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Polymerized colloidal crystal hydrogel films as intelligent chemical sensing materials.

Chemical sensors respond to the presence of a specific analyte in a variety of ways. One of the most convenient is a change in optical properties, and in particular a visually perceptible colour change. Here we report the preparation of a material that changes colour in response to a chemical signal by means of a change in diffraction (rather than absorption) properties. Our material is a crystalline colloidal array of polymer spheres (roughly 100 nm diameter) polymerized within a hydrogel that swells and shrinks reversibly in the presence of certain analytes (here metal ions and glucose). The crystalline colloidal array diffracts light at (visible) wavelengths determined by the lattice spacing, which gives rise to an intense colour. The hydrogel contains either a molecular-recognition group that binds the analyte selectively (crown ethers for metal ions), or a molecular-recognition agent that reacts with the analyte selectively. These recognition events cause the gel to swell owing to an increased osmotic pressure, which increases the mean separation between the colloidal spheres and so shifts the Bragg peak of the diffracted light to longer wavelengths. We anticipate that this strategy can be used to prepare 'intelligent' materials responsive to a wide range of analytes, including viruses.

Barium↗

Insights into phase transition kinetics from colloid science.

Colloids display intriguing transitions between gas, liquid, solid and liquid crystalline phases. Such phase transitions are ubiquitous in nature and have been studied for decades. However, the predictions of phase diagrams are not always realized; systems often become undercooled, supersaturated, or trapped in gel-like states. In many cases the end products strongly depend on the starting position in the phase diagram and discrepancies between predictions and actual observations are due to the intricacies of the dynamics of phase transitions. Colloid science aims to understand the underlying mechanisms of these transitions. Important advances have been made, for example, with new imaging techniques that allow direct observation of individual colloidal particles undergoing phase transitions, revealing some of the secrets of the complex pathways involved.

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Particle dynamics in concentrated colloidal suspensions.

We have studied the dynamical and structural properties of dense charge stabilized colloidal suspensions by a combination of small-angle neutron scattering (SANS), 3D dynamic light scattering (3DDLS) and diffusing wave spectroscopy (DWS). SANS and 3DDLS extend static and dynamic light scattering techniques to the regime of opaque samples while DWS additionally provides information on short length scales, typically from 1-50 nm. This offers an increased range of accessible length and time scales perfectly suited for the (non-invasive) investigation of highly concentrated suspensions. Different systems have been examined ranging from hard sphere like suspensions over strongly repulsive charged spheres to colloidal gels. We furthermore present an extended theoretical frame for DWS to characterize the internal dynamics of turbid gels made from nanosized colloidal particles.

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Rideal lecture. Universal features of the fluid to solid transition for attractive colloidal particles.

Attractive colloidal particles can exhibit a fluid to solid phase transition if the magnitude of the attractive interaction is sufficiently large, if the volume fraction is sufficiently high, and if the applied stress is sufficiently small. The nature of this fluid to solid transition is similar for many different colloid systems, and for many different forms of interaction. The jamming phase transition captures the common features of these fluid to solid translations, by unifying the behavior as a function of the particle volume fraction, the energy of interparticle attractions, and the applied stress. This paper describes the applicability of the jamming state diagram, and highlights those regions where the fluid to solid transition is still poorly understood. It also presents new data for gelation of colloidal particles with an attractive depletion interaction, providing more insight into the origin of the fluid to solid transition.

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Preparation of silver nanoprisms using poly(N-vinyl-2-pyrrolidone) as a colloid-stabilizing agent and the effect of silver nanoparticles on the photophysical properties of cationic dyes.

The synthesis of silver nanoprisms in aqueous solution using poly(N-vinyl-2-pyrrolidone) (PVP) with different molecular weights (29, 55 and 1300 kg mol(-1)) as a stabilizing agent is described. Low molecular weight PVP (55 kg mol(-1)) is indicated for the preparation of a stable blue solution containing Ag nanoprisms via extended irradiation of a yellow colloidal solution of nanospheres with polychromatic visible light. The fluorescence properties of some cationic dyes (acridine, 9-aminoacridine, Nile Blue and auramine), free and bound to poly(methacrylic acid), have been studied in the presence of different shaped Ag colloidal particles in solution. Only auramine displays an amplification of the fluorescence signal with increasing colloid concentration, while the fluorescence of the other dyes is quenched by interaction with the polymer-stabilized metal nanoparticles.

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Papuloverrucous colloid milium: an occupational variant.

We report a case of adult colloid milium in a 47-year-old mechanic with a long history of professional contact with lubricating oils and of sun exposure. In addition to the typical translucent papules seen on the forehead, there were warty papules on the backs of both hands with unusual histological and ultrastructural features: marked hyperplasia of the epidermis with orthokeratotic hyperkeratosis and papillary deposits of colloid material that were contiguous with the basal layer of the epidermis. The hand lesions caused by occupational exposure to mineral oils and solar radiation represent an occupational variant of adult colloid milium.

Dermatitis, Occupational↗

Mucinous (colloid) adenocarcinomas secrete distinct O-acylated forms of sialomucins: a histochemical study of gastric, colorectal and breast adenocarcinomas.

AIMS: Mucinous (colloid) adenocarcinomas represent a distinct group of tumours defined by the presence of large amounts of extracellular mucins. By using histochemical methods, we analysed mucins secreted by mucinous versus non-mucinous adenocarcinomas and looked for differential secretion profiles. METHODS AND RESULTS: Sixty-four adenocarcinomas were studied (23 colorectal, 17 gastric, and 24 breast tumours). Thirty-two tumours were of the colloid type. The following methods were applied to paraffin tissue sections: (i) Alcian blue (pH 2.5) and periodic acid-Schiff (PAS); (ii) high iron diamine and Alcian blue (pH 2.5); (iii) periodic acid borohydride, potassium hydroxide, and PAS; (iv) periodic acid-thionine Schiff, potassium hydroxide, and PAS; and (v) periodic acid-borohydride and PAS. Most adenocarcinomas secreted acidic mucins, with sialomucins predominating over sulfomucins, except for non-mucinous adenocarcinomas of the breast which showed predominant neutral mucins. All mucinous adenocarcinomas contained C9-O-acyl sialic acid as mono, di(C8,C9)-, or tri(C7,C8,C9)-O-acyl forms. Acidic mucins secreted by the majority of non-colloid adenocarcinomas consisted of non-O-acylated sialomucins. CONCLUSIONS: C9-O-acylation of sialic acid is a characteristic feature of mucinous adenocarcinomas and can be readily detected by histochemical methods.

Acetylation↗

Sentinel lymph node identification for patients with breast cancer using large-size radiotracer particles: technetium-99m-labeled tin colloids produced excellent results.

Sentinel lymph node (SLN) biopsies using radioactive tracers have been reported to detect the metastatic status of the axillary lymph nodes in breast cancer patients. However, the optimal radioactive tracer particle sizes remain to be determined. In this study, identification of SLNs with large radiolabeled tin colloid particles was evaluated. Seventy-five patients with T1-2, N0 breast cancer were enrolled. Two hours prior to surgery, 1 to 2.5 mL technetium-99m-labeled tin colloid particles were injected around the tumor under ultrasonographic guidance. Immediately before the operation, dye fluids were also injected around the tumor to increase the interstitial pressure. After axillary dissection, lymph nodes with x100 or more uptake of radioactivity than the mean of the other lymph nodes are considered to be SLN. All lymph nodes from the axillary dissections were pathologically investigated, and the characteristics of SLNs were evaluated. SLNs were clearly identified in 74 of 75 patients (98.7%). Of 37 patients without SLN metastasis, pathological investigation revealed no further involvement of the remaining non-SLNs. The SLNs tended to be larger in size, and more than 50% were located in the lower medial site of the axilla. This is the first study to show that SLNs could successfully be identified with radiolabeled tin colloid particles. When SLNs were negative for metastases, non-SLNs were always negative.

Breast Neoplasms↗

Paroxysmal headache caused by colloid cyst of the third ventricle: case report and review of the literature.

Colloid cysts of the third ventricle are benign tumors that may cause brief, severe headache and, rarely, death. We present a patient with frequent, episodic, brief, severe headaches of 2 weeks' duration who suddenly became obtunded. We reviewed the literature on the symptomatology of colloid cysts and conclude that any patient with less than a 1-year history suggestive of a third ventricular colloid cyst causing brief, severe headaches should be aggressively investigated.

Adult↗

Twenty colloid cysts--comparison of endoscopic and microsurgical management.

The management of colloid cyst remains controversial, evaluation of the competing methods seems to be necessary. We report on our experience with colloid cysts in the last decade: ten were managed solely endoscopically, 10 were resected microsurgically (9 via a transcortical/transventricular, 1 via a transcallosal approach). The outcome in the endoscopic group was excellent in 9 cases and unsatisfying in 1 case (recurrence). In the microsurgical group we achieved a good outcome in 5 of 10 cases, a fair outcome in 4 cases and 1 lethal outcome (caused by pulmonary embolism). Complications in the endoscopic group: one intraoperative bleeding, 1 stitch granuloma, 1 mispuncture of the ventricle, and 1 meningitis. Complications in the microsurgical group: 1 subdural effusion, 1 flap infection, 1 mild hemiparesis, 1 transient impairment of consciousness and 1 pulmonary embolism. Mean operative time and length of hospitalization of the endoscopic group were clearly shorter than in the microsurgical group: 91 min versus 267 min time of surgery, 5.1 days versus 18.9 days of hospitalization. Complete resection was achieved in 8 of 10 cases of microsurgery, and in 3 of 10 cases in endoscopy. Endoscopic management results in lower costs and superior patients' comfort. The reduced number of total resections in the endoscopic group may lead to a higher recurrence rate in long-term follow-up, which might be a serious disadvantage of endoscopy. However, more experience in the endoscopic techniques may result in a higher rate of total resection of colloid cysts.

Adult↗

[99mTc tin colloid scintigraphy in the diagnosis of acute rejection reactions in kidney transplants].

Quantitative measurements of 99MTc-tin colloid uptake in renal transplants permits differentiation of acute rejection from other causes of deteriorating renal function, such as acute tubular necrosis, cyclosporin A nephrotoxicity or chronic rejection. 144 99mTc-tin colloid scintigrams were performed on 71 renal transplants; the results were compared with clinical, biochemical and histological findings. Sensitivity of colloid scintigraphy is 97.4% and specificity is 80%. Compared with other isotope methods, this has the advantage that it does not depend on comparison with repeated examinations.

Cyclosporins↗

[Colloid cysts of the 3d ventricle: an underestimated danger?].

Five cases of colloid cysts of the third ventricle discovered only at autopsy are presented. In 3 cases, colloid cysts were identified as the actual cause of death; clinical symptoms had been unspecific (mostly intermittent headaches) and of varying duration. The pathogenesis of "sudden death" as it may occur in some of these benign, dysembryogenic neoplasms, is still not fully understood. Neither the size of the cyst and the degree of ventricular dilatation, nor the duration of clinical symptoms, seem to provide reliable prognostic indicators of this potentially fatal complication. That an extended indication for surgery might be advisable even in cases of asymptomatic colloid cysts without hydrocephalus, as advocated by some authors, is considered in the discussion.

Adult↗

Interfacial tension and wetting in colloid-polymer mixtures.

We calculate the interfacial tension and the wetting behavior in phase separated colloid-polymer mixtures both for ideal and excluded volume interacting polymers. Within the recently developed extension of the free volume theory to include polymer interactions the interfacial tension of the free interface is calculated by adding a van der Waals squared gradient term. The wetting behavior at a hard wall is calculated following a Cahn-Fisher-Nakanishi approach taking the one- and two-body colloid-wall interactions into account. Comparing results for interacting polymers with those for ideal polymers we find that for interacting polymers the interfacial tension does not increase as steeply as a function of the gas-liquid colloid density difference. Furthermore, the wetting transition shifts to higher polymer concentrations, even to above the triple line. The predictions for both the interfacial tension and the wetting are compared to recent experiments.

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Interpretation of conservative forces from Stokesian dynamic simulations of interfacial and confined colloids.

This paper presents Stokesian dynamics simulations of experiments involving one or two charged colloids near either a single charged wall or confined between parallel charged walls. Equilibrium particle-particle and particle-wall interactions are interpreted from dynamic particle trajectories in simulations involving (1) a single particle levitated above a wall, (2) two particles below a wall, and (3) two particles confined between two parallel walls. By specifying only repulsive electrostatic Derjaguin-Landau-Verwey-Overbeek (DLVO) potentials and including multibody hydrodynamics, we successfully recover expected potentials in some cases, while anomalous attraction is observed in other cases. Attraction inferred in the latter simulations displays quantitative agreement with literature measurements when particle dynamics are interpreted using reported analyses. Because anomalous attraction is reproduced in simulations using only electrostatic repulsive DLVO potentials, our results reveal the one-dimensional analyses to be invalid for configurations that are inherently multidimensional via multibody hydrodynamics. Parameters related to experimental sampling of particle dynamics are also found to be critical for obtaining accurate potentials. We explain the anomalous attraction in each experiment using effective potentials, which can be employed in an a priori fashion to assist the confident design of future experiments involving interfacial and confined colloids. Ultimately, our findings reveal the importance of dimensionality and multibody hydrodynamics for understanding nonequilibrium dynamics of colloids near surfaces.

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Colloidal electroconvection in a thin horizontal cell. I. Microscopic cooperative patterns at low voltage.

Applying an electric field to an aqueous colloidal dispersion establishes a complex interplay of forces among the highly mobile simple ions, the more highly charged but less mobile colloidal spheres, and the surrounding water. This interplay can induce a wide variety of visually striking dynamical instabilities even when the applied field is constant. This paper reports on the highly organized patterns that emerge when electrohydrodynamic forces compete with gravity in thin layers of charge-stabilized colloidal spheres subjected to low voltages between parallel-plate electrodes. Depending on the conditions, these spheres can form levitating clusters with morphologies ranging from tumbling clouds to toroidal vortex rings and to writhing labyrinths.

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Ionic correlations in highly charge-asymmetric colloidal liquids.

We use electrophoretic mobility (mu) measurements of charged colloidal particles under the presence of multivalent counterions as a probe of the electrostatic correlations between them; they become important for sufficiently high surface charge densities of the colloid (sigma) and result in a decreasing mu upon increasing sigma. The physics of this decrease is the same as that giving rise to charge inversion. We account qualitatively for the observations by considering recent theoretical arguments that assume the counterions next to the colloid surface as a strongly correlated liquid of properties similar to that of a Wigner crystal.

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Phase behavior of a suspension of colloidal hard rods and nonadsorbing polymer.

We study the phase behavior of a mixture of colloidal hard rods with a length-to-diameter ratio of L/sigma(c)=5 and nonadsorbing ideal polymer. We map our binary mixture onto an effective one-component system by integrating out the degrees of freedom of the polymer coils. We derive a formal expression for the exact effective Hamiltonian of the colloidal rods, i.e., it includes all effective many-body interactions and it is related to the exact free volume available for the polymer. We determine numerically on a grid the free volume available for the ideal polymer coils "on the fly" for each colloidal rod configuration during our Monte Carlo simulations. This allows us to go beyond first-order perturbation theory, which employs the pure hard-rod system as reference state. We perform free energy calculations for the isotropic, nematic, smectic, and crystal phase using thermodynamic integration and common tangent constructions are used at fixed polymer fugacities to map out the phase diagram. The phase behavior is determined for size ratios q=sigma(p)/sigma(c)=0.15, 0.5, and 1, where sigma(p) is the diameter of the polymer coils. The phase diagrams based on the full effective Hamiltonian are compared with those obtained from first-order perturbation theory, from simulations using the effective pair potential approximation to the effective Hamiltonian, and with those based on an empiric effective depletion potential for the rods. We find that the many-body character of the effective interactions stabilizes the nematic and smectic phases for large q, while the effective pair potential description overestimates the attractive interactions and favors, hence, a broad isotropic-crystal coexistence.

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Colloidal electroconvection in a thin horizontal cell. II. Bulk electroconvection of water during parallel-plate electrolysis.

We recently have reported [J. Chem. Phys. 122, 164701 (2005)] a family of electroconvective patterns that arise when charge-stabilized colloidal dispersions are driven by constant (dc) vertical electric fields. Competition between gravity and electrokinetic forces acting on the individual spheres in this system leads to the formation of highly organized convective instabilities involving hundreds of spheres. Here, we report a distinct class of electroconvective patterns that emerge in confined aqueous dispersions at higher biases. These qualitatively resemble the honeycomb and labyrinthine patterns formed during thermally driven Rayleigh-Benard convection, but arise from a distinct mechanism. Unlike the localized colloidal electroconvective patterns observed at lower biases, moreover, these system-spanning patterns form even without dispersed colloidal particles. Rather, they appear to result from an underlying electroconvective instability during electrolysis in the parallel plate geometry. This contrasts with recent theoretical results suggesting that simple electrolytes are linearly stable against electroconvection.

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