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In this work, we propose to follow the crystallization capability of oils in oil-based paints, during curing, as an indirect index of the matrix status in the early stages of paint film formation that usually are indicative and crucial to understand the process evolution. To proof the concept, the oil crystallization properties were investigated through DSC measurements on samples of both unpigmented linseed oil and two model paints, composed by lead white + linseed oil (LWLO) and ultramarine blue + linseed oil (UBLO), at different ageing time at room and oxygen-limiting conditions. The results indicate that the curing process strongly affects the oil’s ability of forming crystals in the paint layers, and the proposed experimental approach is rather suitable and sensitive enough to discriminate differences between the action of pigments and environmental conditions. On the other hand, despite the simplicity and the potentiality, this approach is limited at the early stages of paint curing offering an index of the overall matrix status and therefore must be intended as a complementary method that has to be integrated with other approaches if the aim is to explore in detail the chemical and physical aspects of the curing process.

Food contamination with pathogenic microorganisms, such as Listeria monocytogenes, Salmonella enterica, Staphylococcus aureus and Bacillus cereus, is a common health concern. Natural products, which have been the main source of antimicrobials for centuries, may represent a turning point in alleviating the antibiotic crisis, and plant polyphenolic compounds are considered a promising source for new antibacterial agents. Resveratrol and resveratrol-derived monomers and oligomers (stilbenoids) have been shown to exert a variegated pattern of efficacy as antimicrobials depending on both the polyphenols’ structure and the nature of the microorganisms, and the bacterial cell membrane seems to be one of their primary targets.In this scenario and based on the thermodynamic information reported in the literature about cell membranes, this study aimed at the investigation of the direct interaction of selected stilbenoids with a simple but informative model cell membrane. Three complete stilbenoid “monomer/dimer/dehydro-dimer” sets were chosen according to different geometries and substitution patterns. Micro-DSC was performed on 2 : 3 DPPC : DSPC small unilamellar vesicles with incorporated polyphenols at physiological pH and the results were integrated using complementary NMR data. The study highlighted the molecular determinants and mechanisms involved in the stilbenoid–membrane interaction, and the results were well correlated with the microbiological evidence previously assessed.

A stepwise micro-DSC study of Small, Large and Giant Unilamellar Vesicles prepared as pure and mixed systems of DMPC, DPPC, DSPC and DOPC was performed, achieving the preparation of final model membranes whose phospholipid compositions represent the 75% in terms of the phospholipids tails and the 50% headgroups of the Insulin Secretory Granules (vesicles located in the pancreatic Langerhans β-cells and which are responsible for insulin and amylin storage and secretion in response to nutrient intake). Moreover, the effect of Free Fatty Acids, whose levels are recurrently altered in diabetic and/or obese subjects, on the thermodynamic stability of the final membranes was eventually investigated. The results allowed to discriminate each single thermodynamic contribution among the main factors that dictate the overall thermodynamic stability of these complex unilamellar systems evidencing mainly entropic effects hierarchically summarized as phospholipid unsaturations > phospholipid tail length > membrane curvature. The effect of the Free Fatty Acids highlighted a strong stabilizing effect on the membranes as well as more pronounced phase segregations in the case of saturated acids (palmitic and stearic), whereas the opposite effect was observed in the case of an unsaturated one (oleic).

To reap its full benefits, 5G must evolve into a scalable decentralized architecture by exploiting intelligence ubiquitously and securely across different technologies, network layers, and segments. In this article, we propose end-to-end and ubiquitous secure machine learning (ML)-powered intent-based networking (IBN). The IBN framework is aware of its state and context to autonomously take proactive actions for service assurance. It is integrated in a zero-touch control and orchestration framework featuring an ML function orchestrator to manage ML pipelines. The objective is to create an elastic and dynamic infrastructure supporting per-domain and end-to-end network and services operation. The solution is supported by a radio access network and forwarding plane, and a cloud/edge virtualization infrastructure with ML acceleration. The resulting framework supports application-level resilience and intelligence through replication and elasticity. An illustrative intelligent application use case is presented. This work was partially supported by the AEI IBON (PID2020-114135RB-I00) project and by the ICREA Institution.

Protocols and guidelines were assessed in order to apply isothermal calorimetry as a complementary/alternative method to monitoring, during the shelf life and the microbial growth/metabolism in commercial fresh cut vegetables with random initial microbial population. Moreover, the endogenous microbial population was used as a biosensor to check the modifications occurred during long storage for aftermarket characterization in the frame of vegetable waste treatments. Validation was obtained following ready-to-use carrots highlighting the effects of the different exposed surfaces (cylinders, sticks and a-la-julienne cut) on the overall spoiling process during shelf life and green salad stored up to 14 days with regard to the aftermarket characterization.

The aim of this study was the shelf life extension of whole-wheat breadsticks through the addition of a rosemary extract and packaging under nitrogen. Shelf life was studied at four temperatures (20, 27, 35, 48 °C) for up to 200 storage days. The minimal changes observed in moisture, water activity and texture of the samples, coupled with the high peroxide values (13–539 meqO2/kgfat) measured at the end of storage, and the exponential increase of hexanal concentrations (up to 13–34 mg/kg) confirmed that quality decay of whole-wheat breadsticks is mainly associated to lipid oxidation. The kinetic study of oxidation development and the consumer sensory acceptance determined by the survival analysis demonstrated that the rosemary extract addition yields a 42% shelf life extension, higher than that observed using nitrogen in the package (24–29%). The combination of the formulation and packaging strategies gave the best result (83% shelf life extension at 25 °C).

The role of water and hematite (Fe2O3) on the stability of ovalbumin-based model paint layers was investigated by means of DSC and FTIR. The aim of this research is to improve our understanding on the stability of paint layers based on proteinaceous media, assessing the water content and the pigment presence effects. Pigments may play a fundamental role in determining the structure of proteins in paint layers, thus affecting the possible interactions among proteins and the external environment, including humidity. Previous studies revealed that hematite affects the secondary structure of OVA in paint layers, although no experimental evidence of hematite/OVA covalent bonds has been reported in the literature. In this paper we investigate the synergic effect of water and hematite on OVA structure and stability. DSC analyses coupled with FTIR measures on protein hydration revealed that below 30 % of humidity the amount of water strongly influence the protein structure and stability: the less the water content, the higher the protein stability. Furthermore, our results suggest that a water phase separation occurs in the presence of hematite for which, in water-limiting condition, the hematite’s hydration shell becomes almost negligible if compared to the bulk water available for the protein hydration because of the high protein-water affinity. Accordingly, the protein phase humidity is higher than the sample’s nominal value. Paints at the same overall humidity exhibit different protein hydration state following the pigment/binder ratio, and in turn different resistance to damages throughout aging.

The influence of free fatty acids (FFAs) on the nisin–membrane interaction was investigated through micro-DSC and fluorescence spectroscopy. A simple but informative model membrane was prepared (5.7 DMPC:3.8 DPPS:0.5 DOPC molar ratio) by considering the presence of different phospholipid headgroups in charge and size and different phospholipid tails in length and unsaturation level, allowing the discrimination of the combined interaction of nisin and FFAs with the single phospholipid constituents. The effects of six FFAs on membrane stability were evaluated, namely two saturated FFAs (palmitic acid and stearic acid), two monounsaturated FFAs (cis-unsaturated oleic acid and trans-unsaturated elaidic acid) and two cis-polyunsaturated FFAs (ω-6 linoleic acid and ω-3 docosahexaenoic acid). The results permitted assessment of a thermodynamic picture of such interactions which indicates that the peptide–membrane interaction does not overlook the presence of FFAs within the lipid bilayer since both FFAs and nisin are able to selectively promote thermodynamic phase separations as well as a general lipid reorganization within the host membrane. Furthermore, the magnitude of the effects may be different depending on the FFA chemical structure as well as the membrane lipid composition.

A fifteen-components model membrane that reflected the 80 % of phospholipids present in Insulin Secretory Granules was obtained and thermodynamic exploitation was performed, through micro-DSC, in order to assess the synergic contributions to the stability of a mixed complex system very close to real membranes. Simpler systems were also stepwise investigated, to complete a previous preliminary study and to highlight a hierarchy of interactions that can be now summarized as phospholipid tail unsaturation > phospholipid tail length > phospholipid headgroup > membrane curvature. In particular, Small Unilamellar Vesicles (SUVs) that consisted in phospholipids with different headgroups (choline, ethanolamine and serine), was step by step considered, following inclusion of sphingomyelins and lysophosphatidylcholines together with a more complete fatty acids distribution characterizing the phospholipid bilayer of the Insulin Secretory Granules. The inclusion of cholesterol was finally considered and the influence of three FFAs (stearic, oleic and elaidic acids) was investigated in comparison with simpler systems, highlighting the magnitude of the effects on such a detailed membrane in the frame of Type 2 Diabetes Mellitus alterations.

This work presents methodologies and techniques for the design of wearable sensor systems to be used for the measurement of physiological and environmental parameters. Such devices are becoming widespread in healthcare, sport and fitness, and are taking part to the Internet-of-Things revolution. The paper aims to describe some of the challenges faced at the design stage and possible solutions to be adopted.

The presented study addressed assays of odorant retention from an essential oil mixture by native corn, sorghum and amaranth starches using capillary gas chromatography (GC) and differential scanning calorimetry (DSC). The essential oil mixture consisted of 30 main compounds, including monoterpene and sesquiterpene hydrocarbons, alcohols, ketone, phenols and ester. The native starches were characterized for their chemical composition (amylose, protein, and surface lipids content), surface properties (surface area, pore diameter), and microstructure (SEM). The starches were mixed with odorants, stirred intensively, and stored at room temperature in the dark for 2 days (reference sample), 3 and 7 months. The chemical properties of odorants, their composition in the mixture as well as starch surface properties were observed to affect the retention of aroma compounds upon storage. Irrespective of starch botanical origin, a significant loss was noticed in monoterpene hydrocarbons throughout the storage period. Alcohols, ketone, phenols and sesquiterpene hydrocarbons were highly retained on amaranth and sorghum starches upon 3 months of storage. However, after prolonged storage their retention diminished, especially in the case of amaranth starch. The DSC results obtained for stored corn and sorghum starches with odorants demonstrated an extra endothermic contribution, which indicated that the aroma compounds were highly retained by the gelatinized starch matrixes. Furthermore, the odorants showed ability to interact with the solubilized amylose.

The use of isothermal TGA with Knudsen-like cells allows determination of the thermodynamic activity of water, a W . The typical experiment implies a slow dehydration of the aqueous solution at constant temperature in dynamic vacuum conditions. The method is alternative to the classical isopiestic approach and offers the advantage of a continuous record on increasing the solute concentration. These data can be directly treated according to the classical thermodynamic relationships drawn from the Gibbs–Duhem expression to evaluate the activity and osmotic coefficient of the aqueous solutions of electrolytes and non-electrolytes, and, in the case of electrolytes, allow determination of solubility of the solute. Discrepancies with respect to the literature data are observed when the viscosity of the systems becomes too high, as in the case of sugars with a very large solubility. Such a mismatch may however be accounted for either slowing the dehydration rate with use of a narrower Knudsen orifice, or correcting the experimental a W with a calibration curve. The same approach can be applied to non-aqueous solutions.

The release of the anticancer drug doxorubicin (DOX) incorporated in a new drug carrier, namely a chimeric nanosystem formed by liposomes and dendrimers, was studied following the influence of the drug on the growth kinetics of the Lactobacillus helveticus bacterium, that would mimic the intestinal microflora. The bacterial growth was followed at 37°C by means of Isothermal Titration Calorimetry (ITC) and the method was assessed to monitor the overall effect of the delivered drug obtaining simple objective parameters to define the encapsulation effectiveness of the system, discriminating dose effects even in cases of very low release. Traditional microbiological investigations and in vitro release tests were also performed in parallel for validation. The achieved results suggest that L. helveticus is an excellent candidate as biosensor to assess the sealing effectiveness of these DOX drug carriers through ITC investigations. This approach can be extended for quantitative comparison of drug delivery systems with the same drug inserted in other supramolecular bodies for quantitative comparison. The peculiar results for the DOX drug carrier system investigated, indicate also that, the use of hydrophilic dendrimers in this case, produce a high sealing effect that seems promising in terms of the intestinal flora protection.

Water deserves a major attention by researchers dealing with biological systems and related materials, like food, since it is ubiquitous and can be used like a "native" probe to garner information about the hosting system, provided it may be freely displaced across. Its thermodynamic potential, namely, the water activity, aW, is related to that of the other compounds of the system considered via the Gibbs-Duhem relationship reflecting the extent of the residual availability of water to solvate further solutes and sustain the molecular mobility of the bio-polymeric compounds. As for the experimental approaches to aw, this short review re-addresses the reader to other publications, while devotes a section to the Knudsen thermo-gravimetry that was used by the authors to determine the desorption isotherms of many food systems and related aqueous compounds. The paper remarks the importance of a preliminary assessment of water mobility and recalls the concept of "critical aw" that takes into account the reduced mobility of water molecules in the vicinity of the glass transition. This opens the question of the reliability of sorption isotherms which encompass a wide aw range and the interpretation of the observed adsorption/desorption hysteresis. The multi-phase character of many biological systems is another issue of interest related to the reliability of the experimental approaches to aw. As examples of the role of aw on the stability of bio-systems and on the practice of a technological treatment, protein unfolding and osmo-dehydration of fruit pulps are reported.

Chimeric advanced Drug Delivery nano Systems (chi-aDDnSs) could be defined as mixed nanosystems due to the combination process of nanobiomaterials and can offer advantages as drug carriers. The role of the release modulator from the liposomal system is undertaken by the dendrimer molecules leading to new pharmacokinetic and, probably, pharmacological properties of the chimeric system. In this work, a conventional DOPC/DPPG liposomal system and a new chi-aDDnS composed of liposomes (DOPC/DPPG) incorporating PAMAM G3,5 has been developed, Doxorubicin (Dox) was loaded in the systems and the final formulations were lyophilized. The physicochemical (spectroscopic and calorimetric) investigation concerning the chi-aDDnS, revealed a strong interaction between both lipophilic and hydrophilic parts of the liposomal membrane and the dendrimer, with the induction of multiple energetic states. These states are probably the basis of higher Dox encapsulation and slower release rate compared to the respective conventional liposome. These results, in conjunction with the increase in TI observed in two investigated cancer cell lines (i.e., MB231 and MCF7), compared to the respective conventional liposomal system and to the free Dox, make this new chi-aDDnS the basic candidate for further in vivo investigations.

Liposomal locked-in dendrimers (LLDs), the combination of liposomes and dendrimers in one formulation, represents a relatively new term in the drug carrier technology. LLDs undergone appropriate physicochemical investigation can merge the benefits of liposomal and dendrimeric nanocarriers. In this study generation 1 and 2 hydroxy-terminated dendrimers were synthesized and were then "locked" in liposomes consisting of DOPC/DPPG. The anticancer drug doxorubicin (Dox) was loaded into pure liposomes or LLDs and the final products were subjected to lyophilization. The loading of Dox as well as its in vitro release rate from all systems was determined and the interaction of liposomes with dendrimers was assessed by thermal analysis and fluorescence spectroscopy. The results were very promising in terms of drug encapsulation and release rate, factors that can alter the therapeutic profile of a drug with low therapeutic index such as Dox. Physicochemical methods revealed a strong, generation dependent, interaction between liposomes and dendrimers that probably is the basis for the higher loading and slower drug release from the LLDs comparing to pure liposomes.

A thermodynamic approach is proposed to describe the osmo-dehydration treatment of apple pulp. The experimental evidence comes from isothermal desorption trends directly drawn from traces of Knudsen thermogravimetry and is strictly related to the water activity, a W, that is continuously recorded during the dehydration progress, thanks to the specific equipment used. The trends recorded concern three kinds of samples, namely, the nontreated and the partially osmo-dehydrated apple pulp and the sugar syrup used for the treatment, the investigations being applied to three different sugar syrups. It was recognized that these desorption trends actually reflect real equilibrium states of the systems considered at every dehydration level. Since the apple pulp may practically be referred to as a two aqueous phase system, namely, intra- and extracellular, the equilibrium condition imposes a W to be the same in either phase. This basic statement supports the view that the desorption trend of the nontreated apple pulp and that of the sugar syrup are actually related to the intra- and extracellular aqueous phases, respectively. The desorption trend of any partially osmo-dehydrated apple pulp remains between them and reflects the bi-phasic nature of the system. The approach also allows a quantitative description of properties and phenomena related to the dehydration, namely, extent of the cell shrinkage, proportion between intra- and extracellular mass, water diffusion coefficient through the cell membrane, expected sensorial differences related to the kind of dehydration process, and heat drying or osmo-dehydration performed with different sugar syrups.

Desorption isotherms for water, ethanol, ethyl acetate and toluene from a sodium smectite clay have been determined by both dynamic vapor sorption (DVS) measurements and Knudsen thermogravimetry (KTGA), at the exception of toluene that was measured only by the DVS method. The results obtained using these two methods were in satisfactory agreement, providing reliable insight into the desorption process, with certain lack of precision for ethyl acetate. The observed desorption behaviour suggests a liquid like phase at high volatile load, and a sorbed state in which molecules interact with the counter ions, at low volatile contents. However, the isotherms for water determined at various temperatures nearly superposed when plotted as a function of water activity, indicating the strength of the interactions in the clay–water system to remain of the same order of magnitude as that in bulk water, consistent with previous ab initio calculations.

Thermal analysis was used to check the role of the main components of buckwheat flour (polysaccharides and proteins) to assess guidelines for novel recipes for bread from wheat and buckwheat flour blends with improved nutritional properties. The structure-related poor protein quality, namely, the lack of network-forming links, severely limits the use of buckwheat flours in bread-making. Data from TG and DSC analysis indicate that the introduction of a de-hulling step in the buckwheat milling diagram and the addition of some buckwheat polysaccharide fractions, isolated from the buckwheat husk, that contribute to the formation of the crumb structure thanks to their effect on the phase separation driven by the thermodynamic incompatibility with wheat gluten proteins, allows one to tune opposite effects and obtain bread from de-hulled buckweat/wheat flour blends with alveolar distribution much close that of the wheat bread.

A suitable thermal treatment of gels of various starch varieties was assessed to achieve the formation of resistant starch (i.e. amylose crystals). On the basis of DSC data, the yield of amylose crystals and their thermal stability did not seem correlated with the amylose content of the starch. This last parameter may not therefore be referred to as the only factor that defines a resistant starch promising starch variety.

A number of new polyhydroxy-dendritic structures have been constructed from a few basic modules. The cores were derived from N-tert(butyloxycarbonyl)tris[(propargyloxy)methyl]aminomethane, N,N'-bis-1,3-(tris-(propargyloxymethyl)methyl)-5-(hydroxymethyl)isophthalamide, and N,N',N″-tris-1,3,5-(tris-(propargyloxymethyl)methyl)-1,3,5-benzene tricarboxamide while the terminal groups were derived from β-azido-galactose and β-azido-lactose leading to six new glycodendrimeric compounds with up to 63 hydroxyl groups on the periphery. The binding ability of the new compounds to peanut agglutinin (PNA), a galactose recognizing lectin from Arachis hypogaea, was investigated by nano-Isothermal Titration Calorimetry and nano-Differential Scanning Calorimetry. We found that the compounds had stronger stabilising effect on the macromolecules compared to the corresponding sugars. The interaction between lectin and the glycodendrimeric unit is entropically driven with only a low enthalpic contribution. A trend was found with increasing number of carbohydrates that is strongly influenced by the steric constraints of the ligands. Our results indicate the significance of multivalency and size control in the successful design of lectin inhibitors.

Ancient, new and artificially aged parchments were investigated with both differential scanning calorimetry (DSC) and thermogravimetry (TGA). Criteria to define a quantitative ranking of the damage experienced by the bulk collagen of historical parchments were assessed. A damage-related correlation was found between the collagen denaturation temperature and the moisture content of the parchment. Qualitative rules for the evaluation of the damage at the nano-and mesoscopic level were achieved on the basis of peculiarities of the shape and width of the DSC signals and confirmed by small angle X-ray scattering patterns.

Large experimental evidence was collected on polymorphous transitions of triacyl glycerols (TAG) in cocoa butter by means of DSC investigations. The cooling treatment (in conditions close to those of the industrial practice) and the annealing temperature significantly affect the overall crystal fraction and the distribution of the various polymorphs. These data allowed a quantitative, although purely phenomenological, kinetic parameterization of polymorphous transitions of cocoa butter. The evaluation of the relevant kinetic constants and their dependence on the temperature allowed prediction of the yield in every polymorph after a given thermal history. Similar evidences were attained for cocoa liquor and dark chocolate where TAG are sided by other ingredients. These results can be the basis for an industrial exploitation.

expression, gene regulation An understanding of the integrated relationships among the principal cellular functions that govern the bioenergetic reactions of an organism is necessary to determine how cells remain viable and optimise their fitness in the environment. Urease is a complex enzyme that catalyzes the hydrolysis of urea to ammonia and carbonic acid. While the induction of urease activity by several microorganisms has been predominantly considered a stress-response that is initiated to generate a nitrogen source in response to a low environmental pH, here we demonstrate a new role of urease in the optimisation of cellular bioenergetics. We show that urea hydrolysis increases the catabolic efficiency of Streptococcus thermophilus, a lactic acid bacterium that is widely used in the industrial manufacture of dairy products. By modulating the intracellular pH and thereby increasing the activity of β-galactosidase, glycolytic enzymes and lactate dehydrogenase, urease increases the overall change in enthalpy generated by the bioenergetic reactions. A cooperative altruistic behaviour of urease-positive microorganisms on the urease-negative microorganisms within the same environment was also observed. The physiological role of a single enzymatic activity demonstrates a novel and unexpected view of the non-transcriptional regulatory mechanisms that govern the bioenergetics of a bacterial cell, highlighting a new role for cytosol-alkalizing biochemical pathways in acidogenic microorganisms.

A new Liposomal-Locked in-Dendrimer (LLD) formed by DPPC-DPPG and PAMAM 3.5 incorporating the anticancer drug DOX was studied by means of spectroscopic and DSC investigations. Multilamellar Lipid Bilayers were also considered for the sake of comparison. The results were in line with a picture of phase separation between DPPC-DPPG lipids and dendrimer that promotes the stability of the liposome membrane and the cooperativity of the relevant gel-to-liquid-crystal transition, which is enhanced in the presence of the dendrimer and the drug. As a result, the inner core of the liposome contained large amounts of dendrimer-DOX complex and was protected by a very stable membrane. This view was given a more general validation through investigations performed with other types of dendrimers, namely PG1 and PG2. The thermodynamic interpretation of the DSC data allowed a better understanding of the physico-chemical factors that justify this behaviour that makes these LLDs very promising as a new class of Modulatory Liposomal Controlled Release System (MLCRS) that could lead to drug formulations with higher safety and efficacy profiles.

The ileal bile acid-binding proteins (I-BABPs), also called ileal lipid-binding proteins or gastrotropins, belong to the family of the fatty acid-binding proteins and play an important role in the solubilization and transport of bile acids in the enterocyte. This article describes the expression, purification, crystallization, and three-dimensional structure determination of zebrafish (Danio rerio) I-BABP both in its apo form and bound to cholic acid. This is the first X-ray structure of an I-BABP. The structure of the apoprotein was determined to a resolution of 1.6 A, and two different monoclinic crystal forms of the holoprotein were solved and refined to 2.2 A resolution. Three protein molecules are present in the asymmetric unit of one of the co-crystal forms and two in the other, and therefore, the results of this study refer to observations made on five different protein molecules in the crystalline state. In every case, two cholate ligands were found bound in approximately the same position in the internal cavity of the protein molecules, but an unexpected result is the presence of clear and unambiguous electron density for several cholate molecules bound on hydrophobic patches on the surface of all the five independent protein molecules examined. Isothermal titration calorimetry was used for the thermodynamic characterization of the binding mechanism and has yielded results that are consistent with the X-ray data. Ligand binding is described in detail, and the conformational changes undergone by the protein molecule in the apo-to-holo transition are examined by superposition of the apo- and holoprotein models. The structure of the holoprotein is also compared with that of the liver BABP from the same species and those of other I-BABPs determined by NMR.

The folding properties of a bile acid binding protein, belonging to a subfamily of the fatty acid binding proteins, have been here investigated both by hydrogen exchange measurements, using the SOFAST NMR approach, and urea denaturation experiments. The urea unfolding profiles of individual residues, acting as single probes, were simultaneously analyzed through a global fit, according to a two-state unfolding model. The resulting conformational stability DeltaG(U)(H(2)O)=7.2+/-0.25kcal mol(-1) is in good agreement with hydrogen exchange stability DeltaG(op). While the majority of protein residues satisfy this model, few amino-acids display a singular behavior, not directly amenable to the presence of a folding intermediate, as reported for other fatty acid binding proteins. These residues are part of a protein patch characterized by enhanced plasticity. To explain this singular behavior a tentative model has been proposed which takes into account the interplay between the dynamic features and the formation of transient aggregates. A functional role for this plasticity, related to translocation across the nuclear membrane, is discussed.

The influence of maltose-modified poly(propylene imine) (PPI) dendrimers on dimyristoylphosphatidylcholine (DMPC) or dimyristoylphosphatidylcholine/dimyristoylphosphatidylglycerol (DMPC/DMPG) (3%) liposomes was studied. Fourth generation (G4) PPI dendrimers with primary amino surface groups were partially (open shell glycodendrimers — OS) or completely (dense shell glycodendrimers — DS) modified with maltose residues. As a model membrane, two types of 100nm diameter liposomes were used to observe differences in the interactions between neutral DMPC and negatively charged DMPC/DMPG bilayers. Interactions were studied using fluorescence spectroscopy to evaluate the membrane fluidity of both the hydrophobic and hydrophilic parts of the lipid bilayer and using differential scanning calorimetry to investigate thermodynamic parameter changes. Pulsed-filed gradient NMR experiments were carried out to evaluate common diffusion coefficient of DMPG and DS PPI in D2O when using below critical micelle concentration of DMPG. Both OS and DS PPI G4 dendrimers show interactions with liposomes. Neutral DS dendrimers exhibit stronger changes in membrane fluidity compared to OS dendrimers. The bilayer structure seems more rigid in the case of anionic DMPC/DMPG liposomes in comparison to pure and neutral DMPC liposomes. Generally, interactions of dendrimers with anionic DMPC/DMPG and neutral DMPC liposomes were at the same level. Higher concentrations of positively charged OS dendrimers induced the aggregation process with negatively charged liposomes. For all types of experiments, the presence of NaCl decreased the strength of the interactions between glycodendrimers and liposomes. Based on NMR diffusion experiments we suggest that apart from electrostatic interactions for OS PPI hydrogen bonds play a major role in maltose-modified PPI dendrimer interactions with anionic and neutral model membranes where a contact surface is needed for undergoing multiple H-bond interactions between maltose shell of glycodendrimers and surface membrane of liposome.