Cyclotrimerization Approach to Symmetric [9]Helical Indenofluorenes: Diverting Cyclization Pathways.

Catalytic cyclotrimerization routes to symmetrical [9]helical indenofluorene were explored by using different transition-metal complexes and thermal conditions. Depending on the reaction conditions, the cyclotrimerizations were accompanied by dehydro-Diels-Alder reaction giving rise to another type of aromatic compounds. Structures of both symmetrical [9]helical cyclotrimerization product as well as the dehydro-Diels-Alder product were confirmed by single-crystal X-ray diffraction analyses. Limits of enantioselective cyclotrimerization were assessed as well. DFT calculations shed light on the reaction course and the origin of diminished enantioselectivity.

Biodegradable Nanohybrid Materials as Candidates for Self-Sanitizing Filters Aimed at Protection from SARS-CoV-2 in Public Areas.

The COVID-19 pandemic has raised the problem of efficient, low-cost materials enabling the effective protection of people from viruses transmitted through the air or via surfaces. Nanofibers can be a great candidate for efficient air filtration due to their structure, although they cannot protect from viruses. In this work, we prepared a wide range of nanofibrous biodegradable samples containing Ag (up to 0.6 at.%) and Cu (up to 20.4 at.%) exhibiting various wettability. By adjusting the magnetron current (0.3 A) and implanter voltage (5 kV), the deposition of TiO2 and Ag+ implantation into PCL/PEO nanofibers was optimized in order to achieve implantation of Ag+ without damaging the nanofibrous structure of the PCL/PEO. The optimal conditions to implant silver were achieved for the PCL-Ti0.3-Ag-5kV sample. The coating of PCL nanofibers by a Cu layer was successfully realized by magnetron sputtering. The antiviral activity evaluated by widely used methodology involving the cultivation of VeroE6 cells was the highest for PCL-Cu and PCL-COOH, where the VeroE6 viability was 73.1 and 68.1%, respectively, which is significantly higher compared to SARS-CoV-2 samples without self-sanitizing (42.8%). Interestingly, the samples with implanted silver and TiO2 exhibited no antiviral effect. This difference between Cu and Ag containing nanofibers might be related to the different concentrations of ions released from the samples: 80 µg/L/day for Cu2+ versus 15 µg/L/day for Ag+. The high antiviral activity of PCL-Cu opens up an exciting opportunity to prepare low-cost self-sanitizing surfaces for anti-SARS-CoV-2 protection and can be essential for air filtration application and facemasks. The rough cost estimation for the production of a biodegradable nanohybrid PCL-Cu facemask revealed ~$0.28/piece, and the business case for the production of these facemasks would be highly positive, with an Internal Rate of Return of 34%.

Rhodium-Catalyzed Enantioselective Synthesis of Highly Fluorescent and CPL-Active Dispiroindeno[2,1-c]fluorenes.

The enantioselective synthesis of chiral [7]-helical dispirodihydro[2,1-c]indenofluorenes (DSF-IFs) was achieved for the first time in good yields with high er values (er up to 99 : 1). The crucial step of the whole reaction sequence was the enantioselective intramolecular [2+2+2] cycloaddition of tethered triynediols to indenofluorenediols, which was catalyzed by a Rh/SEGPHOS® complex. Further transformations led to the corresponding DSF-IFs. The prepared helically chiral DSF-IFs combine circularly polarized luminescence (CPL) activity (glum =∼10-3 ) with exceptionally high fluorescence quantum yields (up to Φlum =0.97).

Straightforward Synthesis and Properties of Highly Fluorescent [5]- and [7]-Helical Dispiroindeno[2,1-c]fluorenes.

This work presents a general approach for synthesis of substituted [5]-helical dispiroindeno[2,1-c]fluorenes based on Rh-catalyzed intramolecular cyclotrimerization of triynes. This approach was further extended for the first synthesis of configurationally stable [7]-helical dispiroindeno[2,1-c]fluorenes. A series of variously substituted derivatives was prepared and their photophysical and electrochemical properties were evaluated. Their fluorescence emission maxima were in the region of 351-428 nm and quantum yields up to 88 % are the highest measured among the full-carbon helical compounds.

Analysis of epoxy functionalized layers synthesized by plasma polymerization of allyl glycidyl ether.

The deposition of epoxide groups by plasma polymerization opens new horizons for robust and quick immobilization of biomolecules on any type of substrate. However, as of now there are just very few papers dealing with the deposition of epoxy layers by plasma polymerization, probably due to the high reactivity of this group leading to a low functionalization efficiency. In this work we carried out an extensive experimental and theoretical investigation of plasma synthesis of epoxide groups from a low pressure allyl glycydyl ether (AGE) plasma. The influence of composite parameter W/F and the working pressure on the density of epoxide groups and the layer stability was thoroughly addressed. It was found that by increasing the working pressure it is possible to sufficiently raise the concentration of epoxide groups. The composite parameter W/F was shown to be a crucial parameter in affecting the density of epoxides. An optimal value of W/F of around 2.3 eV per molecule leading to the highest density of epoxides produced in the process at 15 Pa was revealed through FT-IR and XPS findings. This value correlates well with the ab initio calculations suggesting that the lowest bond dissociation energy belongs to the C-O bond of the epoxide ring. Therefore, in order to increase the density of epoxides deposited by plasma polymerization, a precursor molecule containing at least two epoxide rings is strongly advised to be employed.

Universal dispersion model for characterization of optical thin films over a wide spectral range: application to hafnia.

A dispersion model capable of expressing the dielectric response of a broad class of optical materials in a wide spectral range from far IR to vacuum UV is described in detail. The application of this universal dispersion model to a specific material is demonstrated using the ellipsometric and spectrophotometric characterization of a hafnia film prepared by vacuum evaporation on silicon substrate. The characterization utilizes simultaneous processing of data from multiple techniques and instruments covering the wide spectral range and includes the characterization of roughness, nonuniformity, transition layer, and native oxide layer on the back of the substrate. It is shown how the combination of measurements in light reflected from both sides of the sample and transmitted light allows the separation of weak absorption in films and substrates. This approach is particularly useful in the IR region where the absorption structures in films and substrates often overlap and a prior measurement of the bare substrate may be otherwise necessary for precise separation. Individual phenomena that contribute to the dielectric response, i.e., interband electronic transitions, electronic excitations involving the localized states, and phonon absorption, are discussed in detail. A quantitative analysis of absorption on localized states, permitting the separation of transitions between localized states from transitions between localized and extended states, is utilized to obtain estimates of the density of localized states and film stoichiometry.

Enantioselective Construction of 3-Hydroxypiperidine Scaffolds by Sequential Action of Light and Rhodium upon N-Allylglyoxylamides.

3-Hydroxypiperidine scaffolds were enantioselectively constructed in an atom-economical way by sequential action of light and rhodium upon N-allylglyoxylamides. In a formal sense, the allylic C-H bond was selectively cleaved and enantioselectively added across the ketonic carbonyl group with migration of the double bond (carbonyl-ene-type reaction).

Consolidated series for efficient calculation of the reflection and transmission in rough multilayers.

Fresnel reflectance and transmittance coefficients of a thin film system consisting of an arbitrary number of layers are expressed explicitly in the form of a power series of Fresnel coefficients for individual boundaries and phase terms for the individual films. The series is based on the evaluation of all possible paths light can pass through the system. However, the series is written as consolidated, i. e. all paths corresponding to the same powers are represented using a single term in the series, with multiplicity which is a simple product of binomial coefficients. This result is used to express the normal reflectance of a thin film system with arbitrarily correlated randomly rough boundaries and it is shown that such approach can be computationally efficient in practice.

Measurement of thickness distribution, optical constants, and roughness parameters of rough nonuniform ZnSe thin films.

Epitaxial ZnSe thin films exhibiting two important defects, i.e., boundary roughness and thickness nonuniformity, prepared on GaAs substrates, are optically characterized using a combination of variable-angle spectroscopic ellipsometry, spectroscopic near-normal reflectometry, and imaging spectroscopic reflectometry (ISR). The influence of boundary roughness is incorporated into optical quantity formulas by the Rayleigh-Rice theory. Thickness nonuniformity is included using averaging of the unnormalized Mueller matrices. The dispersion model of the optical constants of the ZnSe films is based on parametrization of the joint density of electronic states. Very thin overlayers represented by thin films with identically rough boundaries are taken into account on the upper boundaries of the ZnSe films. Standard optical techniques are used to determine the spectral dependencies of the optical constants of the ZnSe films, together with the parameters of roughness and thickness nonuniformity. ISR is then used to find the maps of the local thickness and local rms value of height irregularities. The values of roughness parameters, determined using the standard techniques and ISR, are verified by a comparison with results obtained by atomic force microscopy.

Possible charge ordering and anomalous transport in graphene/graphene quantum dot heterostructure.

Observations of superconductivity and charge density waves (CDW) in graphene have been elusive thus far due to weak electron-phonon coupling (EPC) interactions. Here, we report a unique observation of anomalous transport and multiple charge ordering phases at high temperatures (T1∼213K,T2∼325K) in a 0D-2D van der Waals (vdW) heterostructure comprising of single layer graphene (SLG) and functionalized (amine) graphene quantum dots (GQD). The presence of functionalized GQD contributed to charge transfer with shifting of the Dirac point ∼ 0.05 eV above the Fermi level (ab initio simulations) and carrier densityn∼-0.3×1012 cm-2confirming p-doping in SLG and two-fold increase in EPC interaction was achieved. Moreover, we elucidate the interplay between electron-electron and electron-phonon interactions to substantiate high temperature EPC driven charge ordering in the heterostructure through analyses of magnetotransport and weak anti-localization (WAL) framework. Our results provide impetus to investigate strongly correlated phenomena such as CDW and superconducting phase transitions in novel graphene based heterostructures.

The Biomimetic Synthesis of Polyarylated Fluorenes, Relevant to Selaginellaceae Polyphenols, Leading to the Spontaneous Formation of Stable Radicals.

This work reports a biomimetic synthesis of polyarylated fluorene derivatives. The molecules are formed via intramolecular electrophilic aromatic substitution, resembling a cyclization leading towards the natural selaginpulvilins from selaginellins. The scope of the reaction was investigated, and the products were obtained in 60-95 % yields. Some of the compounds decompose to a stable radical. We investigated the nature and the origin of the radical using experimental methods, including EPR or electrochemical measurements, as well as theoretical methods, such as DFT calculations. Based on our observations, we hypothesize, that phenoxy radicals are formed in the first instance, which however undergo internal rearrangement to thermodynamically more stable carbon-centered radicals. The preliminary data also show the cytotoxic properties of some of the molecules.

Scanning Probe Microscopy controller with advanced sampling support.

A low-cost Digital Signal Processor (DSP) unit for advanced Scanning Probe Microscopy measurements is presented. It is based on Red Pitaya board and custom built electronic boards with additional high bit depth AD and DA converters. By providing all the necessary information (position and time) with each data point collected it can be used for any scan path, using either existing libraries for scan path generation or creating adaptive scan paths using Lua scripting interface. The DSP is also capable of performing statistical calculations, that can be used for decision making during scan or for the scan path optimisation on the DSP level.

Enhanced Adhesion of Electrospun Polycaprolactone Nanofibers to Plasma-Modified Polypropylene Fabric.

Excellent adhesion of electrospun nanofiber (NF) to textile support is crucial for a broad range of their bioapplications, e.g., wound dressing development. We compared the effect of several low- and atmospheric pressure plasma modifications on the adhesion between two parts of composite-polycaprolactone (PCL) nanofibrous mat (functional part) and polypropylene (PP) spunbond fabric (support). The support fabrics were modified before electrospinning by low-pressure plasma oxygen treatment or amine plasma polymer thin film or treated by atmospheric pressure plasma slit jet (PSJ) in argon or argon/nitrogen. The adhesion was evaluated by tensile test and loop test adapted for thin NF mat measurement and the trends obtained by both tests largely agreed. Although all modifications improved the adhesion significantly (at least twice for PSJ treatments), low-pressure oxygen treatment showed to be the most effective as it strengthened adhesion by a factor of six. The adhesion improvement was ascribed to the synergic effect of high treatment homogeneity with the right ratio of surface functional groups and sufficient wettability. The low-pressure modified fabric also stayed long-term hydrophilic (ten months), even though surfaces usually return to a non-wettable state (hydrophobic recovery). In contrast to XPS, highly surface-sensitive water contact angle measurement proved suitable for monitoring subtle surface changes.

Injecting hyaluronan in the thoracolumbar fascia: A model study.

Hyaluronan (HA) has been recently identified as a key component of the densification of thoracolumbar fascia (TLF), a potential contributor to non-specific lower back pain (LBP) currently treated with manual therapy and systemic or local delivery of anti-inflammatory drugs. The aim of this study was to establish a novel animal model suitable for studying ultrasound-guided intrafascial injection prepared from HA with low and high Mw. Effects of these preparations on the profibrotic switch and mechanical properties of TLF were measured by qPCR and rheology, respectively, while their lubricating properties were evaluated by tribology. Rabbit proved to be a suitable model of TLF physiology due to its manageable size enabling both TLF extraction and in situ intrafascial injection. Surprisingly, the tribology showed that low Mw HA was a better lubricant than the high Mw HA. It was also better suited for intrafascial injection due to its lower injection force and ability to freely spread between TLF layers. No profibrotic effects of either HA preparation in the TLF were observed. The intrafascial application of HA with lower MW into the TLF appears to be a promising way how to increase the gliding of the fascial layers and target the myofascial LBP.

Advanced Zinc-Magnesium Alloys Prepared by Mechanical Alloying and Spark Plasma Sintering.

Zinc and its alloys are considered as promising materials for the preparation of biodegradable medical devices (stents and bone fixation screws) due to their enhanced biocompatibility. These materials must achieve an ideal combination of mechanical and corrosion properties that can be influenced by alloying or thermomechanical processes. This paper presents the effects of different mechanical alloying (MA) parameters on the composition of Zn-1Mg powder. At the same time, this study describes the influence of preparation by MA on Zn-6Mg and Zn-16Mg alloys. The selected powders were compacted by the spark plasma sintering (SPS) method. Subsequently, their microstructures were studied and their mechanical properties were tested. The overall process led to a significant grain refinement (629 ± 274 nm for Zn-1Mg) and the formation of new intermetallic phases (Mg2Zn11, MgZn2). The compressive properties of the sintered samples were mainly related to the concentration of the alloying elements, where an increase in concentration led to an improvement in strength but a deterioration in ductility. According to the obtained results, the best properties were obtained for the Zn-1Mg alloy.

Ultrafine-Grained Zn-Mg-Sr Alloy Synthesized by Mechanical Alloying and Spark Plasma Sintering.

Zinc materials are considered promising candidates for bioabsorbable medical devices used for the fixation of broken bones or stents. Materials for these applications must meet high mechanical property requirements. One of the ways to fulfil these demands is related to microstructure refinement, particularly the decrease in grain size. In the present work, we combine two powder metallurgy techniques (mechanical alloying-MA, and spark plasma sintering-SPS) to prepare Zn-1Mg-0.5Sr nanograin material. The microstructure of compacted material consisted of Zn grains and particles of Mg2Zn11 intermetallic phases from 100 to 500 nm in size, which resulted in high values of hardness and a compressive strength equal to 86 HV1 and 327 MPa, respectively. In this relation, the combination of the suggested techniques provides an innovative way to form extremely fine microstructures without significant coarsening during powder compaction at increased temperatures.

Roadmap for 2D materials in biotribological/biomedical applications - A review.

The human body involves a large number of systems subjected to contact stresses and thus experiencing wear and degradation. The limited efficacy of existing solutions constantly puts a significant financial burden on the healthcare system, more importantly, patients are suffering due to the complications following a partial or total system failure. More effective strategies are highly dependent on the availability of advanced functional materials demonstrating excellent tribological response and good biocompatibility. In this article, we review the recent progress in implementing two-dimensional (2D) materials into bio-applications involving tribological contacts. We further summarize the current challenges for future progress in the field.

Long-Range Magnetic Order in Nickel Hydroxide-Functionalized Graphene Quantum Dots.

In this work, we demonstrate the prospect of chemically synthesizing transition metal (Ni) doped magnetic graphene quantum dots (GQDs) with the sole aim of shedding light on their magnetic properties. Our results show that adsorption of nickel hydroxide on predominantly paramagnetic GQDs reveals antiferromagnetic ordering in the M-T profile around 10 K with change of the spin exchange coupling deviating from J = 1/2 to J = 1, mainly arising from the d-p mixing hybridization between the p orbital of carbon from the GQD and the d orbital of Ni. Furthermore, our results are well complemented by ab initio simulations showing asymmetry of the up and down spins around the Fermi level for nickel hydroxide-doped GQDs with long-range spin polarization. Furthermore, the magnitude of the net magnetic moment generated for doped GQDs on the carbon atoms is found to be site-dependent (surface or edge).

Modular synthesis of 1-α- and 1-ß-(indol-2-yl)-2'-deoxyribose C-nucleosides.

A simple two-step method for the selective preparation of anomerically pure 1α- and 1ß-(indol-2-yl)deoxyribose derivatives was developed. The synthesis was based on the Sonogashira reaction of 1α- and 1ß-ethynyldeoxyribose and 2-haloanilines followed by a Pd-complex catalyzed cyclization to the corresponding indolyldeoxyribosides.

Synthetic Data in Quantitative Scanning Probe Microscopy.

Synthetic data are of increasing importance in nanometrology. They can be used for development of data processing methods, analysis of uncertainties and estimation of various measurement artefacts. In this paper we review methods used for their generation and the applications of synthetic data in scanning probe microscopy, focusing on their principles, performance, and applicability. We illustrate the benefits of using synthetic data on different tasks related to development of better scanning approaches and related to estimation of reliability of data processing methods. We demonstrate how the synthetic data can be used to analyse systematic errors that are common to scanning probe microscopy methods, either related to the measurement principle or to the typical data processing paths.