Electron beam lithography designed chemical nanosensors based on localized surface plasmon resonance

Efficient nanochemosensors designed by electron beam lithography and based on localized surface plasmon resonance excited on noble metal nanocylinders are presented. Using localized surface plasmon resonance spectroscopy, we report here a high sensitivity corresponding to a density of about 18 × 10⁻²¹ mol of adsorbate per nanocylinders, we present the results obtained with gold and silver nanoparticles. This detection corresponds to less than one monolayer of molecules adsorbate on the nanoparticle. Additionally a subsequent layers deposition of polyelectrolytes is used to detect very thin polymer films. Although the results presented in this work are far from conclusive, the advantages of these nanochemosensors discussed here open the possibilities of further developments in a wide range of chemical and medical applications.     

TiO2 nanotubes: photocatalyst for cancer cell killing

The present work reports on the use of self‐organized TiO₂ nanotube layers for the photocatalytic killing of cancer cells. TiO₂ nanotube layers with different dimensions (diameter 50 nm and 100 nm, thickness 800 nm and 1.3 μm, respectively) were grown by anodization of Ti. Upon low dose of UV irradiation, the vitality of cancer cells cultured on these nanotube layers was significantly affected – the cells reduced their shape and size and a significant amount of the dead cells was found. These results demonstrate that self‐organized TiO₂ nanotube layers can be used for photo‐induced cancer cell killing. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure of colloidal complexes obtained from neutral/poly- electrolyte copolymers and oppositely charged surfactants

We report on the phase behavior and scattering properties of colloidal complexes made from block copolymers and surfactants. The copolymer is poly(sodium acrylate)-b-poly(acrylamide), hereafter abbreviated as PANa-PAM, with molecular weight 5000 g/mol for the first block and 30000 g/mol for the second. In aqueous solutions and neutral pH, poly(sodium acrylate) is a weak polyelectrolyte, whereas poly(acrylamide) is neutral and in good-solvent conditions. The surfactant is dodecyltrimethylammonium bromide (DTAB) and is of opposite charge with respect to the polyelectrolyte block. Combining dynamical light scattering and small-angle neutron scattering, we show that in aqueous solutions PANa-PAM diblocks and DTAB associate into colloidal complexes. For surfactant-to-polymer charge ratios Z lower than a threshold (Z(C) approximately 0.3), the complexes are single surfactant micelles decorated by few copolymers. Above the threshold, the colloidal complexes reveal an original core-shell microstructure. We have found that the core of typical radius 100-200 A is constituted from densely packed surfactant micelles connected by the polyelectrolyte blocks. The outer part of the colloidal complex is a corona and is made from the neutral poly(acrylamide) chains. Typical hydrodynamic sizes for the whole aggregate are around 1000 A. The aggregation numbers expressed in terms of numbers of micelles and copolymers per complex are determined and found to be comprised between 100-400, depending on the charge ratio Z and on the total concentration. We have also shown that the sizes of the complexes depend on the exact procedure of the sample preparation. We propose that the driving mechanism for the complex formation is similar to that involved in the phase separation of homopolyelectrolyte/surfactant systems. With copolymers, the presence of the neutral blocks prevents the macroscopic phase separation from occurring.     

Complexation and distribution of counterions in a grafted polyelectrolyte layer

The complexation and the distribution of various cations, bound to a poly(styrene sulfonate) brush, have been investigated using infra-red spectroscopy and neutron reflectivity. Small counterions (like tetremethylammonium) are distributed throughout the brush in such a way that a local electroneutrality is ensured. They also exchange readily with other bulk small cations. On the other hand, model polycations are irreversibly trapped to the brush despite a relative small number of ionic bonds involved in the complexation. These complexed polycations are localized at the outer border of the brush, forming a macromolecular barrier. However, this spatial segregation does not allow the buildup of polyelectrolyte multilayers. Cationic surfactants are associated stoichiometrically with the brush sulfonates but unlike small counterions, this complexation is “irreversible” and induces a restructuring of the polymer interface. Received 22 August 2000     

Hydration Structure and Intermolecular Interaction in Polyelectrolytes

In hydration, the intermolecular interaction is of decisive importance, since the ions modify the properties of the hydration water molecules, and the water molecules in turn have a strong influence on the interaction between the ions. These processes can be studied in detail with the aid of IR spectroscopy, which in addition provides a picture of the hydration structure. IR spectroscopy also shows that the excess protons are in energy bands and allows the detection of the proton dispersion forces acting between tunneling protons. The results of IR studies on polyelectrolytes contribute to our understanding of the many biological processes that depend on the behavior of ions.     

Zwitterionically modified hydroxypropylcellulose for biomedical applications

Novel polyelectrolytes have been synthesized by grafting sulfobetaine side chains onto hydroxypropylcellulose backbone. Polymers with various degrees of grafting have been obtained. The polymers do not interact with model anionic, cationic and zwitterionic surfactants as found in fluorescence studies using pyrene as a molecular probe. Dynamic light scattering (DLS) studies indicated that in the graft polymer solution two types of polymers are present. The films were formed from the grafted polymers. Using atomic force microscopy (AFM) technique it was found that they are resistant to the adhesion of proteins and can be used for the preparation of antiadhesive surfaces which may find biomedical applications.     

Colloidal micro- and nano-particles as templates for polyelectrolyte multilayer capsules

Colloidal particles play an important role in various areas of material and pharmaceutical sciences, biotechnology, and biomedicine. In this overview we describe micro- and nano-particles used for the preparation of polyelectrolyte multilayer capsules and as drug delivery vehicles. An essential feature of polyelectrolyte multilayer capsule preparations is the ability to adsorb polymeric layers onto colloidal particles or templates followed by dissolution of these templates. The choice of the template is determined by various physico-chemical conditions: solvent needed for dissolution, porosity, aggregation tendency, as well as release of materials from capsules. Historically, the first templates were based on melamine formaldehyde, later evolving towards more elaborate materials such as silica and calcium carbonate. Their advantages and disadvantages are discussed here in comparison to non-particulate templates such as red blood cells. Further steps in this area include development of anisotropic particles, which themselves can serve as delivery carriers. We provide insights into application of particles as drug delivery carriers in comparison to microcapsules templated on them.     

Electron stimulated desorption of H3O from 316L stainless steel

Surface ions generated by electron stimulated desorption from mass spectrometer ion source grids are frequently observed, but often misidentified. For example, in the case of mass 19, the source is often assumed to be surface fluorine, but since the metal oxide on grid surfaces has been shown to form water and hydroxides, a more compelling case can be made for the formation of hydronium. Further, fluorine is strongly electronegative, so it is rarely generated as a positive ion. A commonly used metal for ion source grids is 316L stainless steel. Thermal vacuum processing by bakeout or radiation heating from the filament typically alters the surface composition to predominantly Cr₂O₃. X-ray photoelectron spectral shoulders on the O 1s and Cr 2p_3/2 peaks can be attributed to adsorbed water and hydroxides, the intensity of which can be substantially increased by hydrogen dosing. On the other hand, the sub-peak intensities are substantially reduced by heating and/or by electron bombardment. Electron bombardment diode measurements show an initial work function increase corresponding to predominant hydrogen desorption (H₂) and a subsequent work function decrease corresponding to predominant oxygen desorption (CO). The fraction of hydroxide concentration on the surface was determined from X-ray photoelectron spectroscopy and from the deconvolution of temperature desorption spectra. Electron stimulated desorption yields from the surface show unambiguous H₃O⁺ peaks that can be significantly increased by hydrogen dosing. Time of flight secondary ion mass spectrometry sputter yields show small signals of H₃O⁺, as well as its constituents (H⁺, O⁺ and OH⁺) and a small amount of fluorine as F⁻, but no F⁺ or F⁺ complexes (HF⁺, etc.). An electron stimulated desorption cross-section of σ⁺ ∼ 1.4 × 10⁻²⁰ cm² was determined for H₃O⁺ from 316L stainless steel for hydrogen residing in surface chromium hydroxide.     

聚电解质复合物研究进展

本文介绍了聚电解质复合物的制备及研究方法，对影响聚电解质复合物形成及其结构的因素进行了阐述，简要介绍了其性能并对其应用前景作了展望。     

Essential dynamics and sidechain hydrogen bond cluster studies on eosinophil cationic protein

Eosinophil Cationic Protein (ECP) is a member of RNase A superfamily which carries out the obligatory catalytic role of cleaving RNA. It is involved in a variety of biological functions. Molecular dynamics simulations followed by essential dynamics analysis on this protein are carried out with the goal of gaining insights into the dynamical properties at atomic level. The top essential modes contribute to subspaces and to the transition phase. Further, the sidechain-sidechain/sidechain-mainchain hydrogen bond clusters are analyzed in the top modes, and compared with those of crystal structure. The role of residues identified by these methods is discussed in the context of concerted motion, structure and stability of the protein. Received 16 January 2002 Published online 13 September 2002