Impact of incubation conditions and post-treatment on the properties of bacterial cellulose membranes for pressure-driven filtration.

Bacterial cellulose (BC) has shown potential as a separation material. Herein, the performance of BC in pressure-driven separation is investigated as a function of incubation conditions and post-culture treatment. The pure water flux of never-dried BC (NDBC), was found to be 9 to 16 times higher than that for dried BC (DBC), in a pressure range of 0.25 to 2.5 bar. The difference in pressure response of NDBC and DBC was observed both in cross-flow filtration and capillary flow porometry experiments. DBC and NDBC were permeable to polymers with a hydrodynamic radius of ∼60 nm while protein retention was possible by introducing anionic surface charges on BC. The results of this work are expected to expand the development of BC-based filtration membranes, for instance towards the processing of biological fluids.

Effects of Chloride Concentration on the Water Disinfection Performance of Silver Containing Nanocellulose-based Composites.

The availability of microbially-safe drinking water is a challenge in many developing regions. Due to the well-known antibacterial effect of silver ions, materials used for their controlled release have been widely studied for point-of-use water disinfection. However, even if it is in principle known that chloride anions can suppress the antibacterial efficiency of silver, the majority of previous studies, surprisingly, have not focused on chloride concentrations relevant for freshwaters and thus for practical applications. Here, we prepared low-cost nanocellulose-aluminium oxyhydroxide nanocomposites functionalized with silver nanoparticles. Field samples obtained from Chennai, India were used as a guideline for choosing relevant chloride concentrations for the antibacterial studies, i.e., 10, 90, and 290 ppm. The antibacterial performance of the material against Escherichia coli and Bacillus subtilis was demonstrated and the influence of chloride concentration on the antibacterial effect was studied with E. coli. A 1 h contact time led to bacterial reductions of 5.6 log10, 2.9 log10, and 2.2 log10, respectively. This indicates that an increase of chloride concentration leads to a substantial reduction of antibacterial efficiency, even within chloride concentrations found in freshwaters. This work enables further insights for designing freshwater purification systems that utilize silver-releasing materials.

Cooperative colloidal self-assembly of metal-protein superlattice wires.

Material properties depend critically on the packing and order of constituent units throughout length scales. Beyond classically explored molecular self-assembly, structure formation in the nanoparticle and colloidal length scales have recently been actively explored for new functions. Structure of colloidal assemblies depends strongly on the assembly process, and higher structural control can be reliably achieved only if the process is deterministic. Here we show that self-assembly of cationic spherical metal nanoparticles and anionic rod-like viruses yields well-defined binary superlattice wires. The superlattice structures are explained by a cooperative assembly pathway that proceeds in a zipper-like manner after nucleation. Curiously, the formed superstructure shows right-handed helical twisting due to the right-handed structure of the virus. This leads to structure-dependent chiral plasmonic function of the material. The work highlights the importance of well-defined colloidal units when pursuing unforeseen and complex assemblies.Colloidal self-assembly is a unique method to produce three-dimensional materials with well-defined hierarchical structures and functionalities. Liljeström et al. show controlled preparation of macroscopic chiral wires with helical plasmonic superlattice structure composed of metal nanoparticles and viruses.

Micropatterning of silver nanoclusters embedded in polyvinyl alcohol films.

Direct laser writing has been utilized to fabricate highly photostable fluorescent nanocluster microstructures in an organic polymer poly(methacrylic acid), where the carboxyl functional group is reported to play a vital role in nanocluster stabilization. In this Letter, we demonstrate that not only the polymer containing the carboxyl functional group, but also the polymer comprising the hydroxyl group, namely polyvinyl alcohol (PVA), can act as an appropriate stabilizer matrix for laser-induced synthesis and patterning of silver nanoclusters. The as-formed nanoclusters in the PVA film exhibit broadband emission and photostability comparable to the nanoclusters formed in the poly(methacrylic acid) polymer. As PVA is a widely used, nontoxic, biocompatible and biodegradable polymer, the technique of patterning fluorescent nanoclusters in PVA thin films is expected to find numerous applications in fields like fluorescence imaging, biolabeling, and sensing.

Chiral Plasmonics Using Twisting along Cellulose Nanocrystals as a Template for Gold Nanoparticles.

The right-handed twist along aqueous dispersed cellulose nanocrystals allows right-handed chiral plasmonics upon electrostatic binding of gold nanoparticles in dilute environment, through tuning the particle sizes and concentrations. Simulations using nanoparticle coordinates from cryo-electron tomography confirm the experimental results. The finding suggests generalization for other chiral and helical colloidal templates for nanoscale chiral plasmonics.

Sub-micron scale patterning of fluorescent silver nanoclusters using low-power laser.

Noble metal nanoclusters are ultrasmall nanomaterials with tunable properties and huge application potential; however, retaining their enhanced functionality is difficult as they readily lose their properties without stabilization. Here, we demonstrate a facile synthesis of highly photostable silver nanoclusters in a polymer thin film using visible light photoreduction. Furthermore, the different stages of the nanocluster formation are investigated in detail using absorption and fluorescence spectroscopy, fluorescence microscopy, and atomic force microscopy. A cost-effective fabrication of photostable micron-sized fluorescent silver nanocluster barcode is demonstrated in silver-impregnated polymer films using a low-power continuous-wave laser diode. It is shown that a laser power of as low as 0.75 mW is enough to write fluorescent structures, corresponding to the specifications of a commercially available laser pointer. The as-formed nanocluster-containing microstructures can be useful in direct labeling applications such as authenticity marking and fluorescent labeling.

Key roles of carbon solubility in single-walled carbon nanotube nucleation and growth.

Elucidating the roles played by carbon solubility in catalyst nanoparticles is required to better understand the growth mechanisms of single-walled carbon nanotubes (SWNTs). Here, we highlight that controlling the level of dissolved carbon is of key importance to enable nucleation and growth. We first performed tight binding based atomistic computer simulations to study carbon incorporation in metal nanoparticles with low solubilities. For such metals, carbon incorporation strongly depends on their structures (face centered cubic or icosahedral), leading to different amounts of carbon close to the nanoparticle surface. Following this idea, we then show experimentally that Au nanoparticles effectively catalyze SWNT growth when in a face centered cubic structure, and fail to do so when icosahedral. Both approaches emphasize that the presence of subsurface carbon in the nanoparticles is necessary to enable the cap lift-off, making the nucleation of SWNTs possible.

Rapid Cationization of Gold Nanoparticles by Two-Step Phase Transfer.

Cationic gold nanoparticles offer intriguing opportunities as drug carriers and building blocks for self-assembled systems. Despite major progress on gold nanoparticle research in general, the synthesis of cationic gold particles larger than 5 nm remains a major challenge, although these species would give a significantly larger plasmonic response compared to smaller cationic gold nanoparticles. Herein we present the first reported synthesis of cationic gold nanoparticles with tunable sizes between 8-20 nm, prepared by a rapid two-step phase-transfer protocol starting from simple citrate-capped particles. These cationic particles form ordered self-assembled structures with negatively charged biological components through electrostatic interactions.

Simple and efficient separation of atomically precise noble metal clusters.

There is an urgent need for accessible purification and separation strategies of atomically precise metal clusters in order to promote the study of their fundamental properties. Although the separation of mixtures of atomically precise gold clusters Au25L18, where L are thiolates, has been demonstrated by advanced separation techniques, we present here the first separation of metal clusters by thin-layer chromatography (TLC), which is simple yet surprisingly efficient. This method was successfully applied to a binary mixture of Au25L18 with different ligands, as well as to a binary mixture of different cluster cores, Au25 and Au144, protected with the same ligand. Importantly, TLC even enabled the challenging separation of a multicomponent mixture of mixed-monolayer-protected Au25 clusters with closely similar chemical ligand compositions. We anticipate that the realization of such simple yet efficient separation technique will progress the detailed investigation of cluster properties.

Direct laser writing of photostable fluorescent silver nanoclusters in polymer films.

Metal nanoclusters consist of a few to a few hundred atoms and exhibit attractive molecular properties such as ultrasmall size, discrete energy levels, and strong fluorescence. Although patterning of these clusters down to the micro- or nanoscale could lead to applications such as high-density data storage, it has been reported only for inorganic matrices. Here we present submicron-scale mask-free patterning of fluorescent silver nanoclusters in an organic matrix. The nanoclusters were produced by direct laser writing in poly(methacrylic acid) thin films and exhibit a broadband emission at visible wavelengths with photostability that is superior to that of Rhodamine 6G dye. This fabrication method could open new opportunities for applications in nanophotonics like imaging, labeling, and metal ion sensing. We foresee that this method can be further applied to prepare other metal nanoclusters embedded in compositionally different polymer matrices.

Mixed-Monolayer-Protected Au25 Clusters with Bulky Calix[4]arene Functionalities.

Although various complex, bulky ligands have been used to functionalize plasmonic gold nanoparticles, introducing them to small, atomically precise gold clusters is not trivial. Here, we demonstrate a simple one-pot procedure to synthesize fluorescent magic number Au25 clusters carrying controlled amounts of bulky calix[4]arene functionalities. These clusters are obtained from a synthesis feed containing binary mixtures of tetrathiolated calix[4]arene and 1-butanethiol. By systematic variation of the molar ratio of ligands, clusters carrying one to eight calixarene moieties were obtained. Structural characterization reveals unexpected binding of the calix[4]arenes to the Au25 cluster surface with two or four thiolates per moiety.

Low-cost reduced graphene oxide-based conductometric nitrogen dioxide-sensitive sensor on paper.

The fabrication concept for a low-cost sensor device using reduced graphene oxide (rGO) as the sensing material on a porous paper substrate is presented. The sensors were characterized using conductivity and capacitance measurements, atomic force microscopy and X-ray photoelectron spectroscopy. The effects of different reducing agents, graphene oxide (GO) flake size and film thickness were studied. The sensor was sensitive to NO2, and devices based on a thin (10-nm) hydrazine-reduced GO layer had the best sensitivity, reaching a 70% reduction in resistance after 10 min of exposure to 10 ppm NO2. The sensitivity was high enough for the detection of sub-parts per million levels of NO2. Desorption of gas molecules, i.e. the recovery of the sensor, could be accelerated by UV irradiation. The structure and preparation of the sensor are simple and up-scalable, allowing their fabrication in bulk quantities, and the fabrication concept can be applied to other materials, too.