Graphene oxide-polyamine preprogrammable nanoreactors with sensing capability for corrosion protection of materials.

Corrosion is one of the major issues for sustainable manufacturing globally. The annual global cost of corrosion is US$2.5 trillion (approximately 3.4% of the world's GDP). The traditional ways of corrosion protection (such as barriers or inhibiting) are either not very effective (in the case of barrier protection) or excessively expensive (inhibiting). Here, we demonstrate a concept of nanoreactors, which are able to controllably release or adsorb protons or hydroxides directly on corrosion sites, hence, selectively regulating the corrosion reactions. A single nanoreactor comprises a nanocompartment wrapped around by a pH-sensing membrane represented, respectively, by a halloysite nanotube and a graphene oxide/polyamine envelope. A nanoreactor response is determined by the change of a signaling pH on a given corrosion site. The nanoreactors are self-assembled and suitable for mass-line production. The concept creates sustainable technology for developing smart anticorrosion coatings, which are nontoxic, selective, and inexpensive.

Trends in Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) infection and vaccine antibody prevalence in a multi-ethnic inner-city antenatal population: A cross-sectional surveillance study.

OBJECTIVE: To determine severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) seroprevalence in pregnancy in an inner-city setting and assess associations with demographic factors and vaccination timing. DESIGN: Repeated cross-sectional surveillance study. SETTING: London maternity centre. SAMPLE: A total of 906 pregnant women attending nuchal scans, July 2020-January 2022. METHODS: Blood samples were tested for IgG antibodies against SARS-CoV-2 nucleocapsid (N) and spike (S) proteins. Self-reported vaccination status and coronavirus disease 2019 (COVID-19) infection were recorded. Multivariable regression models determined demographic factors associated with seroprevalence and antibody titres. MAIN OUTCOME MEASURES: Immunoglobulin G N- and S-protein antibody titres. RESULTS: Of the 960 women, 196 (20.4%) were SARS-CoV-2 seropositive from previous infection. Of these, 70 (35.7%) self-reported previous infection. Among unvaccinated women, women of black ethnic backgrounds were most likely to be SARS-CoV-2 seropositive (versus white adjusted risk ratio [aRR] 1.88, 95% CI 1.35-2.61, p < 0.001). Women from black and mixed ethnic backgrounds were least likely to have a history of vaccination with seropositivity to S-protein (versus white aRR 0.58, 95% CI 0.40-0.84, p = 0.004; aRR 0.56, 95% CI 0.34-0.92, p = 0.021, respectively). Double vaccinated, previously infected women had higher IgG S-protein antibody titres than unvaccinated, previously infected women (mean difference 4.76 fold-change, 95% CI 2.65-6.86, p < 0.001). Vaccination timing before versus during pregnancy did not affect IgG S-antibody titres (mean difference -0.28 fold-change, 95% CI -2.61 to 2.04, p = 0.785). CONCLUSIONS: This cross-sectional study demonstrates high rates of asymptomatic SARS-CoV-2 infection with women of black ethnic backgrounds having higher infection risk and lower vaccine uptake. SARS-CoV-2 antibody titres were highest among double-vaccinated, infected women.

Heterocyclic ring expansion yields anthraquinone derivatives potent against multidrug resistant tumor cells.

Chemical modifications of anthraquiones are aimed at novel derivatives with improved antitumor properties. Emergence of multidrug resistance (MDR) due to overexpression of transmembrane ATP binding cassette transporters, in particular, MDR1/P-glycoprotein (Pgp), can limit the use of anthraquinone based drugs. Previously we have demonstrated that annelation of modified five-membered heterocyclic rings with the anthraquinone core yielded a series of compounds with optimized antitumor properties. In the present study we synthesized a series of anthraquinone derivatives with six-membered heterocycles. Selected new compounds showed the ability to kill parental and MDR tumor cell lines at low micromolar concentrations. Molecular docking into the human Pgp model revealed a stronger interaction of 2-methylnaphtho[2,3-g]quinoline-3-carboxamide 17 compared to naphtho[2,3-f]indole-3-carboxamide 3. The time course of intracellular accumulation of compound 17 in parental K562 leukemia cells and in Pgp-positive K562/4 subline was similar. In contrast, compound 3 was readily effluxed from K562/4 cells and was significantly less potent for this subline than for K562 cells. Together with reported strategies of drug optimization of the anthracycline core, these results add ring expansion to the list of perspective modifications of heteroarene-fused anthraquinones.

Graphene-Based Technologies for Tackling COVID-19 and Future Pandemics.

The COVID-19 pandemic highlighted the need for rapid tools and technologies to combat highly infectious viruses. The excellent electrical, mechanical and other functional properties of graphene and graphene-like 2D materials (2DM) can be utilized to develop novel and innovative devices to tackle COVID-19 and future pandemics. Here, the authors outline how graphene and other 2DM-based technologies can be used for the detection, protection, and continuous monitoring of infectious diseases including COVID-19. The authors highlight the potential of 2DM-based biosensors in rapid testing and tracing of viruses to enable isolation of infected patients, and stop the spread of viruses. The possibilities of graphene-based wearable devices are discussed for continuous monitoring of COVID-19 symptoms. The authors also provide an overview of the personal protective equipment, and potential filtration mechanisms to separate, destroy or degrade highly infectious viruses, and the potential of graphene and other 2DM to increase their efficiency, and enhance functional and mechanical properties. Graphene and other 2DM could not only play a vital role for tackling the ongoing COVID-19 pandemic but also provide technology platforms and tools for the protection, detection and monitoring of future viral diseases.

Molecular Mechanisms of the Deregulation of Muscle Contraction Induced by the R90P Mutation in Tpm3.12 and the Weakening of This Effect by BDM and W7.

Point mutations in the genes encoding the skeletal muscle isoforms of tropomyosin can cause a range of muscle diseases. The amino acid substitution of Arg for Pro residue in the 90th position (R90P) in γ-tropomyosin (Tpm3.12) is associated with congenital fiber type disproportion and muscle weakness. The molecular mechanisms underlying muscle dysfunction in this disease remain unclear. Here, we observed that this mutation causes an abnormally high Ca2+-sensitivity of myofilaments in vitro and in muscle fibers. To determine the critical conformational changes that myosin, actin, and tropomyosin undergo during the ATPase cycle and the alterations in these changes caused by R90P replacement in Tpm3.12, we used polarized fluorimetry. It was shown that the R90P mutation inhibits the ability of tropomyosin to shift towards the outer domains of actin, which is accompanied by the almost complete depression of troponin's ability to switch actin monomers off and to reduce the amount of the myosin heads weakly bound to F-actin at a low Ca2+. These changes in the behavior of tropomyosin and the troponin-tropomyosin complex, as well as in the balance of strongly and weakly bound myosin heads in the ATPase cycle may underlie the occurrence of both abnormally high Ca2+-sensitivity and muscle weakness. BDM, an inhibitor of myosin ATPase activity, and W7, a troponin C antagonist, restore the ability of tropomyosin for Ca2+-dependent movement and the ability of the troponin-tropomyosin complex to switch actin monomers off, demonstrating a weakening of the damaging effect of the R90P mutation on muscle contractility.

All-Dielectric Nanostructures with a Thermoresponsible Dynamic Polymer Shell.

We suggest a new strategy for creating stimuli-responsive bio-integrated optical nanostructures based on Mie-resonant silicon nanoparticles covered by an ensemble of similarity negatively charged polyelectrolytes (heparin and sodium polystyrene sulfonate). The dynamic tuning of the nanostructures' optical response is due to light-induced heating of the nanoparticles and swelling of the polyelectrolyte shell. The resulting hydrophilic/hydrophobic transitions significantly change the shell thickness and reversible shift of the scattering spectra for individual nanoparticles up to 60 nm. Our findings bring novel opportunities for the application of smart nanomaterials in nanomedicine and bio-integrated nanophotonics.

Coupling pH-Regulated Multilayers with Inorganic Surfaces for Bionic Devices and Infochemistry.

This article summarizes more than 10 years of cooperation with Prof. Helmuth Möhwald. Here we describe how the research moved from light-regulated feedback sustainable systems and control biodevices to the current focus on infochemistry in aqueous solution. An important advanced characteristic of such materials and devices is the pH concentration gradient in aqueous solution. A major part of the article focuses on the use of localized illumination for proton generation as a reliable, minimal-reagent-consuming, stable light-promoted proton pump. The in situ scanning vibration electrode technique (SVET) and scanning ion-selective electrode technique (SIET) are efficient for the spatiotemporal evolution of ions on the surface. pH-sensitive polyelectrolyte (PEs) multilayers with different PE architectures are composed with a feedback loop for bionic devices. We show here that pH-regulated PE multilayers can change their properties-film thickness and stiffness, permeability, hydrophilicity, and/or fluorescence-in response to light or electrochemical or biological processes instead of classical acid/base titration.

Microbubbles trigger oscillation of crystal size in solids.

An understanding of the nature and conditions of nonlinear processes in open systems is important for modulation of the microstructure of solids at a new level of complexity. We demonstrate that cavitation generated by high intensity ultrasound (HIUS) triggers nonlinear processes in microparticles and layers of titanium. We reveal a non-monotonic dependence of the size of grains in the treated solids on sonication time, and oscillation of titanium grain sizes vs. time of ultrasonic treatment, indicating the influence of two opposing forces: cavitation driven impact of shock heating and shear stress on surfaces. These nonlinear self-organization processes in solids promise new microstructured materials with applications among others in bio- and geosciences.

Shape-Dependent Interactions of Palladium Nanocrystals with Hydrogen.

Elucidation of the nature of hydrogen interactions with palladium nanoparticles is expected to play an important role in the development of new catalysts and hydrogen-storage nanomaterials. A facile scaled-up synthesis of uniformly sized single-crystalline palladium nanoparticles with various shapes, including regular nanocubes, nanocubes with protruded edges, rhombic dodecahedra, and branched nanoparticles, all stabilized with a mesoporous silica shell is developed. Interaction of hydrogen with these nanoparticles is studied by using temperature-programmed desorption technique and by performing density functional theory modeling. It is found that due to favorable arrangement of Pd atoms on their surface, rhombic dodecahedral palladium nanoparticles enclosed by {110} planes release a larger volume of hydrogen and have a lower desorption energy than palladium nanocubes and branched nanoparticles. These results underline the important role of {110} surfaces in palladium nanoparticles in their interaction with hydrogen. This work provides insight into the mechanism of catalysis of hydrogenation/dehydrogenation reactions by palladium nanoparticles with different shapes.

Effect of Cavitation Bubble Collapse on the Modification of Solids: Crystallization Aspects.

This review examines the concepts how cavitation bubble collapse affects crystalline structure, the crystallization of newly formed structures, and recrystallization. Although this subject can be discussed in a broad sense across the area of metastable crystallization, our main focus is discussing specific examples of the inorganic solids: metal, intermetallics, metal oxides, and silicon. First, the temperature up to which ultrasound heats solids is discussed. Cavitation-induced changes in the crystal size of intermetallic phases in binary AlNi (50 wt % of Ni) alloys allow an estimation of local temperatures on surfaces and in bulk material. The interplay between atomic solid-state diffusion and recrystallization during bubble collapses in heterogeneous systems is revealed. Furthermore, cavitation triggered red/ox processes at solid/liquid interfaces and their influence on recrystallization are discussed for copper aluminum nanocomposites, zinc, titanium, magnesium-based materials, and silicon. Cavitation-driven highly nonequilibrium conditions can affect the thermodynamics and kinetics of mesoscopic phase formation in heterogeneous systems and in many cases boost the macroscopic performance of composite materials, notably in catalytic alloy and photocatalytic semiconductor oxide properties, corrosion resistance, nanostructured surface biocompatibility, and optical properties.

Light-Induced Water Splitting Causes High-Amplitude Oscillation of pH-Sensitive Layer-by-Layer Assemblies on TiO2.

We introduce a simple concept of a light induced pH change, followed by high amplitude manipulation of the mechanical properties of an adjacent polymer film. Irradiation of a titania surface is known to cause water splitting, and this can be used to reduce the environmental pH to pH 4. The mechanical modulus of an adjacent pH sensitive polymer film can thus be changed by more than an order of magnitude. The changes can be localized, maintained for hours and repeated without material destruction.

Graphene oxide-DNA/graphene oxide-PDDA sandwiched membranes with neuromorphic function.

The behavior of polyelectrolytes in confined spaces has direct relevance to the protein mediated ion transport in living organisms. In this paper, we govern lithium chloride transport by the interface provided by polyelectrolytes, polycation, poly(diallyldimethylammonium chloride) (PDDA) and, polyanion, double stranded deoxyribonucleic acid (dsDNA), in confined graphene oxide (GO) membranes. Polyelectrolyte-GO interfaces demonstrate neuromorphic functions that were successfully applied with nanochannel ion interactions contributed, resulting in ion memory effects. Excitatory and inhibitory post-synaptic currents were tuned continuously as the number of pulses applied increased accordingly, increasing decay times. Furthermore, we demonstrated the short-term memory of a trained vs untrained device in computation. On account of its simple and safe production along with its robustness and stability, we anticipate our device to be a low dimensional building block for arrays to embed artificial neural networks in hardware for neuromorphic computing. Additionally, incorporating such devices with sensing and actuating parts for a complete feedback loop produces robotics with its own ability to learn by modifying actuation based on sensing data.

Thiadiazole-, selenadiazole- and triazole-fused anthraquinones as G-quadruplex targeting anticancer compounds.

G-quadruplex (G4) ligands attract considerable attention as potential anticancer therapeutics. In this study we proposed an original scheme for synthesis of azole-fused anthraquinones and prepared a series of G4 ligands carrying amino- or guanidinoalkylamino side chains. The heterocyclic core and structure of the terminal groups strongly affect on binding to G4-forming oligonucleotides, cellular accumulation and antitumor potency of compounds. In particular, thiadiazole- and selenadiazole- but not triazole-based ligands inhibit the proliferation of tumor cells (e.g. K562 leukemia) and stabilize primarily telomeric and c-MYC G4s. Anthraselenadiazole derivative 11a showed a good affinity to c-MYC G4 in vitro and down-regulated expression of c-MYC oncogene in cellular conditions. Further studies revealed that anthraselenadiazole 11a provoked cell cycle arrest and apoptosis in a dose- and time-dependent manner inhibiting K562 cells growth. Taken together, this work gives a valuable example that the closely related heterocycles may cause a significant difference in biological properties of G4 ligands.

Interventions in preconception and pregnant women at risk of gestational diabetes; a systematic review and meta-analysis of randomised controlled trials.

BACKGROUND: Women at risk of gestational diabetes mellitus (GDM) need preventative interventions. OBJECTIVE: To evaluate targeted interventions before and during pregnancy for women identified as being at risk of developing GDM. METHODS: Systematic review and meta-analysis conducted following PRISMA guidelines. MEDLINE, EMBASE and the Cochrane Library in addition to reference and citation lists were searched to identify eligible randomised controlled trials (RCTs) utilising risk stratification during the preconception period or in the first/early second trimester. Screening and data extraction were carried out by the authors independently. Quality assessment was conducted based on the Cochrane risk-of-bias tool. Random effects meta-analysis and narrative synthesis were performed. RESULTS: Eighty-four RCTs were included: two during preconception and 82 in pregnancy, with a pooled sample of 22,568 women. Interventions were behavioural (n = 54), dietary supplementation (n = 19) and pharmacological (n = 11). Predictive factors for risk assessment varied; only one study utilised a validated prediction model. Gestational diabetes was reduced in diet and physical activity interventions (risk difference - 0.03, 95% CI 0.06, - 0.01; I2 58.69%), inositol (risk difference - 0.19, 95% CI 0.33, - 0.06; I2 92.19%), and vitamin D supplements (risk difference - 0.16, 95% CI 0.25, - 0.06; I2 32.27%). Subgroup analysis showed that diet and physical activity interventions were beneficial in women with ≥ 2 GDM risk factors (risk difference - 0.16, 95% CI 0.25, - 0.07; I2 11.23%) while inositol supplementation was effective in women with overweight or obesity (risk difference - 0.17, 95% CI 0.22, - 0.11; I2 0.01%). Effectiveness of all other interventions were not statistically significant. CONCLUSIONS: This review provides evidence that interventions targeted at women at risk of GDM may be an effective strategy for prevention. Further studies using validated prediction tools or multiple risk factors to target high-risk women for intervention before and during pregnancy are warranted.

A nanofluidic sensing platform based on robust and flexible graphene oxide/chitosan nanochannel membranes for glucose and urea detection.

We present the development of a health-monitoring nanofluidic membrane utilizing biocompatible and biodegradable graphene oxide, chitosan, and graphene quantum dots. The nanoconfinement provided by graphene oxide nanolayers encapsulates chitosan molecules, allowing for their conformational changes and switchable hydrophobic-hydrophilic behavior in response to pH variations. This low-dimensional membrane operates as an array of nanofluidic channels that can release quantum dots upon pH change. The photoluminescence emission from quantum dots enables rapid and reliable optical visualization of pH changes, facilitating efficient human health monitoring. To ensure fouling prevention and enable multiple usages, we adopt a design approach that avoids direct contact between biomarkers and the nanochannels. This design strategy, coupled with good mechanical properties (Young's modulus of 5.5 ± 0.7 GPa), preserves the integrity and functionality of the sensors for repeated sensing cycles. Furthermore, leveraging the memory effect, our sensors can be reloaded with graphene quantum dots multiple times without significant loss of selectivity, achieving reusability. The wide-ranging capabilities of 2D materials and stimuli-responsive polymers empower our sustainable approach to designing low-dimensional, robust, and flexible sensing materials. This approach allows for the integration of various biorecognition elements and signal transduction modes, expanding the versatility and applications of the designed materials.

Angstrom-Confined Electrochemical Synthesis of Sub-Unit-Cell Non-Van Der Waals 2D Metal Oxides.

Bottom-up electrochemical synthesis of atomically thin materials is desirable yet challenging, especially for non-van der Waals (non-vdW) materials. Thicknesses below a few nanometers have not been reported yet, posing the question how thin can non-vdW materials be electrochemically synthesized. This is important as materials with (sub-)unit-cell thickness often show remarkably different properties compared to their bulk form or thin films of several nanometers thickness. Here, a straightforward electrochemical method utilizing the angstrom-confinement of laminar reduced graphene oxide (rGO) nanochannels is introduced to obtain a centimeter-scale network of atomically thin (<4.3 Å) 2D-transition metal oxides (2D-TMO). The angstrom-confinement provides a thickness limitation, forcing sub-unit-cell growth of 2D-TMO with oxygen and metal vacancies. It is showcased that Cr2 O3 , a material without significant catalytic activity for the oxygen evolution reaction (OER) in bulk form, can be activated as a high-performing catalyst if synthesized in the 2D sub-unit-cell form. This method displays the high activity of sub-unit-cell form while retaining the stability of bulk form, promising to yield unexplored fundamental science and applications. It is shown that while retaining the advantages of bottom-up electrochemical synthesis, like simplicity, high yield, and mild conditions, the thickness of TMO can be limited to sub-unit-cell dimensions.

Large-area organization of pNIPAM-coated nanostars as SERS platforms for polycyclic aromatic hydrocarbons sensing in gas phase.

Here, a new surface enhanced Raman spectroscopy (SERS) platform suitable for gas phase sensing based on the extended organization of poly-N-isopropylacrylamide (pNIPAM)-coated nanostars over large areas is presented. This system yields high and homogeneous SERS intensities, and simultaneously traps organic chemical agents as pollutants from the gas phase. pNIPAM-coated gold nanostars were organized into parallel linear arrays. The optical properties of the fabricated substrates are investigated, and applicability for advanced sensing is demonstrated through the detection in the gas phase of pyrene traces, a well-known polyaromatic hydrocarbon.

Satellite Glial Cells: Morphology, functional heterogeneity, and role in pain.

Neurons in the somatic, sympathetic, and parasympathetic ganglia are surrounded by envelopes consisting of satellite glial cells (SGCs). Recently, it has become clear that SGCs are highly altered after nerve injury, which influences neuronal excitability and, consequently, the development and maintenance of pain in different animal models of chronic pain. However, the exact mechanism underlying chronic pain is not fully understood yet because it is assumed that SGCs in different ganglia share many common peculiarities, making the process complex. Here, we review recent data on morphological and functional heterogeneity and changes in SGCs in various pain conditions and their role in response to injury. More research is required to decipher the role of SGCs in diseases, such as chronic pain, neuropathology, and neurodegenerative diseases.

Heterogeneity and Potency of Peripheral Glial Cells in Embryonic Development and Adults.

This review describes the heterogeneity of peripheral glial cell populations, from the emergence of Schwann cells (SCs) in early development, to their involvement, and that of their derivatives in adult glial populations. We focus on the origin of the first glial precursors from neural crest cells (NCCs), and their ability to differentiate into several cell types during development. We also discuss the heterogeneity of embryonic glia in light of the latest data from genetic tracing and transcriptome analysis. Special attention has been paid to the biology of glial populations in adult animals, by highlighting common features of different glial cell types and molecular differences that modulate their functions. Finally, we consider the communication of glial cells with axons of neurons in normal and pathological conditions. In conclusion, the present review details how information available on glial cell types and their functions in normal and pathological conditions may be utilized in the development of novel therapeutic strategies for the treatment of patients with neurodiseases.

Modeling Doxorubicin-Induced Cardiomyopathy With Fibrotic Myocardial Damage in Wistar Rats.

Background: Cardiovascular complications, arising after anthracycline chemotherapy, cause a significant deterioration in the life quality and expectancy of those patients who were previously successfully treated for malignant neoplasms. A number of clinical studies have demonstrated that patients with cardiotoxicity manifested during anthracyclines therapy also have extensive fibrotic changes in the cardiac muscle in the long term. Given the lack of an unambiguous understanding of the mechanisms of fibrotic changes formation under doxorubicin treatment in the myocardium, there is the obvious necessity to create a relevant experimental model of chronic doxorubicin-induced cardiomyopathy with fibrotic myocardial lesions and delayed development of diastolic dysfunction. Methods: The study was divided into two stages: first stage (creation of acute doxorubicin cardiomyopathy) - 35 male Wistar rats; second stage (creation of chronic doxorubicin cardiomyopathy) - 40 male Wistar rats. The animals were split into eight groups (two control ones and six experimental ones), which determined the doxorubicin dose (first stage: 25, 20.4, 15 mg/kg; second stage: 5, 10, 15 mg/kg, intraperitoneally) and the frequency of injection. Echocardiographic, hematological, histological, and molecular methods were used to confirm the successful modeling of acute and chronic doxorubicin-induced cardiomyopathy with fibrotic lesions. Results: A model of administration six times every other day with a cumulative dose of doxorubicin 20 mg/kg is suitable for evaluation of acute cardiotoxicity. The 15 mg/kg doxorubicin dose is highly cardiotoxic; what's more, it correlates with progressive deterioration of the clinical condition of the animals after 2 months. The optimal cumulative dose of doxorubicin leads to clinical manifestations confirmed by echocardiographic, histological, molecular changes associated with the development of chronic doxorubicin-induced cardiomyopathy with fibrotic lesions of the left ventricular of the cardiac muscle and ensure long-term survival of animals is 10 mg/kg doxorubicin. A dose of 5 mg/kg of the doxorubicin does not ensure the development of fibrous changes formation. Conclusion: We assume that cumulative dose of 10 mg/kg with a frequency of administration of six times in 2 days can be used to study the mechanisms of anthracycline cardiomyopathy development.