Self-Diffusion and Collective Diffusion of Charged colloids Studied by Dynamic Light Scattering

A microemulsion of decane droplets stabilized by a non-ionic surfactant film is progressively charged by substitution of a non-ionic surfactant molecule by a cationic surfactant. We check that the microemulsion droplets remain identical within the explored range of volume fraction (0.02 to 0.18) and of the number of charge per droplets (0 to 40) . We probe the dynamics of these microemulsions by dynamic light scattering. Despite the similar structure of the uncharged and charged microemulsions the dynamics are very different . In the neutral microemulsion the fluctuations of polarization relax, as is well known, via the collective diffusion of the droplets. In the charged microemulsions, two modes of relaxation are observed. The fast one is ascribed classically to the collective diffusion of the charged droplets coupled to the diffusion of the counterions. The slow one has, to our knowledge, not been observed previously neither in similar microemulsions nor in charged spherical colloids. We show that the slow mode is also diffusive and suggest that its possible origine is the relaxation of local charge fluctuations via local exchange of droplets bearing different number of charges . The diffusion coefficient associated with this mode is then the self diffusion coefficient of the droplets

Hypercube orientations with only two in-degrees

We consider the problem of orienting the edges of the $n$-dimensional hypercube so only two different in-degrees $a$ and $b$ occur. We show that this can be done, for two specified in-degrees, if and only if an obvious necessary condition holds. Namely, there exist non-negative integers $s$ and $t$ so that $s+t=2^n$ and $as+bt=n2^{n-1}$. This is connected to a question arising from constructing a strategy for a "hat puzzle."Comment: 9 pages, 4 figure

Nanorods of Well-Defined Length and Monodisperse Cross-Section Obtained from Electrostatic Complexation of Nanoparticles with a Semiflexible Biopolymer

We show by combining small-angle X-ray scattering (SAXS) and cryo-transmission electron microscopy (cryo-TEM) that anionic silica nanoparticles (SiNPs) assemble into well-defined 1D cluster when mixed with a dilute solution of semiflexible chitosan polycation. The nanorods are stable in excess of SiNPs and composed of 10 SiNPs well-ordered into straight single strands with length Lrod \approx 184.0 nm and radius Rrod = 9.2 nm = RSiNPs. We point out that the ratio between the chitosan persistence length and the SiNP radius, which is here equal to 1, can be the determining condition to obtain such original objects

Rodlike Complexes of a Polyelectrolyte (Hyaluronan) and a Protein (Lysozyme) observed by SANS

We study by Small Angle Neutron Scattering (SANS) the structure of Hyaluronan -Lysozyme complexes. Hyaluronan (HA) is a polysaccharide of 9 nm intrinsic persistence length that bears one negative charge per disaccharide monomer (Mmol = 401.3 g/mol); two molecular weights, Mw = 6000 and 500 000 Da were used. The pH was adjusted at 4.7 and 7.4 so that lysozyme has a global charge of +10 and + 8 respectively. The lysozyme concentration was varied from 3 to 40 g/L, at constant HA concentration (10 g/L). At low protein concentration, samples are monophasic and SANS experiments reveal only fluctuations of concentration although, at high protein concentration, clusters are observed by SANS in the dense phase of the diphasic samples. In between, close to the onset of the phase separation, a distinct original scattering is observed. It is characteristic of a rod-like shape, which could characterize "single" complexes involving one or a few polymer chains. For the large molecular weight (500 000) the rodlike rigid domains extend to much larger length scale than the persistence length of the HA chain alone in solution and the range of the SANS investigation. They can be described as a necklace of proteins attached along a backbone of diameter one or a few HA chains. For the short chains (Mw ~ 6000), the rod length of the complexes is close to the chain contour length (~ 15 nm)

New Insight Into the Size Tuning of Monodispersed Colloidal Gold Obtained by Citrate Method

International audienceWe study the effect of citrate to gold molar ratio (X) on the size of citrated gold nanoparticles (AuNPs). This dependence is still a matter of debate for X ≥ 3 where the polydispersity is yet minimized. Indeed, there is no consensus between experiments proposed so far for comparable experimental conditions. Nonetheless, the sole available theoretical prediction has never been validated experimentally in this range of X. We show unambiguously using 3 techniques (UV-Vis spectroscopy, dynamic light scattering and transmission electronic microscopy), 2 different synthetic approaches (Direct, Inverse) and 10 X values for each approach that AuNPs’ size decay as a monoexponential with X. This result is, for the first time, in agreement with the sole available theoretical prediction by Kumar et al. on the whole studied range of X

Role of the ratio of biopolyelectrolyte persistence length to nanoparticle size in the structural tuning of electrostatic complexes

International audienceAbstract. Aggregation of nanoparticles of given size R induced by addition of a polymer strongly depends on its degree of rigidity. This is shown here on a large variety of silica nanoparticle self-assemblies obtained by electrostatic complexation with carefully selected oppositely charged bio-polyelectrolytes of different rigidity. The effective rigidity is quantified by the total persistence length L T representing the sum of the intrinsic (L p) and electrostatic (L e) polyelectrolyte persistence length, which depends on the screening, i.e., on ionic strength due to counterions and external salt concentrations. We experimentally show for the first time that the ratio L T /R is the main tuning parameter that controls the fractal dimension D f of the nanoparticles self-assemblies, which is determined using small-angle neutron scattering: (i) For L T /R1, L e is strongly increased due to the absence of salt and repulsions between nanoparticles cannot be compensated by the polyelectrolyte wrapping, which allow a spacing between nanoparticles and the formation of one dimensional pearl necklace complexes. (iv) Finally, electrostatic 2 screening, i.e. ionic strength, turned out to be a reliable way of controlling D f and the phase diagram behavior. It finely tunes the short-range interparticle potential, resulting in larger fractal dimensions at higher ionic strength

Suppression of Aggregation in Natural-Semiflexible/Flexible Polyanion Mixtures, and Direct Check of the OSF Model using SANS

Aggregation and other interactions are suppressed for a biological semiflexible polyelectrolyte, hyaluronan (HA), when it is embedded in a mixture with another negatively charged and flexible polyelectrolyte chain, sodium polystyrene sulfonate. We see directly HA only in the mixture using Small-Angle Neutron Scattering, isotopic labelling and contrast matching. At low ionic strength, for which aggregation is usually seen for pure HA solutions, an unambiguous set of experimental results shows that we neither observe HA aggregation nor a polyelectrolyte peak (observed for solutions of single species); instead we observe a wormlike chain behaviour characteristic of single chain with a variation of the persistence length with the square of the Debye screening length, Le~\kappa^-2, as formerly predicted by Odijk and not yet observed on a polymer chain

Cx36 makes channels coupling human pancreatic β-cells, and correlates with insulin expression

Previous studies have documented that the insulin-producing β-cells of laboratory rodents are coupled by gap junction channels made solely of the connexin36 (Cx36) protein, and have shown that loss of this protein desynchronizes β-cells, leading to secretory defects reminiscent of those observed in type 2 diabetes. Since human islets differ in several respects from those of laboratory rodents, we have now screened human pancreas, and islets isolated thereof, for expression of a variety of connexin genes, tested whether the cognate proteins form functional channels for islet cell exchanges, and assessed whether this expression changes with β-cell function in islets of control and type 2 diabetics. Here, we show that (i) different connexin isoforms are differentially distributed in the exocrine and endocrine parts of the human pancreas; (ii) human islets express at the transcript level different connexin isoforms; (iii) the membrane of β-cells harbors detectable levels of gap junctions made of Cx36; (iv) this protein is concentrated in lipid raft domains of the β-cell membrane where it forms gap junctions; (v) Cx36 channels allow for the preferential exchange of cationic molecules between human β-cells; (vi) the levels of Cx36 mRNA correlated with the expression of the insulin gene in the islets of both control and type 2 diabetics. The data show that Cx36 is a native protein of human pancreatic islets, which mediates the coupling of the insulin-producing β-cells, and contributes to control β-cell function by modulating gene expressio

Lipid-DNAs as Solubilizers of mTHPC

Hydrophobic drug candidates require innovative formulation agents. We designed and synthesized lipidDNA polymers containing varying numbers of hydrophobic alkyl chains. The hydrophobicity of these amphiphiles is easily tunable by introducing a defined number of alkyl chain-modified nucleotides during standard solid-phase synthesis of DNA using an automated DNA synthesizer. We observed that the resulting self-assembled micelles solubilize the poorly water-soluble drug, meta-tetra-hydroxyphenyl-chlorin (mTHPC) used in photodynamic therapy (PDT) with high loading concentrations and loading capacities. A cell viability study showed that mTHPCloaded micelles exhibit good biocompatibility without irradiation, and high PDT efficacy upon irradiation. LipidDNAs provide a novel class of drug-delivery vehicle, and hybridization of DNA offers a potentially facile route for further functionalization of the drug-delivery system with, for instance, targeting or imaging moieties

Cx36 makes channels coupling human pancreatic β-cells, and correlates with insulin expression

Previous studies have documented that the insulin-producing beta-cells of laboratory rodents are coupled by gap junction channels made solely of the connexin36 (Cx36) protein, and have shown that loss of this protein desynchronizes beta-cells, leading to secretory defects reminiscent of those observed in type 2 diabetes. Since human islets differ in several respects from those of laboratory rodents, we have now screened human pancreas, and islets isolated thereof, for expression of a variety of connexin genes, tested whether the cognate proteins form functional channels for islet cell exchanges, and assessed whether this expression changes with beta-cell function in islets of control and type 2 diabetics. Here, we show that (i) different connexin isoforms are differentially distributed in the exocrine and endocrine parts of the human pancreas; (ii) human islets express at the transcript level different connexin isoforms; (iii) the membrane of beta-cells harbors detectable levels of gap junctions made of Cx36; (iv) this protein is concentrated in lipid raft domains of the beta-cell membrane where it forms gap junctions; (v) Cx36 channels allow for the preferential exchange of cationic molecules between human beta-cells; (vi) the levels of Cx36 mRNA correlated with the expression of the insulin gene in the islets of both control and type 2 diabetics. The data show that Cx36 is a native protein of human pancreatic islets, which mediates the coupling of the insulin-producing beta-cells, and contributes to control beta-cell function by modulating gene expression.The Swiss National Science Foundation (310000-122430 to P.Me), the Juvenile Diabetes Research Foundation (1-2005-1084 to V.C., 1-2007-158 to P.Me), the National Institute of Health (DK55183 to V.C.), the European Union (FP6-Integrated Project EuroDia LSHM-CT-2006-518153 to P.Ma; FP-7 BETAIMAGE 222980 to P.Me), Novo Nordisk (to P.Me) and The Larry L. Hillblom Foundation (to V.C.). Image analysis was performed at The National Center for Microscopy and Imaging Research (NIH grant RR4050 to M. Ellisman). Fresh human islets were provided by the Cell Isolation and Transplantation Cente