Extending molecular dynamics with dipolar NMR tensors as constraints to chiral phosphorus compounds.

Molecular dynamics with orientational constraints (MDOC) simulations use NMR parameters as tensorial constraints in the stereochemical analysis of small molecules. 13C-31P Residual dipolar couplings-aided MDOC simulations of small phosphorus molecules determined the relative configurations of rigid molecules after including 3JH-H-couplings as additional constraints. However, flexible molecules remain a problem.

Microstructure and physical properties of black-aluminum antireflective films.

The microstructure and physical properties of reflective and black aluminum were compared for layers of different thicknesses deposited by magnetron sputtering on fused silica substrates. Reflective Al layers followed the Volmer-Weber growth mechanism classically observed for polycrystalline metal films. On the contrary, the extra nitrogen gas used to deposit the black aluminum layers modified the growth mechanism and changed the film morphologies. Nitrogen cumulated in the grain boundaries, favoring the pinning effect and stopping crystallite growth. High defect concentration, especially vacancies, led to strong columnar growth. Properties reported for black aluminum tend to be promising for sensors and emissivity applications.

Insoluble Network Skeleton and Soluble Components of Nylon 6,6-Sputtered Nanoparticles: Insights from Liquid-State and Solid-State NMR Analysis.

In this study, we performed a detailed analysis of -sputtered-nylon 6,6 plasma polymer nanoparticles (NPs). Following a previous study using standard techniques such as X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy, we employed unconventional approaches, specifically solid- and liquid-state high-resolution nuclear magnetic resonance (NMR) spectroscopy, supplemented by gel permeation chromatography (GPC). Scanning electron microscopy (SEM) was also used to examine changes in the size of the NPs after contact with solvents and after heating. Our investigations revealed suspected strong binding and networking of the NPs, and a soluble monomer/oligomer phase was identified and characterised. This fraction is removable using solvent or heat treatment without significantly affecting the size of the NPs. Additionally, we suggested the chemical structure of this soluble phase. Our findings support the proposed rubber-like character of plasma polymer NPs and explain their strong tendency to reflect from substrates upon high-speed impact.

Laser-Treated MXene as an Electrochemical Agent to Boost Properties of Semitransparent Photoelectrode Based on Titania Nanotubes.

In this study, Ti3C2Tx underwent laser treatment to reshape it, resulting in the formation of a TiO2/Ti3C2Tx heterojunction. The interaction with laser light induced the formation of spherical TiO2 composed of an anatase-rutile phase on the Ti3C2Tx surface. Such a heterostructure was loaded over a titania nanotube (TNT) layer, and the surface area was enhanced through immersion in a TiCl4 solution followed by thermal treatment. Consequently, the photon-to-electron conversion efficiency exhibits a 10-fold increase as compared to bare TNT. Moreover, for the sample produced with optimized conditions, five times higher photoactivity is observed in comparison to bare TNT. It was shown that under visible light irradiation the most photoactive heterojunction based on the tubular layer reveals a substantial drop in the charge transfer resistance of about 32% with respect to the dark condition. This can be attributed to the narrower band gaps of the modified material and improvement of the separation efficiency of the photogenerated electron-hole pairs. Overall results suggest that this investigation underscores TiO2/Ti3C2Tx as a promising noble-metal-free material that enhances both the electrochemical and photoelectrochemical performances of electrode materials based on TNT that can be further used in light-harvesting applications.

One-step synthesis of photoluminescent nanofluids by direct loading of reactively sputtered cubic ZrN nanoparticles into organic liquids.

ZrN nanofluids may exhibit unique optoelectronic properties because of the matching of the solar spectrum with interband transitions and localized surface plasmon resonance (LSPR). Nevertheless, these nanofluids have scarcely been investigated, mainly because of the complexity of the current synthetic routes that involve aggressive chemicals and high temperatures. This work aims to validate reactive dc magnetron sputtering of zirconium in Ar/N2 as an environmentally benign, annealing-free method to produce 22 nm-sized, highly crystalline, stoichiometric, electrically conductive, and plasmonic ZrN nanoparticles (NPs) of cubic shape and to load them into vacuum-compatible liquids of different chemical compositions (polyethylene glycol (PEG), paraffin, and pentaphenyl trimethyl trisiloxane (PTT)) in one step. The nanofluids demonstrate LSPR in the red/near-IR range that gives them a bluish color in transmittance. The nanofluids also demonstrate complex photoluminescence behavior such that ZrN NPs enhance the photoluminescence (PL) intensity of paraffin and PEG, whereas the PL of PTT remains almost invariable. Based on DFT calculations, different energetic barriers to charge transfer between ZrN and the organic molecules are suggested as the main factors that influence the observed optoelectronic response. Overall, our study provides a novel approach to the synthesis of transition metal nitride nanofluids in an environmentally friendly manner, deepens the understanding of the interactions between ZrN and organic molecules, and unveils new optoelectronic phenomena in such systems.

Silver nanoparticles with plasma-polymerized hexamethyldisiloxane coating on 3D printed substrates are non-cytotoxic and effective against respiratory pathogens.

Due to the emerging resistance of microorganisms and viruses to conventional treatments, the importance of self-disinfecting materials is highly increasing. Such materials could be silver or its nanoparticles (AgNPs), both of which have been studied for their antimicrobial effect. In this study, we compared the biological effects of AgNP coatings with and without a plasma-polymerized hexamethyldisiloxane (ppHMDSO) protective film to smooth silver or copper coatings under three ambient conditions that mimic their potential medical use (dry or wet environments and an environment simulating the human body). The coatings were deposited on 3D printed polylactic acid substrates by DC magnetron sputtering, and their surface morphology was visualized using scanning electron microscopy. Cytotoxicity of the samples was evaluated using human lung epithelial cells A549. Furthermore, antibacterial activity was determined against the Gram-negative pathogenic bacterium Pseudomonas aeruginosa PAO1 and antiviral activity was assessed using human rhinovirus species A/type 2. The obtained results showed that overcoating of AgNPs with ppHMDSO creates the material with antibacterial and antiviral activity and at the same time without a cytotoxic effect for the surrounding tissue cells. These findings suggest that the production of 3D printed substrates coated with a layer of AgNPs-ppHMDSO could have potential applications in the medical field as functional materials.

Plasmonic Ag/Cu/PEG nanofluids prepared when solids meet liquids in the gas phase.

Since the time of Faraday's experiments, the optical response of plasmonic nanofluids has been tailored by the shape, size, concentration, and material of nanoparticles (NPs), or by mixing different types of NPs. To date, water-based liquids have been the most extensively investigated host media, while polymers, such as poly(ethylene glycol) (PEG), have frequently been added to introduce repulsive steric interactions and protect NPs from agglomeration. Here, we introduce an inverse system of non-aqueous nanofluids, in which Ag and Cu NPs are dispersed in PEG (400 g mol-1), with no solvents or chemicals involved. Our single-step approach comprises the synthesis of metal NPs in the gas phase using sputtering-based gas aggregation cluster sources, gas flow transport of NPs, and their deposition (optionally simultaneous) on the PEG surface. Using computational fluid dynamics simulations, we show that NPs diffuse into PEG at an average velocity of the diffusion front of the order of µm s-1, which is sufficient for efficient loading of the entire polymer bulk. We synthesize yellow Ag/PEG, green Cu/PEG, and blue Ag/Cu/PEG nanofluids, in which the color is given by the position of the plasmon resonance. NPs are prone to partial agglomeration and sedimentation, with a slower kinetics for Cu. Density functional theory calculations combined with UV-vis data and zeta-potential measurements prove that the surface oxidation to Cu2O and stronger electrostatic repulsion are responsible for the higher stability of Cu NPs. Adopting the De Gennes formalism, we estimate that PEG molecules adsorb on the NP surface in mushroom coordination, with the thickness of the adsorbed layer L < 1.4 nm, grafting density σ < 0.20, and the average distance between the grafted chains D > 0.8 nm. Such values provide sufficient steric barriers to retard, but not completely prevent, agglomeration. Overall, our approach offers an excellent platform for fundamental research on non-aqueous nanofluids, with metal-polymer and metal-metal interactions unperturbed by the presence of solvents or chemical residues.

Push-pull amino-nitro helicenes: synthesis, (chir)optical properties and self-assembly into thin films.

A series of regioisomeric push-pull amino-nitro [6]helicenes and a related [7]helicene derivative were prepared and their racemates resolved into enantiomers. Compared to the parent helicenes, they exhibit red-shifted UV-Vis spectra, pronounced dipole moments, altered chiroptical properties such as remarkable optical rotatory power, and can form nanocrystalline Langmuir-Blodgett films.

Mechanical time-of-flight filter based on slotted disks and helical rotor for measurement of velocities of nanoparticles.

A mechanical time-of-flight filter intended for measurement of velocities of nanoparticles exiting a gas aggregation source has been developed. Several configurations maximizing simplicity, throughput or resolution are suggested and investigated both theoretically and experimentally. It is shown that the data measured using such filters may be easily converted to the real velocity distribution with high precision. Furthermore, it is shown that properly designed filters allow for the monitoring of the velocity of nanoparticles even at the conditions with extremely low intensity of the nanoparticle beam.

Degradable Poly(ethylene oxide)-Like Plasma Polymer Films Used for the Controlled Release of Nisin.

Poly(ethylene oxide) (PEO)-like thin films were successfully prepared by plasma-assisted vapor thermal deposition (PAVTD). PEO powders with a molar weight (Mw) between 1500 g/mol and 600,000 g/mol were used as bulk precursors. The effect of Mw on the structural and surface properties was analyzed for PEO films prepared at a lower plasma power. Fourier transform (FTIR-ATR) spectroscopy showed that the molecular structure was well preserved regardless of the Mw of the precursors. The stronger impact of the process conditions (the presence/absence of plasma) was proved. Molecular weight polydispersity, as well as wettability, increased in the samples prepared at 5 W. The influence of deposition plasma power (0-30 W) on solubility and permeation properties was evaluated for a bulk precursor of Mw 1500 g/mol. The rate of thickness loss after immersion in water was found to be tunable in this way, with the films prepared at the highest plasma power showing higher stability. The effect of plasma power deposition conditions was also shown during the permeability study. Prepared PEO films were used as a cover, and permeation layers for biologically active nisin molecule and a controlled release of this bacteriocin into water was achieved.

Investigation of Ag/a-C:H Nanocomposite Coatings on Titanium for Orthopedic Applications.

One of the leading causes of failure for any bone implant is implant-associated infections. The implant-bone interface is in fact the crucial site of infection where both the microorganisms and cells compete to populate the newly introduced implant surface. Most of the work dealing with this issue has focused on the design of implant coatings capable of preventing infection while ignoring cell proliferation or vice versa. The present study is therefore focused on investigating the antibacterial and biological properties of nanocomposite coatings based on an amorphous hydrocarbon (a-C:H) matrix containing silver nanoparticles (AgNPs). a-C:H coatings with varying silver concentrations were generated directly on medical grade titanium substrates using a combination of a gas aggregation source (GAS) and a plasma-enhanced chemical vapor deposition (PE-CVD) process. The obtained results revealed that the surface silver content increased from 1.3 at % to 5.3 at % by increasing the used DC magnetron current in the GAS from 200 to 500 mA. The in vitro antibacterial assays revealed that the nanocomposites with the highest number of silver content exhibited excellent antibacterial activities resulting in a 6-log reduction of Escherichia coli and a 4-log reduction of Staphylococcus aureus after 24 h of incubation. An MTT assay, fluorescence live/dead staining, and SEM microscopy observations of MC3T3 cells seeded on the uncoated and coated Ti substrates also showed that increasing the amount of AgNPs in the nanocomposites had no notable impact on their cytocompatibility, while improved cell proliferation was especially observed for the nanocomposites possessing a low amount of AgNPs. These controllable Ag/a-C:H nanocomposites on Ti substrates, which simultaneously provide an excellent antibacterial performance and good biocompatibility, could thus have promising applications in orthopedics and other biomedical implants.

Plasma Polymerization of Acrylic Acid for the Tunable Synthesis of Glassy and Carboxylated Nanoparticles.

Polymer nanoparticles (NPs) can be highly attractive in numerous applications, including biomedicine, where the use of inorganic matter may be detrimental for living tissues. In conventional wet chemistry, polymerization and functionalization of NPs with specific chemical groups involves complex and often numerous reactions. Here, we report on a solvent-free, single-step, low-temperature plasma-based synthesis of carboxylated NPs produced by the polymerization of acrylic acid under the conditions of a glow discharge. In a monomer-deficient regime, the strong fragmentation of monomer molecules by electron impact results in the formation of 15 nm-sized NPs with <1% retention of the carboxyl groups. In an energy-deficient regime, larger 90 nm-sized NPs are formed with better retention of carboxyl groups that reaches 16%. All types of NPs exhibit a glass transition above room temperature, which makes them highly stable in an aqueous environment with no dissolution or swelling. The NPs are also found to degrade thermally when heated above 150 °C, with a decrease in the mean NP size but with retention of the chemical composition. Thus, plasma polymerization proves to be a versatile approach for the production of polymer NPs with a tunable size distribution, chemical composition, and physical properties.

Magnetron Sputtering of Polymeric Targets: From Thin Films to Heterogeneous Metal/Plasma Polymer Nanoparticles.

Magnetron sputtering is a well-known technique that is commonly used for the deposition of thin compact films. However, as was shown in the 1990s, when sputtering is performed at pressures high enough to trigger volume nucleation/condensation of the supersaturated vapor generated by the magnetron, various kinds of nanoparticles may also be produced. This finding gave rise to the rapid development of magnetron-based gas aggregation sources. Such systems were successfully used for the production of single material nanoparticles from metals, metal oxides, and plasma polymers. In addition, the growing interest in multi-component heterogeneous nanoparticles has led to the design of novel systems for the gas-phase synthesis of such nanomaterials, including metal/plasma polymer nanoparticles. In this featured article, we briefly summarized the principles of the basis of gas-phase nanoparticles production and highlighted recent progress made in the field of the fabrication of multi-component nanoparticles. We then introduced a gas aggregation source of plasma polymer nanoparticles that utilized radio frequency magnetron sputtering of a polymeric target with an emphasis on the key features of this kind of source. Finally, we presented and discussed three strategies suitable for the generation of metal/plasma polymer multi-core@shell or core-satellite nanoparticles: the use of composite targets, a multi-magnetron approach, and in-flight coating of plasma polymer nanoparticles by metal.

Cu nanoparticles constrain segmental dynamics of cross-linked polyethers: a trade-off between non-fouling and antibacterial properties.

Copper has a strong bactericidal effect against multi-drug resistant pathogens and polyethers are known for their resistance to biofilm formation. Herein, we combined Cu nanoparticles (NPs) and a polyether plasma polymer in the form of nanocomposite thin films and studied whether both effects can be coupled. Cu NPs were produced by magnetron sputtering via the aggregation in a cool buffer gas whereas polyether layers were synthesized by Plasma-Assisted Vapor Phase Deposition with poly(ethylene oxide) (PEO) used as a precursor. In situ specific heat spectroscopy and XPS analysis revealed the formation of a modified polymer layer around the NPs which propagates on the scale of a few nanometers from the Cu NP/polymer interface and then transforms into a bulk polymer phase. The chemical composition of the modified layer is found to be ether-deficient due to the catalytic influence of copper whereas the bulk polymer phase exhibits the chemical composition close to the original PEO. Two cooperative glass transition phenomena are revealed that belong to the modified polymer layer and the bulk phase. The former is characterized by constrained mobility of polymer segments which manifests itself via a 30 K increase of dynamic glass transition temperature. Furthermore, the modified layer is characterized by the heterogeneous structure which results in higher fragility of this layer as compared to the bulk phase. The Cu NPs/polyether thin films exhibit reduced protein adsorption; however, the constrained segmental dynamics leads to the deterioration of the non-fouling properties for ultra-thin polyether coatings. The films are found to have a bactericidal effect against multi-drug resistant Gram-positive Methicillin-Resistant Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa.

Magnetron-sputtered copper nanoparticles: lost in gas aggregation and found by in situ X-ray scattering.

Magnetron discharge in a cold buffer gas represents a liquid-free approach to the synthesis of metal nanoparticles (NPs) with tailored structure, chemical composition and size. Despite a large number of metal NPs that were successfully produced by this method, the knowledge of the mechanisms of their nucleation and growth in the discharge is still limited, mainly because of the lack of in situ experimental data. In this work, we present the results of in situ Small Angle X-ray Scattering measurements performed in the vicinity of a Cu magnetron target with Ar used as a buffer gas. Condensation of atomic metal vapours is found to occur mainly at several mm distance from the target plane. The NPs are found to be captured preferentially within a region circumscribed by the magnetron plasma ring. In this capture zone, the NPs grow to the size of 90 nm whereas smaller ones sized 10-20 nm may escape and constitute a NP beam. Time-resolved measurements of the discharge indicate that the electrostatic force acting on the charged NPs may be largely responsible for their capturing nearby the magnetron.

Comparative study of antibacterial properties of polystyrene films with TiO x and Cu nanoparticles fabricated using cluster beam technique.

Background: Antibacterial materials are of high importance for medicine, and for the production and conservation of food. Among these materials, polymer films with metal nanoparticles (NPs) are of considerable interest for many practical applications. Results: The paper describes a novel approach for the formation of bactericidal polymer thin films (polystyrene in this case), produced by spin-coating, with Ti and Cu NPs deposited from cluster beams. Ti NPs are treated in three different ways in order to study different approaches for oxidation and, thus, efficiency in formation of the particles with semiconducting properties required for the catalytic formation of reactive oxygen species. Cu NPs are used as deposited. Partial NP embedding into polystyrene is realised in a controllable manner using thermal annealing in order to improve surface adhesion and make the particles resistant against wash-out. The formed composite films with TiO x and Cu species are tested as bactericidal media using E.coli bacteria as model microorganisms. Conclusion: The obtained results show considerable efficiency in destroying the bacteria and a good possibility of multiple re-use of the same composite films making the suggested approach attractive for the cases requiring reusable polymer-based antibacterial media.

Carboxyl-Functionalized Nanoparticles Produced by Pulsed Plasma Polymerization of Acrylic Acid.

Carboxyl-enriched and size-selected polymer nanoparticles (NPs) may prove to be very useful in biomedical applications for linker-free binding of biomolecules and their transport to cells. In this study, we report about the synthesis of such NPs by low-pressure low-temperature pulsed plasma polymerization of acrylic acid. Gas aggregation cluster source was adapted to operate plasma with a constant pulse period of 50 µs and with varying duty cycle. The NPs were produced with the size ranging from 31 ± 5 to 93 ± 14 nm and with retention of the carboxyl groups ranging from 4.0 to 12.0 atom %. Two regimes of the NP formation were identified. In the large duty cycle regime, the NP growth was interfered with by positive ion bombardment which resulted in the ion-driven detachment of the carboxyl species and in the formation of carboxyl-deficient NPs. In the small duty cycle regime, the NP growth was accompanied by the radical-driven chain propagation with the attachment of intact monomer molecules. Improved efficacy of the monomer retention resulted in increased concentration of the carboxyl groups.

Advances and challenges in the field of plasma polymer nanoparticles.

This contribution reviews plasma polymer nanoparticles produced by gas aggregation cluster sources either via plasma polymerization of volatile monomers or via radio frequency (RF) magnetron sputtering of conventional polymers. The formation of hydrocarbon, fluorocarbon, silicon- and nitrogen-containing plasma polymer nanoparticles as well as core@shell nanoparticles based on plasma polymers is discussed with a focus on the development of novel nanostructured surfaces.

Comparison of Reflectance Measurements Acquired with a Contact Probe and an Integration Sphere: Implications for the Spectral Properties of Vegetation at a Leaf Level.

Laboratory spectroscopy in visible and infrared regions is an important tool for studies dealing with plant ecophysiology and early recognition of plant stress due to changing environmental conditions. Leaf optical properties are typically acquired with a spectroradiometer coupled with an integration sphere (IS) in a laboratory or with a contact probe (CP), which has the advantage of operating flexibility and the provision of repetitive in-situ reflectance measurements. Experiments comparing reflectance spectra measured with different devices and device settings are rarely reported in literature. Thus, in our study we focused on a comparison of spectra collected with two ISs on identical samples ranging from a Spectralon and coloured papers as reference standards to vegetation samples with broadleaved (Nicotiana Rustica L.) and coniferous (Picea abies L. Karst.) leaf types. First, statistical measures such as mean absolute difference, median of differences, standard deviation and paired-sample t-test were applied in order to evaluate differences between collected reflectance values. The possibility of linear transformation between spectra was also tested. Moreover, correlation between normalised differential indexes (NDI) derived for each device and all combinations of wavelengths between 450 nm and 1800 nm were assessed. Finally, relationships between laboratory measured leaf compounds (total chlorophyll, carotenoids and water content), NDI and selected spectral indices often used in remote sensing were studied. The results showed differences between spectra acquired with different devices. While differences were negligible in the case of the Spectralon and they were possible to be modelled with a linear transformation in the case of coloured papers, the spectra collected with the CP and the ISs differed significantly in the case of vegetation samples. Regarding the spectral indices calculated from the reflectance data collected with the three devices, their mean values were in the range of the corresponding standard deviations in the case of broadleaved leaf type. Larger differences in optical leaf properties of spruce needles collected with the CP and ISs are implicated from the different measurement procedure due to needle-like leaf where shoots with spatially oriented needles were measured with the CP and individual needles with the IS. The study shows that a direct comparison between the spectra collected with two devices is not advisable as spectrally dependent offsets may likely exist. We propose that the future studies shall focus on standardisation of measurement procedures so that open access spectral libraries could serve as a reliable input for modelling of optical properties on a leaf level.

Response of green reflectance continuum removal index to the xanthophyll de-epoxidation cycle in Norway spruce needles.

A dedicated field experiment was conducted to investigate the response of a green reflectance continuum removal-based optical index, called area under the curve normalized to maximal band depth between 511 nm and 557 nm (ANMB511-557), to light-induced transformations in xanthophyll cycle pigments of Norway spruce [Picea abies (L.) Karst] needles. The performance of ANMB511-557 was compared with the photochemical reflectance index (PRI) computed from the same leaf reflectance measurements. Needles of four crown whorls (fifth, eighth, 10th, and 15th counted from the top) were sampled from a 27-year-old spruce tree throughout a cloudy and a sunny day. Needle optical properties were measured together with the composition of the photosynthetic pigments to investigate their influence on both optical indices. Analyses of pigments showed that the needles of the examined whorls varied significantly in chlorophyll content and also in related pigment characteristics, such as the chlorophyll/carotenoid ratio. The investigation of the ANMB511-557 diurnal behaviour revealed that the index is able to follow the dynamic changes in the xanthophyll cycle independently of the actual content of foliar pigments. Nevertheless, ANMB511-557 lost the ability to predict the xanthophyll cycle behaviour during noon on the sunny day, when the needles were exposed to irradiance exceeding 1000 µmol m(-2) s(-1). Despite this, ANMB511-557 rendered a better performance for tracking xanthophyll cycle reactions than PRI. Although declining PRI values generally responded to excessive solar irradiance, they were not able to predict the actual de-epoxidation state in the needles examined.