fondamentale de l’organisation supramoléculaire nous a permis d’une part de démontrer l’existence de deux modes d’empilement des molécules organogélatrices : tête-à-tête (monocristaux) et tête-à-queue (gels), caractérisées par une signature infrarouge propre à des pseudo-cycles respectivement en C12 et C10/C14. D’autre part, nous avons étudié le mécanisme de formation séquentiel de ces gels et abouti à un modèle complet d’organisation de la molécule isolée à la fibre basé sur une symétrie hexagonale. En vue d’une commercialisation d’un isolant à base d’aérogel organique, nous avons tout d’abord optimisé le protocole d’obtention des aérogels pour ensuite travailler à l’amélioration des propriétés thermiques et mécaniques. Nous sommes parvenus à un nouvel isolant hydrophobe présentant une conductivité thermique de l’ordre de celles des super-isolants et de bonnes propriétés mécaniques compatibles avec les pré-requis industriels pour une application dans le bâtiment / Since 1973, France's main objective in this domain has been to reduce the consumption of energy in heating residential and industrial buildings, which represents more than 40% of the national consumption. Consequently, the development of heat insulators has been the subject of research which has resulted in new materials: super thermal insulators with a thermal conductivity of less than 25 mW.m-1.K-1. Organic aerogels with a low density of Z-Phe-NH-Napht have been studied at LCPM for the past 10 years. Despite their very weak mechanical resistance they present a fibrillar structure which gives them very interesting thermal properties. A fundamental study of the supermolecular self-assembly allowed us to demonstrate the existence of two stacking methods of gelling molecules: head-to-head (monocrystals) and head-to-tail (gels) which are characterized by a specific infrared signature to the pseudo-cycles respectively on C12 and C10/C14. In addition, we also studied the sequential formation mechanism of these gels which resulted in a full model of their molecular organization from the single molecule to the fiber and based on a hexagonal packing symmetry. In aim of commercializing an insulator made from organic aerogels, we firstly optimized the protocol for obtaining aerogels to then work on improving their thermal and mechanical properties. We created a new hydrophobic insulator which has both a thermal conductivity in the range of the super heat insulators' and good mechanical properties that are compatible with industrial prerequisites for the construction of buildings

Here, we report on a new temperature responsive polymer brush system with a terminal “click” functionality. Bifunctionalized poly(N-isopropylacrylamide) (PNiPAAm) with distinct functional end groups was synthesized by atom transfer radical polymerization (ATRP) and grafted to a modified silicon substrate. The presence of the active terminal alkyne functionality is validated using an azide-modified rhodamine B (N3-RhB) via copper(I) catalyzed alkyne–azide cycloaddition (CuAAC). The optical properties and swelling dynamics of an N3-RhB modified PNiPAAm brush are analyzed in dry state and in situ by VIS-spectroscopic ellipsometry (SE). The best-fit results are obtained using a Gaussian oscillator model and are confirmed by UV/VIS-spectroscopy. We observed evidence of interactions between the aromatic residues of the dye and the PNiPAAm amide groups, which significantly affect the swelling behavior of the modified polymer brush. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.