A sensorised surgical glove to improve training and detection of obstetric anal sphincter injury: A preclinical study on a pig model.

OBJECTIVE: To create a sensorised surgical glove that can accurately identify obstetric anal sphincter injury to facilitate timely repair, reduce complications and aid training. DESIGN: Proof-of-concept. SETTING: Laboratory. SAMPLE: Pig models. METHODS: Flexible triboelectric pressure/force sensors were mounted onto the fingertips of a routine surgical glove. The sensors produce a current when rubbed on materials of different characteristics which can be analysed. A per rectum examination was performed on the intact sphincter of pig cadavers, analogous to routine examination for obstetric anal sphincter injuries postpartum. An anal sphincter defect was created by cutting through the vaginal mucosa and into the external anal sphincter using a scalpel. The sphincter was then re-examined. Data and signals were interpreted. MAIN OUTCOME MEASURES: Sensitivity and specificity of the glove in detecting anal sphincter injury. RESULTS: In all, 200 examinations were performed. The sensors detected anal sphincter injuries in a pig model with sensitivities between 98% and 100% and a specificity of 100%. The current produced when examining an intact sphincter and sphincter with a defect was significantly different (p < 0.001). CONCLUSION: In this preliminary study, the sensorised glove accurately detected anal sphincter injury in a pig model. Future plans include its clinical translation, starting with an in-human study on postpartum women, to determine whether it can accurately detect different types of obstetric anal sphincter injury in vivo.

Inhibition Conversion of Aspirin into Salicylic Acid in Presence of Glycine.

Aspirin (AS) is a common drug having anti-pyretic and anti-inflammatory properties which is widely used in diverse medical conditions. The intake of AS may cause adverse effects such as gastrointestinal ulcer, tinnitus and Reye's syndrome. The adverse effects of AS arise due to conversion of AS into salicylic acid (SAL). Glycine (Gly) is a simplest non essential amino acid having anti-oxidative and anti-inflammatory effects. It also reduces the risk of obesity, hypertension, and diabetes mellitus. AS with Gly is well accepted form of the drug for the treatment of rheumatic conditions in comparisons to the bare AS. In the present work using UV-Visible absorption, fluorescence and DFT/ TD-DFT techniques confirmed that in presence of Gly inhibited the conversion of AS into SAL effectively.

The Effect of Enzymatic Treatment with Mutanase, Beta-Glucanase, and DNase on a Saliva-Derived Biofilm Model.

INTRODUCTION: The dental biofilm matrix is an important determinant of virulence for caries development and comprises a variety of extracellular polymeric substances that contribute to biofilm stability. Enzymes that break down matrix components may be a promising approach to caries control, and in light of the compositional complexity of the dental biofilm matrix, treatment with multiple enzymes may enhance the reduction of biofilm formation compared to single enzyme therapy. The present study investigated the effect of the three matrix-degrading enzymes mutanase, beta-glucanase, and DNase, applied separately or in combinations, on biofilm prevention and removal in a saliva-derived in vitro-grown model. METHODS: Biofilms were treated during growth to assess biofilm prevention or after 24 h of growth to assess biofilm removal by the enzymes. Biofilms were quantified by crystal violet staining and impedance-based real-time cell analysis, and the biofilm structure was visualized by confocal microscopy and staining of extracellular DNA (eDNA) and polysaccharides. RESULTS: The in vitro model was dominated by Streptococcus spp., as determined by 16S rRNA gene amplicon sequencing. All tested enzymes and combinations had a significant effect on biofilm prevention, with reductions of >90% for mutanase and all combinations including mutanase. Combined application of DNase and beta-glucanase resulted in an additive effect (81.0% ± 1.3% SD vs. 36.9% ± 21.9% SD and 48.2% ± 14.9% SD). For biofilm removal, significant reductions of up to 73.2% ± 5.5% SD were achieved for combinations including mutanase, whereas treatment with DNase had no effect. Glucans, but not eDNA decreased in abundance upon treatment with all three enzymes. CONCLUSION: Multi-enzyme treatment is a promising approach to dental biofilm control that needs to be validated in more diverse biofilms.

Preferred Mode of Atmospheric Water Vapor Condensation on Nanoengineered Surfaces: Dropwise or Filmwise?

Condensing atmospheric water vapor on surfaces is a sustainable approach to addressing the potable water crisis. However, despite extensive research, a key question remains: what is the optimal combination of the mode and mechanism of condensation as well as the surface wettability for the best possible water harvesting efficacy? Here, we show how various modes of condensation fare differently in a humid air environment. During condensation from humid air, it is important to note that the thermal resistance across the condensate is nondominant, and the energy transfer is controlled by vapor diffusion across the boundary layer and condensate drainage from the condenser surface. This implies that, unlike condensation from pure steam, filmwise condensation from humid air would exhibit the highest water collection efficiency on superhydrophilic surfaces. To demonstrate this, we measured the condensation rates on different sets of superhydrophilic and superhydrophobic surfaces that were cooled below the dew points using a Peltier cooler. Experiments were performed over a wide range of degrees of subcooling (10-26 °C) and humidity-ratio differences (5-45 g/kg of dry air). Depending upon the thermodynamic parameters, the condensation rate is found to be 57-333% higher on the superhydrophilic surfaces compared to the superhydrophobic ones. The findings of the study dispel ambiguity about the preferred mode of vapor condensation from humid air on wettability-engineered surfaces and lead to the design of efficient atmospheric water harvesting systems.

Use of portable air purifiers to reduce aerosols in hospital settings and cut down the clinical backlog.

SARS-CoV-2 has severely affected capacity in the National Health Service (NHS), and waiting lists are markedly increasing due to downtime of up to 50 min between patient consultations/procedures, to reduce the risk of infection. Ventilation accelerates this air cleaning, but retroactively installing built-in mechanical ventilation is often cost-prohibitive. We investigated the effect of using portable air cleaners (PAC), a low-energy and low-cost alternative, to reduce the concentration of aerosols in typical patient consultation/procedure environments. The experimental setup consisted of an aerosol generator, which mimicked the subject affected by SARS-CoV-19, and an aerosol detector, representing a subject who could potentially contract SARS-CoV-19. Experiments of aerosol dispersion and clearing were undertaken in situ in a variety of rooms with two different types of PAC in various combinations and positions. Correct use of PAC can reduce the clearance half-life of aerosols by 82% compared to the same indoor-environment without any ventilation, and at a broadly equivalent rate to built-in mechanical ventilation. In addition, the highest level of aerosol concentration measured when using PAC remains at least 46% lower than that when no mitigation is used, even if the PAC's operation is impeded due to placement under a table. The use of PAC leads to significant reductions in the level of aerosol concentration, associated with transmission of droplet-based airborne diseases. This could enable NHS departments to reduce the downtime between consultations/procedures.

Self-assembled porous polymer films for improved oxygen sensing.

Absolute oxygen sensors based on quenching of phosphorescence have been the subject of numerous studies for the monitoring of biological environments. Here, we used simple fabrication techniques with readily available polymers to obtain high performance phosphorescent films. Specifically, evaporation-based phase separation and the breath figure technique were used to induce porosity. The pore sizes ranged from ∼37 nm to ∼141 µm while the maximum average porosity achieved was ∼74%. The oxygen sensing properties were evaluated via a standarised calibration procedure with an optoelectronic setup in both transmission and reflection based configurations. When comparing non-porous and porous films, the highest improvements achieved were a factor of ∼7.9 in dynamic range and ∼7.3 in maximum sensitivity, followed by an improved linearity with a half-sensitivity point at 43% O2 V/V. Also, the recovery time was reduced by an order of magnitude in the high porosity film and all samples prepared were not affected by variations in the humidity of the surrounding environment. Despite the use of common polymers, the fabrication techniques employed led to the significant enhancement of oxygen sensing properties and elucidated the relation between porous film morphologies and sensing performance.

A Deep Learning Approach to Classify Surgical Skill in Microsurgery Using Force Data from a Novel Sensorised Surgical Glove.

Microsurgery serves as the foundation for numerous operative procedures. Given its highly technical nature, the assessment of surgical skill becomes an essential component of clinical practice and microsurgery education. The interaction forces between surgical tools and tissues play a pivotal role in surgical success, making them a valuable indicator of surgical skill. In this study, we employ six distinct deep learning architectures (LSTM, GRU, Bi-LSTM, CLDNN, TCN, Transformer) specifically designed for the classification of surgical skill levels. We use force data obtained from a novel sensorized surgical glove utilized during a microsurgical task. To enhance the performance of our models, we propose six data augmentation techniques. The proposed frameworks are accompanied by a comprehensive analysis, both quantitative and qualitative, including experiments conducted with two cross-validation schemes and interpretable visualizations of the network's decision-making process. Our experimental results show that CLDNN and TCN are the top-performing models, achieving impressive accuracy rates of 96.16% and 97.45%, respectively. This not only underscores the effectiveness of our proposed architectures, but also serves as compelling evidence that the force data obtained through the sensorized surgical glove contains valuable information regarding surgical skill.

Structural Basis for Dityrosine-Mediated Inhibition of α-Synuclein Fibrillization.

α-Synuclein (α-Syn) is an intrinsically disordered protein which self-assembles into highly organized ß-sheet structures that accumulate in plaques in brains of Parkinson's disease patients. Oxidative stress influences α-Syn structure and self-assembly; however, the basis for this remains unclear. Here we characterize the chemical and physical effects of mild oxidation on monomeric α-Syn and its aggregation. Using a combination of biophysical methods, small-angle X-ray scattering, and native ion mobility mass spectrometry, we find that oxidation leads to formation of intramolecular dityrosine cross-linkages and a compaction of the α-Syn monomer by a factor of √2. Oxidation-induced compaction is shown to inhibit ordered self-assembly and amyloid formation by steric hindrance, suggesting an important role of mild oxidation in preventing amyloid formation.

Transparent and Robust Amphiphobic Surfaces Exploiting Nanohierarchical Surface-grown Metal-Organic Frameworks.

Highly amphiphobic (repelling both water and low surface tension liquids) and optically transparent surface treatments have widespread demand. By combining a rational growth of metal-organic frameworks (MOFs) with functionalization by environmentally safe, flexible alkyl groups, here we present surfaces with nanohierarchical morphology, comprising two widely differing nanoscale features. These nanohierarchical MOF films show excellent amphiphobicity. We further present three key features. First, we demonstrate the need to use flexible alkyl chains to achieve low drop sliding angles and self-cleaning. Second, our thin (∼200 nm) MOF films display excellent optical transparency and robustness. Third, the nanohierarchical morphology enables a unique combination of additional desirable properties, e.g., resistance to high-speed liquid impact (up to ∼35 m/s, Weber number >4 × 104), thermal stability up to 200 °C, scratch resistance, low ice adhesion for >10 icing/deicing cycles, stability in harsh acidic and basic environments, and capability to remove carcinogenic pollutants from water.

Delayed Lubricant Depletion of Slippery Liquid Infused Porous Surfaces Using Precision Nanostructures.

Slippery liquid infused porous surfaces (SLIPS) are an important class of repellent materials, comprising micro/nanotextures infused with a lubricating liquid. Unlike superhydrophobic surfaces, SLIPS do not rely on a stable air-liquid interface and thus can better manage low surface tension fluids, are less susceptible to damage under physical stress, and are able to self-heal. However, these collective properties are only efficient as long as the lubricant remains infused, which has proved challenging. We hypothesized that, in comparison to a nanohole and nanopillar morphology, the "hybrid" morphology of a hole within a nanopillar, namely a nanotube, would be able to retain and redistribute lubricant more effectively, owing to capillary forces trapping a reservoir of lubricant within the tube, while lubricant between tubes can facilitate redistribution to depleted areas. By virtue of recent fabrication advances in spacer defined intrinsic multiple patterning (SDIMP), we fabricated an array of silicon nanotubes and equivalent arrays of nanoholes and nanopillars (pitch, 560 nm; height, 2 µm). After infusing the nanostructures (prerendered hydrophobic) with lubricant Krytox 1525, we probed the lubricant stability under dynamic conditions and correlated the degree of the lubricant film discontinuity to changes in the contact angle hysteresis. As a proof of concept, the durability test, which involved consecutive deposition of droplets onto the surface amounting to 0.5 L, revealed 2-fold and 1.5-fold enhancements of lubricant retention in nanotubes in comparison to nanopillars and nanoholes, respectively, showing a clear trajectory for prolonging the lifetime of a slippery surface.

Detection and Characterization of a Novel Copper-Dependent Intermediate in a Lytic Polysaccharide Monooxygenase.

Lytic polysaccharide monooxygenases (LPMOs) are copper-containing enzymes capable of oxidizing crystalline cellulose which have large practical application in the process of refining biomass. The catalytic mechanism of LPMOs still remains debated despite several proposed reaction mechanisms. Here, we report a long-lived intermediate (t1/2 =6-8 minutes) observed in an LPMO from Thermoascus aurantiacus (TaLPMO9A). The intermediate with a strong absorption around 420 nm is formed when reduced LPMO-CuI reacts with sub-equimolar amounts of H2 O2 . UV/Vis absorption spectroscopy, electron paramagnetic resonance, resonance Raman and stopped-flow spectroscopy suggest that the observed long-lived intermediate involves the copper center and a nearby tyrosine (Tyr175). Additionally, activity assays in the presence of sub-equimolar amounts of H2 O2 showed an increase in the LPMO oxidation of phosphoric acid swollen cellulose. Accordingly, this suggests that the long-lived copper-dependent intermediate could be part of the catalytic mechanism for LPMOs. The observed intermediate offers a new perspective into the oxidative reaction mechanism of TaLPMO9A and hence for the biomass oxidation and the reactivity of copper in biological systems.

Fluorine-Free Transparent Superhydrophobic Nanocomposite Coatings from Mesoporous Silica.

In recent decades, there has been a growing interest in the development of functional, fluorine-free superhydrophobic surfaces with improved adhesion for better applicability into real-world problems. Here, we compare two different methods, spin coating and aerosol-assisted chemical vapor deposition (AACVD), for the synthesis of transparent fluorine-free superhydrophobic coatings. The material was made from a nanocomposite of (3-aminopropyl)triethoxysilane (APTES) functional mesoporous silica nanoparticles and titanium cross-linked polydimethylsiloxane with particle concentrations between 9 to 50 wt %. The silane that was used to lower the surface energy consisted of a long hydrocarbon chain without fluorine groups to reduce the environmental impact of the composite coating. Both spin coating and AACVD resulted in the formation of superhydrophobic surfaces with advancing contact angles up to 168°, a hysteresis of 3°, and a transparency of 90% at 550 nm. AACVD has proven to produce more uniform coatings with concentrations as low as 9 wt %, reaching superhydrophobicity. The metal oxide cross-linking improves the adhesion of the coating to the glass. Overall, AACVD was the more optimal method to prepare superhydrophobic coatings compared to spin coating due to higher contact angles, adhesion, and scalability of the fabrication process.

Spectroscopic Studies of CDPy Molecule in Different Protic and Aprotic Solvents and Investigation of Antioxidant Property.

The properties of 3-Cyano-4, 6-Dimethyl-2-Pyridone (CDPy) were analyzed to study the antioxidant behavior. The UV-Visible absorption and fluorescence properties of CDPy have been studied in two protic (water and methanol) and two aprotic (acetonitrile and dimethyl sulfoxide) solvents. Its antioxidant properties were compared with well known antioxidant ascorbic acid. This compound, CDPy was found to exhibits moderate antioxidant properties. The experimental results were reproduced by theoretical density functional methods, which helped to understand the experimental result better.

Phe-140 Determines the Catalytic Efficiency of Arylacetonitrilase from Alcaligenes faecalis.

Arylacetonitrilase from Alcaligenes faecalis ATCC8750 (NitAF) hydrolyzes various arylacetonitriles to the corresponding carboxylic acids. A systematic strategy of amino acid residue screening through sequence alignment, followed by homology modeling and biochemical confirmation was employed to elucidate the determinant of NitAF catalytic efficiency. Substituting Phe-140 in NitAF (wild-type) to Trp did not change the catalytic efficiency toward phenylacetonitrile, an arylacetonitrile. The mutants with nonpolar aliphatic amino acids (Ala, Gly, Leu, or Val) at location 140 had lower activity, and those with charged amino acids (Asp, Glu, or Arg) exhibited nearly no activity for phenylacetonitrile. Molecular modeling showed that the hydrophobic benzene ring at position 140 supports a mechanism in which the thiol group of Cys-163 carries out a nucleophilic attack on a cyanocarbon of the substrate. Characterization of the role of the Phe-140 residue demonstrated the molecular determinant for the efficient formation of arylcarboxylic acids.

Formation and Structure of Fluorescent Silver Nanoclusters at Interfacial Binding Sites Facilitating Oligomerization of DNA Hairpins.

Fluorescent, DNA-stabilized silver nanoclusters (DNA-AgNCs) are applied in a range of applications within nanoscience and nanotechnology. However, their diverse optical properties, mechanism of formation, and aspects of their composition remain unexplored, making the rational design of nanocluster probes challenging. Herein, a synthetic procedure is described for obtaining a high yield of emissive DNA-AgNCs with a C-loop hairpin DNA sequence, with subsequent purification by size-exclusion chromatography (SEC). Through a combination of optical spectroscopy, gel electrophoresis, inductively coupled plasma mass spectrometry (ICP-MS), and small-angle X-ray scattering (SAXS) in conjunction with the systematic study of various DNA sequences, the low-resolution structure and mechanism of the formation of AgNCs were investigated. Data indicate that fluorescent DNA-AgNCs self-assemble by a head-to-head binding of two DNA hairpins, bridged by a silver nanocluster, resulting in the modelling of a dimeric structure harboring an Ag12 cluster.

Asp271 is critical for substrate interaction with the surface binding site in ß-agarase a from Zobellia galactanivorans.

In the marine environment agar degradation is assured by bacteria that contain large agarolytic systems with enzymes acting in various endo- and exo-modes. Agarase A (AgaA) is an endo-glycoside hydrolase of family 16 considered to initiate degradation of agarose. Agaro-oligosaccharide binding at a unique surface binding site (SBS) in AgaA from Zobellia galactanivorans was investigated by computational methods in conjunction with a structure/sequence guided approach of site-directed mutagenesis probed by surface plasmon resonance binding analysis of agaro-oligosaccharides of DP 4-10. The crystal structure has shown that agaro-octaose interacts via H-bonds and aromatic stacking along 7 subsites (L through R) of the SBS in the inactive catalytic nucleophile mutant AgaA-E147S. D271 is centrally located in the extended SBS where it forms H-bonds to galactose and 3,6-anhydrogalactose residues of agaro-octaose at subsites O and P. We propose D271 is a key residue in ligand binding to the SBS. Thus AgaA-E147S/D271A gave slightly decreasing KD values from 625 ± 118 to 468 ± 13 µM for agaro-hexaose, -octaose, and -decaose, which represent 3- to 4-fold reduced affinity compared with AgaA-E147S. Molecular dynamics simulations and interaction analyses of AgaA-E147S/D271A indicated disruption of an extended H-bond network supporting that D271 is critical for the functional SBS. Notably, neither AgaA-E147S/W87A nor AgaA-E147S/W277A, designed to eliminate stacking with galactose residues at subsites O and Q, respectively, were produced in soluble form. W87 and W277 may thus control correct folding and structural integrity of AgaA.

All-organic superhydrophobic coatings with mechanochemical robustness and liquid impalement resistance.

Superhydrophobicity is a remarkable evolutionary adaption manifested by several natural surfaces. Artificial superhydrophobic coatings with good mechanical robustness, substrate adhesion and chemical robustness have been achieved separately. However, a simultaneous demonstration of these features along with resistance to liquid impalement via high-speed drop/jet impact is challenging. Here, we describe all-organic, flexible superhydrophobic nanocomposite coatings that demonstrate strong mechanical robustness under cyclic tape peels and Taber abrasion, sustain exposure to highly corrosive media, namely aqua regia and sodium hydroxide solutions, and can be applied to surfaces through scalable techniques such as spraying and brushing. In addition, the mechanical flexibility of our coatings enables impalement resistance to high-speed drops and turbulent jets at least up to ~35 m s-1 and a Weber number of ~43,000. With multifaceted robustness and scalability, these coatings should find potential usage in harsh chemical engineering as well as infrastructure, transport vehicles and communication equipment.

Effects of Cu(II) on the aggregation of amyloid-ß.

Aberrant aggregation of the Aß protein is a hallmark of Alzheimer's disease (AD), but no complete characterization of the molecular level pathogenesis has been achieved. A promising hypothesis is that dysfunction of metal ion homeostasis, and consequently, the undesired interaction of metal ions with Aß, may be central to the development of AD. Qualitatively, most data indicate that Cu(II) induces rapid self-assembly of both Aß40 and Aß42 during the initial phase of the aggregation, while at longer time scales fibrillation may occur, depending on the experimental conditions. For Aß40 and Cu(II):Aß ≤ 1, most data imply that low concentration of Aß40 favors nucleation and rapid fibril elongation, while high concentration of Aß40 favors formation of amorphous aggregates. However, there are conflicting reports on this issue. For Aß42 and Cu(II):Aß ≤ 1, there is consensus that the lag time is extended upon addition of Cu(II). For Cu(II):Aß > 1, the lag time is increased upon interaction with Cu(II), and in most cases fibrillation is not observed, presumably because Cu(II) occupies a second more solvent-exposed binding site, which is more prone to form metal ion-bridged species and cause rapid formation of non-fibrillar aggregates. The interesting N-terminally truncated Aß11-40 with high affinity for Cu(II), exhibits delay of fibrillation upon addition of 0.4 eq. Cu(II). In our view, there are still problems achieving reproducible results in this field, and we provide a shortlist of some of the pitfalls. Finally, we propose a consensus model for the effects of Cu(II) on the aggregation kinetics of Aß.

The Pathogenic A2V Mutant Exhibits Distinct Aggregation Kinetics, Metal Site Structure, and Metal Exchange of the Cu2+ -Aß Complex.

A prominent current hypothesis is that impaired metal ion homeostasis may contribute to Alzheimer's disease (AD). We elucidate the interaction of Cu2+ with wild-type (WT) Aß1-40 and the genetic variants A2T and A2V which display increasing pathogenicity as A2T