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Multicomponent self-assembly has been explored to create novel metamaterials from nanoparticles of different sizes and compositions, but the assembly of nanoparticles with complementary shapes remains rare. Recent binary assemblies were mediated by DNA base pairing or induced by solvent evaporation. Here, we introduce depletion-induced self-assembly (DISA) as a novel approach to constructing tunable binary lattices. In situ structural analysis in the real and reciprocal spaces demonstrates DISA of a binary mixture of octahedra and tetrahedra into extended supercrystals with Fm 3̅ m symmetry. The interparticle distance, adjustable by depletant concentration, offers a versatile method for assembling nanoparticles into ordered structures while they remain dispersed in a liquid phase. We show that DISA can control the packing fraction of such binary supercrystals between φ = 0.37 and φ = 0.66, much lower than dense packing in the dry state. These findings highlight DISA's potential for creating complex and highly ordered metamaterials with tailored properties.

Imogolite nanotubes (INTs) are predicted as a unique 1D material with spatial separation of conduction and valence band edges but their large band gaps have inhibited their use as photocatalysts. The first step toward using these NTs in photocatalysis and exploiting the polarization-promoted charge separation across their walls is to reduce their band gap. Here, the modification of double-walled aluminogermanate INTs by incorporation of titanium into the NT walls is explored. The precursor ratio x = [Ti]/([Ge]+[Ti]) is modulated between 0 and 1. Structural and optical properties are determined at different scales and the photocatalytic performance is evaluated for H 2 production. Although the incorporation of Ti atoms into the structure remains limited, the optimal condition is found around x = 0.4 for which the resulting NTs reveal a remarkable hydrogen production of ≈1500 µmol g -1 after 5 h for a noble metal-free photocatalyst, a 65-fold increase relative to a commercial TiO 2 -P25. This is correlated to a lowering of the recombination rate of photogenerated charge carriers for the most active structures. These results confirm the theoretical predictions regarding the potential of modified INTs as photoactive nanoreactors and pave the way for investigating and exploiting their polarization properties for energy applications., (© 2023 The Authors. Small Methods published by Wiley‐VCH GmbH.)

The limitations of conventional template-based methods for the deposition of nanoparticle assemblies into defined patterns on solid substrates call for the development of techniques that do not require templates or lithographic masks. The use of optically-induced thermal gradients to drive the migration of colloids toward or away from a laser spot, known as opto-thermophoresis, has shown promise for the low-power trapping and optical manipulation of a variety of colloidal species. However, the printing of colloids using this technique has so far not been established. Herein, a method for the optically directed printing of noble metal nanoparticles, specifically gold nanospheres is reported. The thermophoresis of the polymer polyvinylpyrrolidone and gold nanospheres toward a laser spot led to the deposition of nanoparticle aggregates, capable of serving as surface-enhanced Raman scattering substrates. The influence of heating laser power and the concentrations of polymer, salt, and surfactant on the nanoparticle deposition rate and structure of the printed pattern are studied, showing that a variety of conditions can permit printing, suggesting facile generalization to different nanoparticle compositions, sizes, and shapes. These findings will greatly benefit future efforts for directed nanoparticle assembly, and drive applications in sensing, photothermal heating, and relevant applications in biomedicine and devices., (© 2024 The Author(s). Small Methods published by Wiley‐VCH GmbH.)

Hypothesis: Imogolite nanotubes (INTs) are unique anisometric particles with monodisperse nanometric diameters. Aluminogermanate double-walled INTs (Ge-DWINTs) are obtained with variable aspect ratios by controlling the synthesis conditions. It thus appears as an interesting model system to investigate how aspect ratio and ionic valence influence the colloidal behavior of highly anisometric rods., Experiments: The nanotubes were synthesized by hydrothermal treatment for 5 or 20 days to modify the aspect ratio while the electrostatic interactions were investigated by comparing the colloidal stability in symmetric and asymmetric electrolytes. The phase behavior and their related microstructure were determined by optical observations and small-angle X-ray scattering measurements, coupled with interparticle distance modelling., Findings: We revealed that colloidal suspensions of Ge-DWINTs prepared in NaCl are guided by repulsive double layer forces, undergoing different liquid crystal phase transitions before stiffen into a glass-like state. We found that the microstructure can be rationalized by taking into account the anisometric nature of the particles. By contrast, dispersions prepared with asymmetric electrolytes are governed by strong attractive forces and thus form space-filling gels containing large nanotubes aggregates., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

Manganese (Mn) is of particular concern in groundwater, as low-level chronic exposure to aqueous Mn concentrations in drinking water can result in a variety of health and neurodevelopmental effects. Much of the global population relies on drinking water sourced from karst aquifers. Thus, we seek to assess the relative risk of Mn contamination in karst by investigating the Shenandoah Valley, VA region, as it is underlain by both karst and non-karst aquifers and much of the population relies on water wells and spring water. Water and soil samples were collected throughout the Shenandoah Valley, to supplement pre-existing well water and spring data from the National Water Information System and the Virginia Household Water Quality Program, totaling 1815 wells and 119 springs. Soils were analyzed using X-ray fluorescence and Mn K-Edge X-ray absorption near-edge structure spectroscopy. Factors such as soil type, soil geochemistry, and aquifer lithology were linked with each location to determine if correlations exist with aqueous Mn concentrations. Analyzing the distribution of Mn in drinking water sources suggests that water wells and springs within karst aquifers are preferable with respect to chronic Mn exposure, with < 4.9% of wells and springs in dolostone and limestone aquifers exceeding 100 ppb Mn, while sandstone and shale aquifers have a heightened risk, with > 20% of wells exceeding 100 ppb Mn. The geochemistry of associated soils and spatial relationships to various hydrologic and geologic features indicates that water interactions with aquifer lithology and soils contribute to aqueous Mn concentrations. Relationships between aqueous Mn in spring waters and Mn in soils indicate that increasing aqueous Mn is correlated with decreasing soil Mn(IV). These results point to redox conditions exerting a dominant control on Mn in this region., (© 2024. The Author(s).)

Throughout history scientists have looked to Nature for inspiration and attempted to replicate intricate complex structures formed by self-assembly. In the context of synthetic supercrystals, achieving such complexity remains a challenge due to the highly symmetric nature of most nanoparticles (NPs). Previous works have shown intricate coupling between the self-assembly of NPs and confinement in templates, such as emulsion droplets (spherical confinement) or tubes (cylindrical confinement). This study focuses on the interplay between anisotropic NP shape and tunable "prismatic confinement" leading to the self-assembly of supercrystals in cavities featuring polygonal cross sections. A multiscale characterization strategy is employed to investigate the orientation and structure of the supercrystals locally and at the ensemble level. Our findings highlight the role of the mold interface in guiding the growth of distinct crystal domains: each side of the mold directs the formation of a monodomain that extends until it encounters another, leading to the creation of grain boundaries. Computer simulations in smaller prismatic cavities were conducted to predict the effect of an increased confinement. Comparison between prismatic and cylindrical confinements shows that flat interfaces are key to orienting the growth of supercrystals. This work shows a method of inducing orientation in plasmonic supercrystals and controlling their textural defects, thus offering insight into the design of functional metasurfaces and hierarchically structured devices.

We report here the highly ordered restacking of the layered phosphatoantimonic dielectric materials H 3(1- x ) M 3 x Sb 3 P 2 O 14 , (where M = Li, Na, K, Rb, Cs and 0 ≤ x ≤ 1), from their nanosheets dispersed in colloidal suspension, induced by a simple pH change using alkaline bases. H 3 Sb 3 P 2 O 14 aqueous suspensions are some of the rare examples of colloidal suspensions based on 2D materials exhibiting a lamellar liquid crystalline phase. Because the lamellar period can reach several hundred nanometers, the suspensions show vivid structural colors and because these colors are sensitive to various chemicals, the suspensions can be used as sensors. The structures of the lamellar liquid crystalline phase and the restacked phase have been studied by X-ray scattering (small and wide angle), which has followed the dependence of the lamellar/restacked phase equilibrium on the cation exchange rate, x . The X-ray diffraction pattern of the restacked phase is almost identical to that of the M 3 Sb 3 P 2 O 14 crystalline phase, showing that the restacking is highly accurate and avoids the turbostratic disorder of the nanosheets classically observed in nanosheet stacking of other 2D materials. Strikingly, the restacking process exhibits features highly reminiscent of a first-order phase transition, with the existence of a phase coexistence region where both ∼1 nm (interlayer spacing of the restacked phase) and ∼120 nm lamellar periods can be observed simultaneously. Furthermore, this first-order phase transition is well described theoretically by incorporating a Lennard-Jones-type lamellar interaction potential into an entropy-based statistical physics model of the lamellar phase of nanosheets. Our work shows that the precise cation exchange produced at room temperature by a classical neutralization reaction using alkaline bases leads to a crystal-like restacking of the exfoliated free Sb 3 P 2 O 14 3- nanosheets from suspension, avoiding the turbostratic disorder typical of van der Waals 2D materials, which is detrimental to the controlled deposition of nanosheets into complex integrated electronic, spintronic, photonic or quantum structures.

Depletion-induced self-assembly is routinely used to separate plasmonic nanoparticles (NPs) of different shapes, but less often for its ability to create supercrystals (SCs) in suspension. Therefore, these plasmonic assemblies have not yet reached a high level of maturity and their in-depth characterization by a combination of in situ techniques is still very much needed. In this work, gold triangles (AuNTs) and silver nanorods (AgNRs) are assembled by depletion-induced self-assembly. Small Angle X-ray Scattering (SAXS) and scanning electron microscopy (SEM) analysis shows that the AuNTs and AgNRs form 3D and 2D hexagonal lattices in bulk, respectively. The colloidal crystals are also imaged by in situ Liquid-Cell Transmission Electron Microscopy. Under confinement, the affinity of the NPs for the liquid cell windows reduces their ability to stack perpendicularly to the membrane and lead to SCs with a lower dimensionality than their bulk counterparts. Moreover, extended beam irradiation leads to disassembly of the lattices, which is well described by a model accounting for the desorption kinetics highlighting the key role of the NP-membrane interaction in the structural properties of SCs in the liquid-cell. The results shed light on the reconfigurability of NP superlattices obtained by depletion-induced self-assembly, which can rearrange under confinement., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

We report here an extensive high pressure small-angle X-ray scattering study on 3D supercrystals self-assembled from colloidal spherical gold crystalline nanoparticule (NPs). We used a large variety of NPs with different gold core diameter, from 2 to 10 nm, grafted with different ligands: alkane-thiols or oleylamine. The self assembly of these various NPs leads to supercrystals of different structures: face centered cubic (FCC), body centered cubic (BCC), as well as the C14 Frank and Kasper phase. Using a Diamond Anvil Cell to apply pressure on these wide range of samples, we provide a unique overview on the mechanical properties of gold NPs supercrystals. In particular, bulk modulii have been determined from low pressure regime and the different behavior between FCC and BCC structures has been interpreted as due to an easier restructuring of the ligand conformation in the FCC structure compared to the BCC structure. At higher pressure, a fingerprint of irreversible structural transition has been observed. We have ascribed this irreversibility to the sintering of nanoparticles and confirmed this interpretation by transmission electron microscopy.

Packing solid shapes into regular lattices can yield very complex assemblies, not all of which achieve the highest packing fraction. In two dimensions, the regular pentagon is paradigmatic, being the simplest shape that does not pave the plane completely. In this work, we demonstrate the packing of plasmonic nanoprisms with pentagonal cross section, which form extended supercrystals. We do encounter the long-predicted ice-ray and Dürer packings (with packing fractions of 0.921 and 0.854, respectively) but also a variety of novel polymorphs that can be obtained from these two configurations by a continuous sliding transformation and exhibit an intermediate packing fraction. Beyond the fundamental interest of this result, fine control over the density and symmetry of such plasmonic assemblies opens the perspective of tuning their optical properties, with potential applications in metamaterial fabrication, catalysis, or molecular detection.

Accurate shape description is a challenge in materials science. Small-angle X-ray scattering (SAXS) can provide the shape, size and polydispersity of nanoparticles by form factor modelling. However, simple geometric models such as the ellipsoid may not be enough to describe objects with complex shapes. This work shows that the form factor of gold nanobipyramids is accurately described by a truncated bicone model, which is validated by comparison with transmission electron microscopy (TEM) data for nine different synthesis batches; the average shape parameters (width, height and truncation) and the sample polydispersity are obtained. In contrast, the ellipsoid model yields worse fits of the SAXS data and exhibits systematic discrepancies with the TEM results., (© Jieli Lyu et al. 2023.)

Marangoni flow is among the most intriguing effects in complex fluids and interfacial science. We report here on a fluorescent surfactant that enables to monitor Marangoni flows under quasi-steady conditions, without the need of invasive tracers. The Marangoni zone is clearly visible, and its dynamics can be quantitatively probed both at the air-water interface and within the bulk. In particular, we show that the Marangoni zone exhibits unexpected dependencies with the container size and water depth with the pyrene-tailed surfactant. Additionally, recirculation flows are evidenced by fluorescence near the bottom of the container. This fluorescent probe may find other useful applications in deciphering the complexity of the ubiquitous Marangoni effect.

We report a seed-mediated synthesis strategy to control the size of gold nanoparticles at the atomic scale in the 2-5 nm size range. Starting from 2 nm seeds, a regrowth in organic solvent with a designed amount of precursor can achieve in a predictive fashion a precise mean size with a 0.3 nm resolution. We show that these monodisperse nanoparticles assemble into a 2D hexagonal lattice over a distance that can span tens of micrometers.

Aqueous suspensions of nanosheets are readily obtained by exfoliating low-dimensional mineral compounds like H 3 Sb 3 P 2 O 14 . The nanosheets self-organize, at low concentration, into a periodic stack of membranes, i.e. a lamellar liquid-crystalline phase. Due to the dilution, this stack has a large period of a few hundred nanometres, it behaves as a 1-dimensional photonic material and displays structural colours. We experimentally investigated the dependence of the period on the nanosheet concentration. We theoretically showed that it cannot be explained by the usual DLVO interaction between uniform lamellae but that the particulate nature of nanosheet-laden membranes must be considered. Moreover, we observed that adding small amounts of 100 kDa poly(ethylene oxide) (PEO) decreases the period and allows tuning the colour throughout the visible range. PEO adsorbs on the nanosheets, inducing a strong reduction of the nanosheet charge. This is probably due to the Lewis-base character of the EO units of PEO that become protonated at the low pH of the system, an interpretation supported by theoretical modeling. Oddly enough, adding small amounts of 1 MDa PEO has the opposite effect of increasing the period, suggesting the presence of an additional intermembrane repulsion not yet identified. From an applied perspective, our work shows how the colours of these 1-dimensional photonic materials can easily be tuned not only by varying the nanosheet concentration (which might entail a phase transition) but also by adding PEO. From a theoretical perspective, our approach represents a necessary step towards establishing the phase diagram of aqueous suspensions of charged nanosheets.

Objective: To develop an instrument for the observation of therapeutic communication interactions during rehabilitation sessions and test its inter-rater reliability. Methods: The new instrument THER-I-ACT (THERapy-related Inter-ACTion) has been designed to assess both the frequency and timing of therapeutic interactions in the thematic fields information provision, feedback, other motivational interaction, and bonding. For this inter-rater reliability study, a sample of stroke survivors received arm rehabilitation as either arm ability training, arm basis training, or mirror therapy, or neglect training as individually indicated. Therapy sessions were video-recorded (one for each participant) and therapeutic interactions rated by two independent raters using THER-I-ACT. Results: With regard to the instrument's comprehensiveness to document therapeutic interactions with pre-defined categories the data from 29 sessions suggested almost complete coverage. Inter-rater reliability was very high both for individual categories of therapeutic interaction (frequency and time used for interaction) (intraclass correlation coefficient, ICC 0.91-1.00) and summary scores for the thematic fields of interaction (again for frequency and time used for interaction) (ICC 0.98-1.00). The inter-rater reliability for rating engagement and being focussed for both the therapist and patient was substantial (ICC 0.71 and 0.86). Conclusions: The observational study documented that by use of the newly designed THER-I-ACT various types of therapy-related communication interactions performed by therapists can be assessed with a very high inter-rater reliability. In addition, the thematic fields and categories of therapeutic interaction as defined by the instrument comprehensively covered the type of interaction that occurred in the therapeutic sessions observed., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Platz, Seidel, Müller, Goldmann and Pedersen.)

Many soft matter systems are composed of roughly spherical objects that can self-assemble in ordered structures. Unlike hard spheres, at high volume fraction these soft spheres adapt their shape to the local geometrical constraints and the question of space filling needs to be entirely revisited. Hydrophobically coated gold nanocrystals self-assemble in supercrystals and are good candidates to explore this question. When the soft coating is thin compared to the rigid core, a FCC structure is obtained, with a behaviour similar to that of hard spheres. In the opposite case, for a thick soft coating, a BCC structure is found instead. This paper focus on the intermediate region between these two classical structures. By varying the gold core radius R and the ligand fully extended length L, we establish a structure diagram based on a large experimental data set. The hexagonal Frank-Kasper C14 structure is observed for various values of R and L and can coexist with a FCC phase. Depending on the structure, values of the minimum thickness e of the ligand shell compared to L are different. These experimental results confirm that the C14 Frank-Kasper phase is a solution to the problem of filling the space with soft particles even with a rigid core and should help to establish pertinent models in order to predict the structures of the superlattices built by gold nanoparticles.

Zinc-blende CdSe semiconducting nanoplatelets (NPL) show outstanding quantum confinement properties thanks to their small, atomically-controlled, thickness. For example, they display extremely sharp absorption peaks and ultra-fast recombination rates that make them very interesting objects for optoelectronic applications. However, the presence of a ground-state electric dipole for these nanoparticles has not yet been investigated. We therefore used transient electric birefringence (TEB) to probe the electric dipole of 5-monolayer thick zinc blende CdSe NPL with a parallelepipedic shape. We studied a dilute dispersion of isolated NPL coated with branched ligands and we measured, as a function of time, the birefringence induced by DC and AC field pulses. The electro-optic behavior proves the presence of a large dipolar moment (>245 D) oriented along the length of the platelets. We then induced the slow face-to-face stacking of the NPL by adding oleic acid. In these stacks, the in-plane dipole components of consecutive NPL cancel whereas their normal components add. Moreover, interestingly, the excess polarizability tensor of the NPL stacks gives rise to an electro-optic contribution opposite to that of the electric dipole. By monitoring the TEB signal of the slowly-growing stacks over up to a year, we extracted the evolution of their average length with time and we showed that their electro-optic response can be explained by the presence of a 80 D dipolar component parallel to their normal. In spite of the 4[combining macron]3m space group of bulk zinc blende CdSe, these NPL thus bear an important ground-state dipole whose magnitude per unit volume is twice that found for wurtzite CdSe nanorods. We discuss the possible origin of this electric dipole, its consequences for the optical properties of these nanoparticles, and how it could explain their strong stacking propensity that severely hampers their colloidal stability.

Rational nanoparticle design is one of the main goals of materials science, but it can only be achieved via a thorough understanding of the growth process and of the respective roles of the molecular species involved. We demonstrate that a combination of complementary techniques can yield novel information with respect to their individual contributions. We monitored the growth of long aspect ratio silver rods from gold pentatwinned seeds by three in situ techniques (small-angle X-ray scattering, optical extinction spectroscopy and liquid-cell transmission electron microscopy). Exploiting the difference in reaction speed between the bulk synthesis and the nanoparticle formation in the TEM cell, we show that the anisotropic growth is thermodynamically controlled (rather than kinetically) and that ascorbic acid, widely used for its mild reductive properties, plays a shape-directing role, by stabilizing the {100} facets of the silver cubic lattice, in synergy with the halide ions. This approach can easily be applied to a wide variety of synthesis strategies.

Engineering plasmonic hot spots is essential for applications of plasmonic nanoparticles. A particularly appealing route is to weld plasmonic nanoparticles together to form more complex structures sustaining plasmons with symmetries targeted to given applications. However, control of the welding and subsequent hot spot characteristics is still challenging. Herein, we demonstrate an original method that connects gold particles to their neighbors by another metal of choice. We first assemble gold bipyramids in a tip-to-tip configuration, yielding short chains of variable length, and grow metallic junctions in a second step. We follow the chain formation and the deposition of the second metal (i.e., silver or palladium) via UV/vis spectroscopy, and we map the plasmonic properties using electron energy loss spectroscopy. The formation of silver bridges leads to a huge red shift of the longitudinal plasmon modes into the mid-infrared region, while the addition of palladium results in a red shift accompanied by significant plasmon damping.

In this article, we revisit the colloidal stability of clay imogolite nanotubes by studying the effect of electrostatic interactions on geo-inspired synthetic nanotubes in aqueous dispersions. The nanotubes in question are double-walled aluminogermanate imogolite nanotubes (Ge-DWINTs) with a well-defined diameter (4.3 nm) and with an aspect ratio around 4. Surface charge properties are assessed by electrophoretic measurements, revealing that the outer surfaces of Ge-DWINT are positively charged up to high pH values. A series of Ge-DWINT dispersions have been prepared by osmotic stress to control both the ionic strength of the dispersion and the volume fraction in nanotubes. Optical observations coupled to small and wide-angle X-ray scattering (SAXS/WAXS) experiments allow us to unravel different nanotube organizations. At low ionic strength (IS < 10 -2 mol L -1 ), Ge-DWINTs are fully dispersed in water while they form an arrested gel phase above a given concentration threshold, which shifts toward higher volume fraction with increasing ionic strength. The swelling law, derived from the evolution of the mean intertube distance as a function of the nanotube concentration, evidences a transition from isotropic swelling at low volume fractions to one-dimensional swelling at higher volume fractions. These results show that the colloidal stability of Ge-DWINT is driven by repulsive interactions for ionic strengths lower than 10 -2 mol L -1 . By contrast, higher salt concentrations lead to attractive interactions that destabilize the colloid suspension, inducing nanotube coagulation into larger structures that settle over time or form opaque gels. Detailed simulations of the WAXS diagram reveal that aggregates are mainly formed by an isotropic distribution of small bundles (less than four nanotubes) in which the nanotubes organized themselves in parallel orientation. Altogether, these measurements allow us to give the first overview of the phase diagram of colloidal dispersions based on geo-inspired imogolite-like nanotubes.

Tailoring the crystal structure of plasmonic nanoparticle superlattices is a crucial step in controlling the collective physical response of these nanostructured materials. Various strategies can achieve this goal for isotropic nanoparticles, but few of them have been successful with anisotropic building blocks. In this work we use hybrid particles, consisting of gold nanorods encased in silver shells with a thickness that can be controlled from a few atomic layers to tens of nanometers. The particles were synthesized, characterized by a combination of techniques and assembled into supercrystals with a smectic B configuration, i.e. a 2D in-plane periodic order without interplane lateral correlations. We showed that, by tuning the silver shell thickness, the in-plane order can be changed from hexagonal to square and the lattice parameters can be adjusted. The spatial distribution of the supercrystal was systematically studied by optical and electron microscopy and by small-angle X-ray scattering. Through optimized surface chemistry, we obtain homogeneous, millimeter-size films of standing nanoparticles, which hold promise for all applications using plasmon-enhanced technologies.

Nanophase segregation of a bicomponent thiol self-assembled monolayer is predicted using atomistic molecular dynamics simulations and experimentally confirmed. The simulations suggest the formation of domains rich in acid-terminated chains, on one hand, and of domains rich in amide-functionalized ethylene glycol oligomers, on the other hand. In particular, within the amide-ethylene glycol oligomers region, a key role is played by the formation of interchain hydrogen bonds. The predicted phase segregation is experimentally confirmed by the synthesis of 35 and 15 nm gold nanoparticles functionalized with several binary mixtures of ligands. An extensive study by transmission electron microscopy and electron tomography, using silica selective heterogeneous nucleation on acid-rich domains to provide electron contrast, supports simulations and highlights patchy nanoparticles with a trend toward Janus nano-objects depending on the nature of the ligands and the particle size. These results validate our computational platform as an effective tool to predict nanophase separation in organic mixtures on a surface and drive further exploration of advanced nanoparticle functionalization.

A basic understanding of the driving forces for the formation of multiligand coronas or self-assembled monolayers over metal nanoparticles is mandatory to control and predict the properties of ligand-protected nanoparticles. Herein, 1 H nuclear magnetic resonance experiments and advanced density functional theory (DFT) modeling are combined to highlight the key parameters defining the efficiency of ligand exchange on dispersed gold nanoparticles. The compositions of the surface and of the liquid reaction medium are quantitatively correlated for bifunctional gold nanoparticles protected by a range of competing thiols, including an alkylthiol, arylthiols of varying chain length, thiols functionalized by ethyleneglycol units, and amide groups. These partitions are used to build scales that quantify the ability of a ligand to exchange dodecanethiol. Such scales can be used to target a specific surface composition by choosing the right exchange conditions (ligand ratio, concentrations, and particle size). In the specific case of arylthiols, the exchange ability scale is exploited with the help of DFT modeling to unveil the roles of intermolecular forces and entropic effects in driving ligand exchange. It is finally suggested that similar considerations may apply to other ligands and to direct biligand synthesis., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Although gold nanoparticles stabilized by organic thiols are the building blocks in a wide range of applications, the role of the ligands on the plasmon resonance of the metal core has been mostly ignored until now. Herein, a methodology based on the combination of spectroscopic ellipsometry and UV-vis spectroscopy is applied to extract dielectric functions of the different components. It is shown that aromatic thiols allow a significant charge transfer at the hybrid interface with the s and d bands of the gold core that yields "giant" red shifts of the plasmon band, up to 40 nm for spherical particles in the size range of 3-5 nm. These results suggest that hybrid nanoplasmonic devices may be designed through the suitable choice of metal core and organic components for optimized charge exchange.

There are only a few cytogenetic analysis (CA) studies that directly compare the novel cultivation technique using immunostimulatory CpG-oligonucleotide DSP30/interleukin-2 (DSP30/IL2) with other culture methods. Therefore, parallel cultures of peripheral blood of 129 chronic lymphocytic leukemia (CLL) patients were set up in unstimulated cultures, in the presence of pokeweed medium (PWM), and with DSP30/IL2. Furthermore, CA results were compared with data obtained by FISH. Clonal aberrations were observed by CA in 6% of the cases in unstimulated cultures, in 27% of the cases with PWM, and in 40% of the cases with DSP30/IL2. Some clonal aberrations were detected by CA only with one culture method. Using 3 different culture methods, clonal aberrations were detected in 41% of the cases by CA and in 71% of the cases by FISH. Altogether, 78% of the cases exhibited clonal aberrations discovered by CA and FISH. Also, CA detected clonal aberrations not targeted by FISH in 7% of the cases, and FISH identified clonal aberrations not detected by CA in 36% of the cases. Our study demonstrates that the combined use of CA with different culture methods together with FISH increases our knowledge of the genetic complexity and heterogeneity in CLL pathogenesis., (© 2014 S. Karger AG, Basel.)

This study illustrates the application of asymmetrical flow field-flow fractionation (AF4) and light scattering analysis during the development of a gene delivery vehicle based on virus-like particles (VLPs) derived from the human polyoma JC virus. The analytical system was created by connecting an AF4 apparatus to the following detectors: diode array, fluorescence, multiangle light scattering, dynamic light scattering, and refractometer. From a single analysis, the molar mass, root mean square and hydrodynamic radii, composition, and purity of the sample could be determined. The VLPs were purified from baculovirus-infected Sf158 insect cells overexpressing the recombinant VP1 protein using weak anion exchange chromatography. The VLPs were dissociated to VP1 pentamers, and the contaminating DNA and proteins were removed using strong anion exchange chromatography. The gene delivery vehicle was created by reassembling the VP1 pentamers in the presence of the desired DNA. The newly formed VLPs encapsulated the DNA and were shown to be capable of delivering the gene of interest to target cells where it was translated into protein. This paper describes the scalable process that was derived to produce the VLPs and demonstrates how the AF4-based analytical characterization was indispensable during the development process.

A major challenge in the field of gene therapy is the development of new carrier/delivery systems that lack the disadvantages of current transfer systems. In the past, some time has been spent developing such modified or alternative vectors. A new candidate is represented by virus-like particles (VLPs). It has been shown that recombinant expression of the major structural proteins of many viruses leads to the formation of VLPs. Such VLPs exhibit morphology similar to the empty capsids of the virus from which they are derived. VLPs are non-infectious, have a similar tropism to the natural virus, and show comparable cellular uptake and intracellular trafficking. Since its discovery, VLP technology has gained importance in biomedical research. Although most investigations into VLP technology have dealt with vaccine development, some research groups have demonstrated that VLPs could also represent a useful gene therapy delivery system. This review will focus on studies performed with VLPs from members of the Papillomaviridae and Polyomaviridae families.

Objective: Patients who have an operation under general anaesthesia with muscle relaxation often complain about neck pain if the head needs to be placed in extreme reclination to facilitate surgical access. Patients complain about vertigo, light muscle tenseness but also about severe joint blockages in the neck region. Due to this complication the standard practise in some hospitals is to refer these patients routinely to a physiotherapist postoperatively. This study investigated the influence of an axial traction - a treatment which can easily be learned by anaesthesiologists - on blockages of the cervical spine in those patients., Methods: In two randomised groups (n = 15 each) of preoperative inconspicuous patients the following directions of motion were investigated: Ante- and retroflexion of C0/1, side inclination C0/1, side nodding and side movement C2/3 to C6/T1, dorsal movement C5/Th2. The examinations took place at the preoperative anaesthetic round, shortly before extubation, two hours after extubation and the next day. Additionally the patients were asked about their discomfort. An axial traction of the cervical spine was performed in one group after extubation. The number of new blockages and the subjective discomfort of the patients was compared with the Chi-Square test., Results: An axial traction of the cervical spine reduces the frequency and the intensity of symptoms significantly., Conclusion: It was investigated whether an axial traction of the cervical spine - a treatment that can easily be learned by anaesthesiologists - could improve patients' comfort. The study showed that an axial traction of the cervical spine immediately after extubation reduces the frequency and intensity of symptoms significantly. This treatment is highly effective, not very time consuming and, if done correctly, without any risk for the patient. By using this treatment routinely, additional expenses for physiotherapeutic interventions could be reduced.

Progressive multifocal leukoencephalopathy (PML) is a fatal, demyelinating disease caused by JC virus (JCV) in patients with severe immunosuppression. We studied the JCV-specific cellular and humoral immune response in 7 healthy donors (HD), 6 human immunodeficiency virus-1 (HIV-1)-infected patients without PML (HIV), 4 HIV-1-negative patients with PML (PML), and 8 HIV-1-positive patients with PML (HIV/PML). As antigens, recombinant virus-like particles of the major structural protein VP1 (VP1-VLP) of JCV, tetanus toxoid (TT), or the mitogen phytohemagglutinin (PHA) were used. Proliferation of peripheral blood mononuclear cells (PBMC) after stimulation with the VP1-VLP was significantly suppressed in PML and HIV/PML patients compared to HD. After antigen stimulation the production of interferon-gamma (IFN-gamma) was reduced in PML, in HIV/PML, and in HIV patients. The production of interleukin-10 (IL-10), however, was elevated in HIV/PML patients. Neither proliferation nor cytokine production correlated with the presence of JCV DNA in PBMC. The immunoglobulin G serum antibody titer to the VP1-VLP was slightly elevated in HIV, elevated in PML, and highly elevated in HIV/PML patients compared to HD. The development of PML appears to coincide with a general impairment of the Th1-type T-helper cell function of cell-mediated immunity.

Recombinantly expressed VP1-virus-like particles (VP1-VLP) of human polyomavirus JC virus (JCV) were described recently as a new DNA transporter system. It was shown that DNA molecules could be packaged into VP1-VLP during a controlled chemical reassociation/dissociation process. In the present study VP1-VLP were studied as carriers for pharmaceutical substances. Propidium iodide (PI) was packaged into VP1-VLP as a reporter molecule. The PI-containing VP1-VLP could be detected directly by flow cytometry. The fluorescence intensity of the VP1-VLP depended strongly on the initial PI concentration. This packaging method is easy to handle and applicable to viruses and VP1-VLP which can be dissociated and reassociated chemically.

Objective: In burned patients, activation of the complement and clotting systems is suggested to play an important role in the development of the capillary leak syndrome and inflammatory tissue destruction. In an animal model of thermal trauma, the possible protective effect of C1 inhibitor (C1Inh), a major control protein of both the complement and clotting systems, was investigated., Design: Prospective, controlled study., Setting: Animal model., Subjects: Healthy pigs weighing 30 kg., Interventions: Pigs were scalded for 25 secs with 75 degrees C hot water to achieve a 30% total body surface deep partial-thickness burn. The treatment group (n = 8) received C1Inh concentrate at an initial dose of 100 units/kg body weight immediately after thermal trauma, followed by three further applications every 12 hrs. Two control groups included animals that were either scalded (n = 8) or not scalded (n = 7) and treated with lactated Ringer's solution., Measurements: Before and at various time points after trauma blood samples were analyzed for complement activation (APH50, CH50, SC5b-9, C3). Continuous monitoring of hemodynamic variables was performed and postmortem histologic examination of specimens from lung, heart, liver, kidney, stomach, duodenum, jejunum, ileum, and colon was carried out. Aseptically collected mesenteric lymph nodes were pooled and screened for bacterial translocation. For evaluation of the burn wound, biopsies from defined scalded and not scalded areas were taken daily. As a measure for edema formation, the weight of the animals was recorded every 2 hrs., Results: After C1Inh treatment, which led to a significantly reduced complement activation, the clinical outcome was clearly improved, as indicated by vital signs and as demonstrated by reduced edema formation. Treated animals presented a diminished bacterial translocation. Pathologic alterations were clearly diminished in the burned skin, in shock-related organs, and in the intestines., Conclusion: Application of C1Inh appears to be an effective means to prevent capillary leakage and inflammatory tissue destruction after thermal trauma.

Anesthesia of the pig poses great problems for experimental animal-based research and particularly in shock research. In this study, five mechanically ventilated domestic pigs were given long-term anesthesia with a combination of ketamine plus pentobarbital. Circulatory parameters were recorded every 2 h via an arterial catheter placed in the right common carotid artery, a Swan-Gans thermodilution catheter (7F), that was placed in the pulmonary artery of the right middle-lobe in a wedge position through the external jugular vein, and another catheter in the internal jugular vein for measuring central venous pressure. Moreover, body weight, blood gases, pH, blood cells, electrolytes and serum enzymes were measured. Further serum traits as total protein and glucose and pathological alterations in different organs were recorded. The animals were observed for a period of 96 h and then killed painlessly. It was shown that pigs can survive 96-h anesthesia with the combination of ketamine and pentobarbital. Optimum, carefully controlled anesthesia did not impair the integrity of the regulatory mechanisms of circulation.

The major structural viral protein, VP1, of the human polyomavirus JC virus (JCV), the causative agent of progressive multifocal leukoencephalopathy (PML), was expressed by using recombinant baculoviruses. Recombinant VP1 formed virus-like particles (VLP) with the typical morphology of empty JCV capsids. Purified VP1 VLP bind to SVG, B, and T cells, as well as to monkey kidney cells. After binding, VP1 VLP were also internalized with high efficiency and transported to the nucleus. Immunization studies revealed these particles as highly immunogenic when administered with adjuvant, while immunization without adjuvant induced no immune response. VP1 VLP hyperimmune serum inhibits binding to SVG cells and neutralizes natural JCV. Furthermore, the potential of VP1 VLP as an efficient transporter system for gene therapy was demonstrated. Exogenous DNA could be efficiently packaged into VP1 VLP, and the packaged DNA was transferred into COS-7 cells as shown by the expression of a marker gene. Thus, VP1 VLP are useful for PML vaccine development and represent a potential new transporter system for human gene therapy.

To test the effects of C1-esterase inhibitor in scald burns on bacterial translocation and intestinal damage, standardized deep partial-thickness burns were inflicted on domestic pigs, scalding 30% of the skin surface for 25 s with 75 degrees C hot water. The animals (n = 17; weight 25-35 kg) were divided into three groups: I) the control group (n = 5) without scald burn; II) the group (n = 6) with scald burn; and III) the group with C1-inhibitor (n = 6): scald burn and treatment with C1-inhibitor (C1-INH; BERINERT, Behring, Marburg, Germany). Parameters measured and compared in this model were activity of complement system, hemodynamics, body weight, pathological organ alterations including intestinal lesions, bacterial translocation, and skin damage. C1-INH administration significantly decreased the plasma levels of the specific soluble membrane attack complex (SC5b-9), bacterial translocation, and the degree of intestinal ischemia in the postburn period compared with untreated animals. Moreover, animals treated with C1-INH exhibited a minor degree of organ alterations including damage of the skin and development of edema. The favorable effects of C1-INH may be explained by the protection of the intestinal and dermal microcirculation in the acute phase of thermal injury.

Standardized deep partial-thickness burns were inflicted on domestic pigs by scalding 30 per cent of the skin surface for 25 s with 75 degrees C hot water. The animals (n = 18; weight 25-35 kg) were divided into three groups: I, control group (n = 6), Ringer's lactate only; II, haemodialysate group (n = 6), Ringer's lactate and a protein-free haemodialysate of calf-blood (ACTIHAEMYL20%; AH) and III, C1-inhibitor group (n = 6), Ringer's lactate and C1-inhibitor (C1-INH; BERINERT). Skin biopsies were taken at defined time points (4, 28, 52 and 76 h) and investigated histologically. Depth of burn was determined morphometrically after coloration with a modified MTT-staining on frozen sections of the skin biopsies. Fluid therapy with C1-INH decelerated significantly the progression of the burn wound in the postburn-period compared to Ringer's lactate alone. In comparison with C1-INH, the treatment with AH demonstrated a less beneficial influence on the depth of scald burns. The favourable effects of C1-INH are explained by the protection of the dermal microcirculation during the acute phase of thermal injury.

The monoclonal antibody anti-APO-1 recognises a 52 kD cell membrane protein (APO-1) on some lymphoid tumour cell lines and on activated T cells. Binding of anti-APO-1 to cells expressing APO-1 results in programmed cell death, apoptosis, the most common form of death in eukaryotic cells. Expression of the antigen and sensitivity to the induction of cell death by anti-APO-1 were studied in human T-cell lines transformed by human leukaemia virus type 1 (HTLV-I) and in cultured cells from patients with adult T-cell leukaemia (ATL). APO-1 was strongly expressed on both types of cells and incubation of the cells with anti-APO-1 resulted in inhibition of proliferation and apoptosis. Induction of apoptosis may therefore be a possible therapeutic tool in HTLV-I-associated malignant disorders.

Cytological follow-up and histological results of 2336 patients with Pap III and 10584 with Pap II control of 1973 and 1974 were checked up to May 1976 and compared with new literature. 50% of Pap III became to negatives, 10% of Pap III and 0,82% of Pap II control became positive (Pap IV and Pap V). Up to now histological findings has been resulted in 10% invasive cancers; in 53% carcinomata in situ and severe dysplasia, in 16% moderate and mild dysplasias, and in 5% normal epithelium from repeated Pap III. To avoid to many conizations we have introduced Pap IIID for moderate and mild dysplasia into screening cytology.

348 cases of carcinoma in situ are reported, which were diagnosed, without exception, by conization from 1966 to 1971. The atypical changes could be removed without leaving any detectable malignant cells in situ in 226 patients (65 per cent). These cases did not need any further therapy. In 45 cases (12,9 per cent) was doubtful if the conization could be performed without leaving malignant cells. In 77 cases (22,1 per cent) the conization was done leaving malignant cells in situ. 49 women of this group had a continued treatment, the vast majority was hysterectomized. All the other cases were strictly controlled. The 5-year healing quotient was 91,7 per cent. 7,1 per cent of the patients have not been heard of again. Only 3 patients (0,9 per cent) suffered a recurrence. They belong, without exception, to the control group in which the carcinoma in situ could not be primarily removed without leaving malignant cells in situ. The significance of an exact method of conization and a careful histotechnical perparation of the specimens in serial sections is especially pointed out. The necessity of a continued treatment by means of hysterectomy with vaginal cuff is stressed in carcinoma in situ which could not be removed without leaving malignant cells in situ.