Gold Nanoparticles Bioproduced in Cyanobacteria in the Initial Phase Opened an Avenue for the Discovery of Corresponding Cerium Nanoparticles.

The production of isolated metallic nanoparticles with multifunctionalized properties, such as size and shape, is crucial for biomedical, photocatalytic, and energy storage or remediation applications. This study investigates the initial particle formations of gold nanoparticles (AuNPs) bioproduced in the cyanobacteria Anabaena sp. using high-resolution transmission electron microscopy images for digital image analysis. The developed method enabled the discovery of cerium nanoparticles (CeNPs), which were biosynthesized in the cyanobacteria Calothrix desertica. The particle size distributions for AuNPs and CeNPs were analyzed. After 10 h, the average equivalent circular diameter for AuNPs was 4.8 nm, while for CeNPs, it was approximately 5.2 nm after 25 h. The initial shape of AuNPs was sub-round to round, while the shape of CeNPs was more roundish due to their amorphous structure and formation restricted to heterocysts. The local PSDs indicate that the maturation of AuNPs begins in the middle of vegetative cells and near the cell membrane, compared to the other regions of the cell.

High-resolution particle size and shape analysis of the first Samarium nanoparticles biosynthesized from aqueous solutions via cyanobacteria Anabaena cylindrica.

Samarium (Sm) is one of the most sought-after rare earth metals. Price trends and dwindling resources are making recovery increasingly attractive. In this context, the use of cyanobacteria is highly promising. For Sm it was unclear whether Anabaena cylindrica produces particles through metabolically active Sm3+ uptake. High-resolution (HR) imaging now clearly demonstrates microbe generated biosynthesis of Sm nano-sized particles (Sm NPs) in vivo. Furthermore, a simple method to determine particle size and shape with high accuracy is presented. Digital image analysis with ImageJ of HR-TEMs is used to characterize Sm NPs revealing a nearly uniform local size distribution. Assuming round particles, the overall average area size is 135.5 nm2, resp. 11.9 nm diameter. In HR, where different cell sections of the same cell are averaged, the mean particle is smaller, 76.7 nm2 resp. 8.9 nm diameter. The reciprocal aspect ratio is 0.63. The Feret major axis ratio is calculated as shape factor, with 35% of the particles between 1.2 and 1.4. A roundness classification shows that 38% of particles are fairly round and 41% are very round. Consequently, A. cylindrica represents a suitable microorganism for possible Sm recovery and biosynthesis of roundish nano-sized particles.

Time-Dependent Size and Shape Evolution of Gold and Europium Nanoparticles from a Bioproducing Microorganism, a Cyanobacterium: A Digitally Supported High-Resolution Image Analysis.

Herein, the particle size distributions (PSDs) and shape analysis of in vivo bioproduced particles from aqueous Au3+ and Eu3+ solutions by the cyanobacterium Anabaena sp. are examined in detail at the nanoscale. Generally, biosynthesis is affected by numerous parameters. Therefore, it is challenging to find the key set points for generating tailored nanoparticles (NPs). PSDs and shape analysis of the Au and Eu-NPs were performed with ImageJ using high-resolution transmission electron microscopy (HR-TEM) images. As the HR-TEM image analysis reflects only a fraction of the detected NPs within the cells, additional PSDs of the complete cell were performed to determine the NP count and to evaluate the different accuracies. Furthermore, local PSDs were carried out at five randomly selected locations within a single cell to identify local hotspots or agglomerations. The PSDs show that particle size depends mainly on contact time, while the particle shape is hardly affected. The particles formed are distributed quite evenly within the cells. HR-PSDs for Au-NPs show an average equivalent circular diameter (ECD) of 8.4 nm (24 h) and 7.2 nm (51 h). In contrast, Eu-NPs preferably exhibit an average ECD of 10.6 nm (10 h) and 12.3 nm (244 h). Au-NPs are classified predominantly as "very round" with an average reciprocal aspect ratio (RAR) of ~0.9 and a Feret major axis ratio (FMR) of ~1.17. Eu-NPs mainly belong to the "rounded" class with a smaller RAR of ~0.6 and a FMR of ~1.3. These results show that an increase in contact time is not accompanied by an average particle growth for Au-NPs, but by a doubling of the particle number. Anabaena sp. is capable of biosorbing and bioreducing dissolved Au3+ and Eu3+ ions from aqueous solutions, generating nano-sized Au and Eu particles, respectively. Therefore, it is a low-cost, non-toxic and effective candidate for a rapid recovery of these sought-after metals via the bioproduction of NPs with defined sizes and shapes, providing a high potential for scale-up.

Plasma Supported Deposition of Amorphous Hydrogenated Carbon (a-C:H) on Polyamide 6: Determining Interlayer Completion and Dehydrogenation Effects during Layer Growth.

Polyamide 6 (PA6) is a commonly used material in many different sectors of modern industry. Herein, PA6 samples were coated with amorphous carbon layers (a-C:H) with increasing thickness up to 2 µm using radio frequency plasma enhanced chemical vapor deposition for surface adjustment. The morphology of the carbon coatings was inspected by ex situ atomic force microscopy and scanning electron microscopy. Surface wettability was checked by contact angle measurements. The chemical composition was analyzed using the surface sensitive synchrotron X-ray-based techniques near-edge X-ray absorption fine structure and X-ray photoelectron spectroscopy, supported by diffuse reflectance infrared Fourier transform spectroscopy. Particular attention was paid to the coating interval from 0 to 100 nm, to specify the interlayer thickness between the PA6 polymer and a-C:H coating, and the region between 1000 and 2000 nm, where dehydrogenation of the a-C:H layer occurs. The interlayer is decisive for the linkage of the deposited carbon layer on the polymer: the more pronounced it is, the better the adhesion. The thickness of the interlayer could be narrowed down to 40 nm in all used methods, and the dehydrogenation process takes place at a layer thickness of 1500 nm.

Comparing the Influence of Residual Stress on Composite Materials Made of Polyhydroxybutyrate (PHB) and Amorphous Hydrogenated Carbon (a-C:H) Layers: Differences Caused by Single Side and Full Substrate Film Attachment during Plasma Coating.

Polyhydroxybutyrate (PHB) is a bio-based, biodegradable and commercially used polymer, which in its native form is unfortunately not generally applicable. A widely used technique to adapt polymers to a wider range of applications is the surface modification with amorphous hydrogenated carbon (a-C:H) layers, realized by plasma-enhanced chemical vapor deposition (PE-CVD). However, this process creates intrinsic stress in the layer-polymer system which can even lead to full layer failure. The aim of this study was to investigate how the carbon layer is affected when the basic polymer film to be coated can follow the stress and bend (single side attachment) and when it cannot do so because it is firmly clamped (full attachment). For both attachment methods, the a-C:H layers were simultaneously deposited on PHB samples. Ex-situ characterization was performed using a scanning electron microscope (SEM) for surface morphology and contact angle (CA) measurements for wettability. In addition, the stress prevailing in the layer was calculated using the Stoney equation. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) measurements were used to investigate the chemical composition of the coating surface.

Reaction-diffusion fronts and the butterfly set.

A single-species reaction-diffusion model is used for studying the coexistence of multiple stable steady states. In these systems, one can define a potential-like functional that contains the stability properties of the states, and the essentials of the motion of wave fronts in one- and two-dimensional space. Using a quintic polynomial for the reaction term and taking advantage of the well-known butterfly bifurcation, we analyze the different scenarios involving the competition of two and three stable steady states, based on equipotential curves and points in parameter space. The predicted behaviors, including a front splitting instability, are contrasted to numerical integrations of reaction fronts in two dimensions.

Competing ternary surface reaction CO + O2 + H2 on Ir(111).

The CO oxidation on platinum-group metals under ultra-high-vacuum conditions is one of the most studied surface reactions. However, the presence of disturbing species and competing reactions are often neglected. One of the most interesting additional gases to be treated is hydrogen, due to its importance in technical applications and its inevitability under vacuum conditions. Adding hydrogen to the reaction of CO and O2 leads to more adsorbed species and competing reaction steps towards water formation. In this study, a model for approaching the competing surface reactions CO+O 2 + H2 is presented and discussed. Using the framework of bifurcation theory, we show how the steady states of the extended system correspond to a swallowtail catastrophe set with a tristable regime within the swallowtail. We explore numerically the possibility of reaching all stable states and illustrate the experimental challenges such a system could pose. Lastly, an approximative first-principle approach to diffusion illustrates how up to three stable states balance each other while forming heterogeneous patterns.

Refinement of Sustainable Polybutylene Adipate Terephthalate (PBAT) with Amorphous Hydrogenated Carbon Films (a-C:H) Revealing Film Instabilities Influenced by a Thickness-Dependent Change of sp2/sp3 Ratio.

The increasing use of polymers is related to a growing disposal problem. Switching to biodegradable polymers such as polybutylene adipate terephthalate (PBAT) is a feasible possibility, but after industrial production of commercially available material PBAT is not suitable for every application. Therefore, surface refinements with amorphous hydrogenated carbon films (a-C:H) produced by plasma-assisted chemical vapor deposition (PE-CVD) changing the top layer characteristics are used. Here, 50 µm-thick PBAT films are coated with a-C:H layers up to 500 nm in 50 nm steps. The top surface sp2/sp3 bonding ratios are analyzed by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) both synchrotron-based. In addition, measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) were performed for detailed chemical composition. Surface topography was analyzed by scanning electron microscopy (SEM) and the surface wettability by contact angle measurements. With increasing a-C:H layer thickness not only does the topography change but also the sp2 to sp3 ratio, which in combination indicates internal stress-induced phenomena. The results obtained provide a more detailed understanding of the mostly inorganic a-C:H coatings on the biodegradable organic polymer PBAT via in situ growth and stepwise height-dependent analysis.

Cyanobacterial promoted enrichment of rare earth elements europium, samarium and neodymium and intracellular europium particle formation.

In the recovery of rare earth elements (REE) microbial biosorption has shown its theoretical ability as an extremely economically and environmentally friendly production method in the last few years. To evaluate the ability of two cyanobacterial strains, namely Anabaena spec. and Anabaena cylindrica to enrich dissolved trivalent REE, a simple protocol was followed. The REE tested in this study include some of the most prominent representatives, such as europium (Eu), samarium (Sm) and neodymium (Nd). Within the experiments, a fast decrease of the REE3+ concentration in solution was tracked by inductively coupled plasma mass spectrometry (ICP-MS). It revealed an almost complete (>99%) biosorption of REE3+ within the first hour after the addition of metal salts. REE3+ uptake by biomass was checked using laser-induced breakdown spectroscopy (LIBS) and showed that all three selected REE3+ species were enriched in the cyanobacterial biomass and the process is assigned to a biosorption process. Although the biomass stayed alive during the experiments, up to that, a distinction whether the REE3+ was intra- or extracellularly sorbed was not possible, since biosorption is a metabolism independent process which occurs on living as well as non-living biomass. For europium it was shown by TEM that electron dense particles, presumably europium particles with particle sizes of about 15 nm, are located inside the vegetative cyanobacterial cells. This gave clear evidence that Eu3+ was actively sorbed by living cyanobacteria. Eu3+ biosorption by cell wall precipitation due to interaction with extracellular polysaccharides (EPS) could therefore be excluded. Finally, with XRD analysis it was shown that the detected europium particles had an amorphous instead of a crystalline structure. Herein, we present a fast biosorptive enrichment of the rare earth elements europium, samarium and neodymium by Anabaena spec. and Anabaena cylindrica and for the first time the subsequent formation of intracellular europium particles by Anabaena spec.

Detailed analysis of transitions in the CO oxidation on palladium(111) under noisy conditions.

It has been shown that CO oxidation on Pd(111) under ultrahigh vacuum conditions can suffer rare transitions between two stable states triggered by weak intrinsic perturbations. Here we study the effects of adding controlled noise by varying the concentrations of O2 and CO that feed the vacuum chamber, while the total flux stays constant. In addition to the regime of rare transitions between states of different CO2 reaction rates induced by intrinsic fluctuations, we found three distinct effects of external noise depending on its strength: small noise suppresses transitions and stabilizes the upper rate state; medium noise induces bursting; and large noise gives rise to reversible transitions in both directions. To explain some of the features present in the dynamics, we propose an extended stochastic model that includes a global coupling through the gas phase to account for the removal of CO gas caused by the adsorption of the Pd surface. The numerical simulations based in the model show a qualitative agreement with the noise-induced transitions found in experiments, but suggest that more complex spatial phenomena are present in the observed fluctuations.

Time-dependent growth of crystalline Au(0)-nanoparticles in cyanobacteria as self-reproducing bioreactors: 2. Anabaena cylindrica.

Microbial biosynthesis of metal nanoparticles as needed in catalysis has shown its theoretical ability as an extremely environmentally friendly production method in the last few years, even though the separation of the nanoparticles is challenging. Biosynthesis, summing up biosorption and bioreduction of diluted metal ions to zero valent metals, is especially ecofriendly, when the bioreactor itself is harmless and needs no further harmful reagents. The cyanobacterium Anabaena cylindrica (SAG 1403.2) is able to form crystalline Au(0)-nanoparticles from Au(3+) ions and does not release toxic anatoxin-a. X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and laser-induced breakdown spectroscopy (LIBS) are applied to monitor the time-dependent development of gold nanoparticles for up to 40 hours. Some vegetative cells (VC) are filled with nanoparticles within minutes, while the extracellular polymeric substances (EPS) of vegetative cells and the heterocyst polysaccharide layer (HEP) are the regions, where the first nanoparticles are detected on most other cells. The uptake of gold starts immediately after incubation and within four hours the average size remains constant around 10 nm. Analyzing the TEM images with an image processing program reveals a wide distribution for the diameter of the nanoparticles at all times and in all regions of the cyanobacteria. Finally, the nanoparticle concentration in vegetative cells of Anabaena cylindrica is about 50% higher than in heterocysts (HC). These nanoparticles are found to be located along the thylakoid membranes.

Morphological and Chemical Evolution of Gradually Deposited Diamond-Like Carbon Films on Polyethylene Terephthalate: From Subplantation Processes to Structural Reorganization by Intrinsic Stress Release Phenomena.

Diamond-like carbon (DLC) films on polyethylene terephthalate (PET) are nowadays intensively studied composites due to their excellent gas barrier properties and biocompatibility. Despite their applicative features being highly explored, the interface properties and structural film evolution of DLC coatings on PET during deposition processes are still sparsely investigated. In this study two different types of DLC films were gradually deposited on PET by radio frequency plasma-enhanced chemical vapor deposition (RF-PECVD) using acetylene plasma. The surface morphology of the deposited samples has been analyzed by atomic force microscopy (AFM). Their chemical composition was investigated by diffusive reflectance infrared Fourier transform (DRIFT) and Raman spectroscopy analysis and the surface wettability by contact angle measurements. Subplantation processes and interface effects are revealed through the morphological and chemical analysis of both types. During plasma deposition processes the increasing carbon load causes the rise of intrinsic film stress. It is proven that stress release phenomena cause the transition between polymer-like to a more cross-linked DLC network by folding dehydrogenated chains into closed 6-fold rings. These findings significantly lead to an enhanced understanding in DLC film growth mechanism by RF-PECVD processes.

Travelling fronts of the CO oxidation on Pd(111) with coverage-dependent diffusion.

In this work, we study a surface reaction on Pd(111) crystals under ultra-high-vacuum conditions that can be modeled by two coupled reaction-diffusion equations. In the bistable regime, the reaction exhibits travelling fronts that can be observed experimentally using photo electron emission microscopy. The spatial profile of the fronts reveals a coverage-dependent diffusivity for one of the species. We propose a method to solve the nonlinear eigenvalue problem and compute the direction and the speed of the fronts based on a geometrical construction in phase-space. This method successfully captures the dependence of the speed on control parameters and diffusivities.

CO oxidation on Ir(111) surfaces under large non-gaussian noise.

In this article we consider the CO oxidation on Ir(111) surfaces under large external noise with large autocorrelation imposed on the composition of the feed gas, both in experiments and in theory. We report new experimental results that show how the fluctuations force the reaction rate to jump between two well defined states. The statistics of the reaction rate depend on those of the external noise, and neither of them have a gaussian distribution, and thus they cannot be modeled by white or colored noise. A continuous-time discrete-state Markov process is proposed as a suitable model for the observed phenomena. The model captures the main features of the observed fluctuations and can be modified to accommodate other surface reactions and other systems under non-gaussian external noise.

A technique for extending the precision and the range of temperature programmed desorption toward extremely low coverages.

In this paper, an improvement of the temperature programmed desorption (TPD) technique is introduced, which facilitates fully automated sampling of TPD spectra with excellent reproducibility, especially useful for extremely low coverages. By averaging many sampled TPD spectra, the range of the TPD technique can be extended toward lower coverages, as well as the quality of the spectra can be improved. This allows for easy extraction of information about the adsorbate-surface bond. A state of the art TPD apparatus with a two chamber setup and a high quality quadrupole mass spectrometer was extended by automated components. These are an automated gas dosing system, ensuring precise dosing of gas, combined with a motor driven sample manipulation unit and a liquid nitrogen cryostat with automatic refilling. In addition all components were controlled by a computer. A large number of TPD cycles could be sampled without the need of interaction of an operator. Here, it is shown for up to more than 400 TPD cycles. This opens a wide range of new interesting applications for the TPD technique, especially in the limit of zero coverage. Here, basic experiments on well known adsorbate systems are shown to view the ability and limit of this approach.

Reaction hysteresis of the CO + O --> CO2 reaction on palladium(111).

Rate measurements of the reaction CO + O --> CO(2) on palladium(111) single crystal surfaces have been performed by means of mass spectroscopy under ultrahigh vacuum conditions. The total flux Phi of the impinging reactants CO and O(2) was held constant at 1 ML s(-1), whereas its CO fraction Y was varied between 0 (pure O(2)) and 1 (pure CO). The measurements have been performed for surface temperatures between 370 and 510 K and with a wide range of sampling times, evaluating the system parameter range for bistable behavior. Long-time measurements lasting several days proved the bistable behavior to result from two stable states rather than from slow processes not visible on usual experimental time scales. Pulselike modulations of the feed gas composition revealed the mechanisms confining the experimentally observed bistable range: the high CO fraction border of the bistability is given by the equistability condition of both states, whereas the other border is found to be associated with a saddle-node bifurcation in the corresponding system of reaction diffusion equations.

Noise-induced spatiotemporal patterns in a bistable reaction-diffusion system: photoelectron emission microscopy experiments and modeling of the oxidation reaction on Ir(111).

We use photoelectron emission microscopy (PEEM) measurements to study the spatiotemporal patterns obtained for the CO oxidation reaction on Ir(111) as a function of the noise strength we superpose on the CO and the oxygen fractions of the constant total reactant gas flux. The investigations are focused on the bistable regime this reaction displays including its monostable vicinity. Simultaneously we analyze numerically the underlying reaction-diffusion (RD) equations in two spatial dimensions. For intrinsic and/or small strength of the external noise we find transitions from the locally stable to the globally stable branch via slow nucleation and growth of islands of the globally stable state: oxygen or CO, respectively. With increasing noise strength the number of islands as well as their growth rate increases. These phenomena are very well reproduced by numerical calculations of the RD model. For sufficiently large noise strength we observe bursts from CO rich to oxygen rich and back as well as switching between the two states. While such phenomena are also obtained from the model calculations, their experimentally observed spatial scales were not satisfactorily reproduced using the same approach as for the lower noise strengths.

Spatiotemporal patterns of external noise-induced transitions in a bistable reaction-diffusion system: photoelectron emission microscopy experiments and modeling.

The rate of CO oxidation on Ir(111) surfaces exhibits bistability at T=500 K in a range of the CO fraction Y in the CO+O reactant gas flux. Measured CO2 rates as a function of the noise strength imposed on Y are well reproduced by parameter-free modeling. We present photoelectron emission microscopy measurements and 2D calculations of the spatiotemporal patterns of CO- and O-rich domains. The role of combined multiplicative and additive noise on Y for CO and O domain wall motion and island nucleation-growth-coalescence processes is analyzed.

External noise imposed on the reaction-diffusion system CO+O2-->CO2 on Ir(111) surfaces: experiment and theory.

We study experimentally and theoretically the influence of noise on the fractions of CO and oxygen in the constant gas flow directed at an Ir(111) surface during CO oxidation. Depending on the noise strength and the fraction Y of CO we observe in the deterministically bistable region a large variety of different types of behavior. These include bistable behavior for small noise intensities, transitions from the upper to the lower branch of the bistable loop and vice versa, island nucleation and growth and noise-induced switching. Near the boundary of the bistable region and in the presence of noise the transition between the two branches takes place via very slow domain wall motion with time scales of the order of 10(4)-10(5) s. The experiments were carried out in an UHV system for which the mass flow could be controlled very precisely. The modeling was using the reaction-diffusion system underlying the reaction studied for which all the kinetic coefficients are known rather precisely. Our numerical analysis was performed for one and two spatial dimensions showing qualitatively similar behavior. The comparison between the experimental results and the modeling shows semiquantitative to quantitative agreement.