Engineering inorganic nanozyme architectures for decomposition of reactive oxygen species.

Enzyme-mimicking nanomaterials (nanozymes) with antioxidant activity are at the forefront of research efforts towards biomedical and industrial applications. The selection of enzymatically active substances and their incorporation into novel inorganic nanozyme structures is critically important for this field of research. To this end, the fabrication of composites can be desirable as these can either exhibit multiple enzyme-like activities in a single material or show increased activity compared to the nanozyme components. Conversely, by modifying the structure of a nanomaterial, enzyme-like activities can be induced in formerly inert particles. We identify herein the three main routes of composite nanozyme synthesis, namely, surface functionalization of a particle with another compound, heteroaggregation of individual nanozymes, and modification of the bulk nanozyme structure to achieve optimal antioxidant activity. We discuss in particular the different inorganic support materials used in the synthesis of nanozyme architectures and the advantages brought forth by the use of composites.

Change in Endogenous Pain Modulation Depending on Emotional States in Healthy Subjects: A Randomized Controlled Trial.

INTRODUCTION: Chronic pain is a public health issue, leading to substantial healthcare costs and diminished quality of life for sufferers. While the role of anxiety in pain modulation has been extensively studied, the effects of other emotional states on the body's pain control mechanisms remain less understood. This study sought to explore how different emotions (happiness, anger, sadness, and interest) affect conditioned pain modulation (CPM) and the wind-up phenomenon in healthy adults. METHODS: This randomized controlled, cross-over trial involved 28 healthy participants aged 18-60. Participants watched video clips designed to induce specific emotions: happiness, anger, sadness, and interest. Emotional states were assessed using a 7-point Likert scale. Pain modulation was measured using CPM and the wind-up phenomenon. CPM was assessed with a hot water bath as the conditioning stimulus and pressure pain tolerance as the test stimulus. Wind-up was measured using pinprick needle stimulators and a visual analog scale. Data were analyzed using paired t tests to compare pre- and post-emotion induction values. RESULTS: Significant changes in emotional self-assessment values were observed for all emotions. Happiness increased CPM (4.6 ± 11.4, p = 0.04277), while sadness - 9.9 ± 23.1, p = 0.03211) and anger - 9.1 ± 23.3, p = 0.04804) decreased it. Interest did not significantly alter CPM (- 5.1 ± 25.8, p = 0.31042). No significant effects were found for the wind-up phenomenon across any emotional states. CONCLUSION: This study shows that emotional states significantly affect the body's ability to modulate pain. Positive emotions like happiness enhance pain inhibition, while negative emotions such as sadness and anger impair it. These findings suggest that emotional modulation techniques could be integrated into pain management strategies to improve patient outcomes. Further research should explore a broader range of emotions and include objective measures to validate these results.

Chronic pain is a widespread problem that affects millions of people and leads to high healthcare costs and decreased quality of life. Understanding how emotions impact pain can help us find better ways to manage it. This study looked at how different emotions (happiness, anger, sadness, and interest) affect the ability of the body to naturally control pain in healthy adults. Participants experienced different tests in a random order, like flipping a coin to decide the order. Each participant took part in all the tests to compare how different conditions affected them. We measured changes in their pain perception using two methods: conditioned pain modulation, which reflects how well the body can suppress pain after experiencing another painful stimulus, and the wind-up phenomenon, which measures how pain intensity increases with repeated stimulation. We found that emotions affected the body's ability to control pain. Sadness and anger reduced the efficacy of conditioned pain modulation, making it harder for the body to reduce pain. Happiness improved CPM, enhancing the body's natural ability to stop pain. Interest did not significantly change how pain was felt. We also did not find any significant changes in the wind-up phenomenon for any of the emotions tested. The results suggest that positive emotions like happiness can help reduce pain, while negative emotions like sadness and anger can make pain worse. This could lead to new pain management approaches that include methods to boost positive emotions and reduce negative ones.

The Impact of Polyphosphates on the Colloidal Stability of Laponite Particles.

The effect of polyphosphate (polyP) adsorption on the colloidal properties of disc-shaped laponite (LRD) particles was examined in aqueous dispersions with a focus on elucidating the interparticle forces that govern the colloidal stability of the systems. The charge and aggregation rate data of bare LRD exhibited an ionic strength-dependent trend, confirming the presence of double-layer repulsion and van der Waals attraction as major surface interactions. The charge of LRD particles significantly increased in magnitude at elevated polyP concentrations as a result of polyP adsorption and subsequent overcharging of the positively charged sites on the edges of the LRD discs. A transition from stable to unstable LRD colloids was observed with increasing polyP doses indicating the formation of aggregates in the latter systems due to depletion forces and/or bridging interactions induced by dissolved or adsorbed polyP, respectively. The degree of phosphate polymerization influenced neither the charge nor the aggregation mechanism. The findings clearly confirm that polyP adsorption was the driving phenomenon to induce particle aggregation in contrast to other clay types, where phosphate derivatives act as dispersion stabilizing agents. This study provides valuable insights into the early stages of aggregation in colloidal systems involving LRD and polyPs, which have a crucial role in predicting further material properties that are important to designing LRD-polyP composites for applications such as potential phosphate sources in chemical fertilizers.

Optimization of Interfacial Properties Improved the Stability and Activity of the Catalase Enzyme Immobilized on Plastic Nanobeads.

The immobilization of catalase (CAT), a crucial oxidoreductase enzyme involved in quenching reactive oxygen species, on colloids and nanoparticles presents a promising strategy to improve dispersion and storage stability while maintaining its activity. Here, the immobilization of CAT onto polymeric nanoparticles (positively (AL) or negatively (SL) charged) was implemented directly (AL) or via surface functionalization (SL) with water-soluble chitosan derivatives (glycol chitosan (GC) and methyl glycol chitosan (MGC)). The interfacial properties were optimized to obtain highly stable AL-CAT, SL-GC-CAT, and SL-MGC-CAT dispersions, and confocal microscopy confirmed the presence of CAT in the composites. Assessment of hydrogen peroxide decomposition ability revealed that applying chitosan derivatives in the immobilization process not only enhanced colloidal stability but also augmented the activity and reusability of CAT. In particular, the use of MGC has led to significant advances, indicating its potential for industrial and biomedical applications. Overall, the findings highlight the advantages of using chitosan derivatives in CAT immobilization processes to maintain the stability and activity of the enzyme as well as provide important data for the development of processable enzyme-based nanoparticle systems to combat reactive oxygen species.

Spatial organization of the ions at the free surface of imidazolium-based ionic liquids.

HYPOTHESIS: Experimental information on the molecular scale structure of ionic liquid interfaces is controversial, giving rise to two competing scenarios, namely the double layer-like and "chessboard"-like structures. This issue can be resolved by computer simulation methods, at least for the underlying molecular model. Systematically changing the anion type can elucidate the relative roles of electrostatic interactions, hydrophobic (or, strictly speaking, apolar) effects and steric restrictions on the interfacial properties. SIMULATIONS: Molecular dynamics simulation is combined with intrinsic analysis methods both at the molecular and atomic levels, supplemented by Voronoi analysis of self-association. FINDINGS: We see no evidence for the existence of a double-layer-type arrangement of the ions, or for their self-association at the surface of the liquid. Instead, our results show that cation chains associate into apolar domains that protrude into the vapour phase, while charged groups form domains that are embedded in this apolar environment at the surface. However, the apolar chains largely obscure the cation groups, to which they are bound, while the smaller and more mobile anions can more easily access the free surface, leading to a somewhat counterintuitive net excess of negative charge at the interface. Importantly, this excess charge could only be identified by applying intrinsic analysis.

Abusive head trauma and crying infant-Public awareness of newborn and infant trauma.

AIM: Crying seems to be a common trigger for abusive head trauma (AHT), which is the leading cause of fatalities from physical abuse in infants. Our objective was to evaluate knowledge of AHT, crying infants and correct behavioural measures in a general population. METHODS: An online questionnaire (LimeSurvey) was created to assess the risk of shaking. The online survey contained a total of 41 questions, including a demonstration of a previously recorded video in which an infant doll is shaken. RESULTS: A total of 319 people, 245 of them (76.8%) with own children, participated in the study. Almost all respondents (98.4%) were aware of serious injuries due to shaking, even to the point of death (98.1%). Most participants (97.5%) had heard the term 'shaking trauma' prior but did not receive any professional information, neither before nor after birth (85.2% or 86%), or during follow-up examinations (88.5%). The majority of the participants (95%) considered that useful coping strategies in infant crying were inappropriate. CONCLUSION: The consequences of shaking an infant were common knowledge in a normal population, whereas there was a knowledge gap regarding the management of excessive crying infants. Prevention programmes should mainly focus on male caregivers during postnatal care.

Reduction of intracellular oxidative stress with a copper-incorporated layered double hydroxide.

Biocompatible Cu(II)-doped layered double hydroxide (CMA) nanoparticles were developed to combat reactive oxygen species. The 2-dimensional nanozymes showed both superoxide dismutase- and catalase-like activities in chemical assays, while proving as efficient antioxidants in the reduction of intracellular oxidative stress. The results indicate the great promise of CMA in antioxidant therapies.

Aptamer Clicked Poly(ferrocenylsilanes) at Au Nanoparticles as Platforms with Multiple Function[†].

Aptamers are widely used in biosensing due to their specific sensitivity toward many targets. Thus, gold nanoparticle (AuNP) aptasensors are subject to intense research due to the complementary properties of aptamers as sensing elements and AuNPs as transducers. We present herein a novel method for the functional coupling of thrombin-specific aptamers to AuNPs via an anionic, redox-active poly(ferrocenylsilane) (PFS) polyelectroyte. The polymer acts as a co-reductant and stabilizer for the AuNPs, provides grafting sites for the aptamer, and can be used as a redox sensing element, making the aptamer-PFS-AuNP composite (aptamer-AuNP) a promising model system for future multifunctional sensors. The aptamer-AuNPs exhibit excellent colloidal stability in high ionic strength environments owing to the combined electrosteric stabilizing effects of the aptamer and the PFS. The synthesis of each assembly element is described, and the colloidal stability and redox responsiveness are studied. As an example to illustrate applications, we present results for thrombin sensitivity and specificity using the specific aptamer.

Formulation of Antioxidant Composites by Controlled Heteroaggregation of Cerium Oxide and Manganese Oxide Nanozymes.

Antioxidant composites based on nanozymes [manganese oxide microflakes (MnO2 MFs) and cerium oxide nanoparticles (CeO2 NPs)] were formulated by controlled heteroaggregation. The interparticle attraction via electrostatic forces was systematically tuned with surface functionalization by the poly(diallyldimethyl chloride) (PDADMAC) polyelectrolyte. The PDADMAC-coated MnO2 MFs (PMn) were heteroaggregated with oppositely charged CeO2 NPs to generate the Ce-PMn composite, while the PDADMAC-functionalized CeO2 NPs (PCe) were immobilized onto bare MnO2 MFs, resulting in the Mn-PCe composite. Both the adsorption of PDADMAC and the self-assembly of oppositely charged particles resulted in charge neutralization and charge reversal at appropriately high doses. The interparticle force regimes, the aggregation states, and the physicochemical properties of the relevant dispersions were also highly dependent on the dose of PDADMAC, as well as that of PDADMAC-functionalized metal oxides (PMO) enabling the fine-tuning and control of colloidal stability. The individual enzyme-like activity of either metal oxide was not compromised by PDADMAC adsorption and/or heteroaggregation, leading to the formation of broad-spectrum antioxidant composites exhibiting multiple enzyme-like activities such as superoxide dismutase, oxidase, and peroxidase-type functions. The low cost and ease of preparation, as well as controllable colloidal properties render such composites potential enzyme mimicking agents in various industrial fields, where processable antioxidant systems are needed.

Molecular Antioxidants Maintain Synergistic Radical Scavenging Activity upon Co-Immobilization on Clay Nanoplatelets.

Unbalanced levels of reactive oxygen species (ROS) result in oxidative stress, affecting both biomedical and industrial processes. Antioxidants can prevent ROS overproduction and thus delay or inhibit their harmful effects. Herein, activities of two molecular antioxidants (gallic acid (GA), a well-known phenolic compound, and nicotinamide adenine dinucleotide (NADH), a vital biological cofactor) were tested individually and in combination to assess possible synergistic, additive, or antagonistic effects in free radical scavenging and in redox capacity assays. GA was a remarkable radical scavenger, and NADH exhibited moderate antioxidant activity, while their combination at different molar ratios led to a synergistic effect since the resulting activity was superior to the sum of the individual GA and NADH activities. Their coimmobilization was performed on the surface of delaminated layered double hydroxide clay nanoplatelets by electrostatic interactions, and the synergistic effect was maintained upon such a heterogenization of these molecular antioxidants. The coimmobilization of GA and NADH expands the range of their potential applications, in which separation of antioxidant additives is important during treatments or manufacturing processes.

Colloidal Interactions of Microplastic Particles with Anionic Clays in Electrolyte Solutions.

Homoaggregation of polystyrene microplastics (MPs) and heteroaggregation of MPs with anionic clay minerals, namely, layered double hydroxide (LDH), in different salt (NaCl, CaCl2, and Na2SO4) solutions were systematically investigated using light scattering techniques. The salt type and ionic strength had significant effects on the stability of both MPs and LDH particles individually and the results could be explained by DLVO theory and the Schulze-Hardy rule. However, once stable colloidal dispersions of the individual particles were mixed, heteroaggregation occurred between the oppositely charged MPs and LDH, which was also confirmed by transmission electron microscopy and X-ray scattering. Adsorption of the LDH particles resulted in neutralization and reversal of MPs surface charge at appropriate LDH doses. Once LDH adsorption neutralized the negative charges of the MP spheres, rapid aggregation was observed in the dispersions, whereas stable samples formed at high and low LDH concentrations. The governing interparticle interactions included repulsive electrical double-layer forces, as well as van der Waals and patch-charge attractions, the strength of which depended on the mass ratio of the interacting particles and the composition of the aqueous solvent. Our results shed light on the colloidal behavior of MPs in a complex aquatic environment and, in the long term, are also useful for developing LDH-based approaches for water remediation to remove contamination with MP particles.

Dual functionality of ferrocene-based metallopolymers as radical scavengers and nanoparticle stabilizing agents.

The beneficial redox properties of ferrocene-based polymers have been utilized during in situ preparation of metallic nanoparticles, while such redox features also indicate a great promise in applications as free radical scavengers. Here, colloidal dispersions of an antioxidant nanozyme composed of amidine-functionalized polystyrene latex (AL) nanoparticles, negatively charged poly(ferrocenylsilane) (PFS(-)) organometallic polyions, and ascorbic acid (AA) were formulated. The AL was first functionalized with PFS(-). Increasing the polymer dose resulted in charge neutralization and subsequent charge reversal of the particles. The strength of repulsive interparticle forces of electrostatic nature was significant at low and high doses leading to stable colloids, while attractive forces dominated near the charge neutralization point giving rise to unstable dispersions. The saturated PFS(-) layer adsorbed on the surface of the AL (p-AL nanozyme) enhanced the colloidal stability against salt-induced aggregation without affecting the pH-dependent charge and size of the particles. The joint effect of PFS(-) and the AA in radical decomposition was observed indicating the antioxidant potential of the system. The immobilization of PFS(-) deteriorated its scavenging activity, yet the combination with AA improved this feature. The results indicate that p-AL-AA is a promising radical scavenger since the high colloidal stability of the particles allows application in heterogeneous systems, such as in industrial manufacturing processes, where antioxidants are required to maintain acceptable product quality.

Impact of the pandemic and its containment measures in Europe upon aspects of affective impairments: a Google Trends informetrics study.

BACKGROUND: In late 2019, a new virus began spreading in Wuhan, China. By the end of 2021, more than 260 million people worldwide had been infected and 5.2 million people had died because of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Various countermeasures have been implemented to contain the infections, depending on the country, infection prevalence, and political and infrastructural resources. The pandemic and the containment measures have induced diverse psychological burdens. Using internet queries as a proxy, this study examines the psychological consequences on a European level of SARS-CoV-2 containment measures. METHODS: Using informetric analyses, this study reviews within 32 European countries a total of 28 search parameters derived from the International Statistical Classification of Diseases and Related Health Problems (ICD-10) as aspects of affective disorder. RESULTS: Our results show that there are several psychological aspects which are significantly emphasized during the pandemic and its containment measures: 'anxiety', 'dejection', 'weariness', 'listlessness', 'loss of appetite', 'loss of libido', 'panic attack', and 'worthlessness'. These terms are significantly more frequently part of a search query during the pandemic than before the outbreak. Furthermore, our results revealed that search parameters such as 'psychologist', 'psychotherapist', 'psychotherapy' have increased highly significantly (p < 0.01) since the pandemic. CONCLUSIONS: The psychological distress caused by the pandemic correlates significantly with the frequency of people searching for psychological and psychotherapeutic support on the Internet.

Palmitoylethanolamide in the Treatment of Chronic Pain: A Systematic Review and Meta-Analysis of Double-Blind Randomized Controlled Trials.

Chronic pain is a major source of morbidity for which there are limited effective treatments. Palmitoylethanolamide (PEA), a naturally occurring fatty acid amide, has demonstrated utility in the treatment of neuropathic and inflammatory pain. Emerging reports have supported a possible role for its use in the treatment of chronic pain, although this remains controversial. We undertook a systematic review and meta-analysis to examine the efficacy of PEA as an analgesic agent for chronic pain. A systematic literature search was performed, using the databases MEDLINE and Web of Science, to identify double-blind randomized controlled trials comparing PEA to placebo or active comparators in the treatment of chronic pain. All articles were independently screened by two reviewers. The primary outcome was pain intensity scores, for which a meta-analysis was undertaken using a random effects statistical model. Secondary outcomes including quality of life, functional status, and side effects are represented in a narrative synthesis. Our literature search identified 253 unique articles, of which 11 were ultimately included in the narrative synthesis and meta-analysis. Collectively, these articles described a combined sample size of 774 patients. PEA was found to reduce pain scores relative to comparators in a pooled estimate, with a standard mean difference of 1.68 (95% CI 1.05 to 2.31, p = 0.00001). Several studies reported additional benefits of PEA for quality of life and functional status, and no major side effects were attributed to PEA in any study. The results of this systematic review and meta-analysis suggest that PEA is an effective and well-tolerated treatment for chronic pain. Further study is warranted to determine the optimal dosing and administration parameters of PEA for analgesic effects in the context of chronic pain.

Confinement of Triple-Enzyme-Involved Antioxidant Cascade in Two-Dimensional Nanostructure.

Application of antioxidant enzymes in medical or industrial processes is limited due to their high sensitivity to environmental conditions. Incorporation of such enzymes in nanostructures provides a promising route to obtain highly efficient and robust biocatalytic system to scavenge reactive oxygen species (ROS). Here, this question was addressed by confinement of superoxide dismutase (SOD), horseradish peroxidase (HRP), and catalase (CAT) enzymes into nanostructures containing polyelectrolyte building blocks (alginate (Alg) and trimethyl chitosan (TMC)) and delaminated layered double hydroxide (dLDH) nanoparticle support. The nanocomposite possessed excellent structural and colloidal stability, while antioxidant tests revealed that the enzymes remained active upon immobilization and the developed composite greatly reduced intracellular oxidative stress in two-dimensional cell cultures. Moreover, it effectively prevented hydrogen peroxide-induced double stranded DNA breaks, which is a common consequence of oxidative stress. The results provide important tools to design complex nanostructures with multienzymatic antioxidant activities for ROS scavenging.

Molecular orientation rules the efficiency of immobilized antioxidants.

Tannic acid (TA) and glutathione (GSH) are important molecular antioxidants against reactive oxygen species. Their efficiency is limited by low solubility and high sensitivity, which may be solved by confinement in composite materials. Here, effect of immobilization of these antioxidants on their radical scavenging activity was investigated using layered double hydroxide (LDH) nanoparticles as hosts. Different preparation methods were applied to build composite systems leading to variations in the molecular orientation of both TA and GSH on the surface or among the layers of LDHs. Systematic combination of spectroscopy (FT-IR, Raman, UV-VIS-NIR-DRS), diffraction (XRD) and microscopy (SEM) methods revealed perpendicular or parallel orientation of TA on the surface of LDH depending on the preparation approach applied. Immobilization of GSH protected the antioxidant molecules from degradation. Radical scavenging tests evidenced that the activity of the antioxidants strongly depends on the molecular orientation. The LDH supported GSH and TA proved as durable and reusable antioxidant agents to be applied as radical scavengers in medical therapies or in industrial processes.

The Effect of Smoking Cessation on Acute Pain: A Systematic Review.

Smoking is a known risk factor for developing various pain-related disorders. However, acute pain often triggers the craving for cigarette consumption, resulting in a positive feedback mechanism. In addition, there is evidence of decreased pain tolerance during the early stages of abstinence. Therefore, in this study, we aimed to investigate whether a period of decreased pain tolerance and increased pain intensity occurs during smoking cessation. A systematic literature search was conducted through PubMed and Web of Science databases for controlled studies investigating the influence of smoking cessation on acute (defined as pain presentation of < 3 months) and postoperative pain. The outcomes of interest included pain perception threshold, pain tolerance, pain intensity, and postoperative opioid requirements. The search strategy yielded 1478 studies, of which 13 clinical studies met our inclusion criteria. The included studies collectively represented data from 1721 participants from four countries. Of these, 43.3% of the included individuals were females. The mean age of the included subjects was 44.2 ± 8.2 years. The duration of smoking cessation varied considerably. The shortest duration was 2 h; others investigated the effect after more than 1 month of smoking cessation. Smokers had a history of 14.6 ± 9.9 years of nicotine abuse. The mean number of daily smoked cigarettes was 17.5 ± 10.3. Most studies examined in this systematic review show a negative influence of smoking cessation on acute pain. However, the affected pain modalities, the duration of the altered pain perception, and whether male and female smokers are equally affected could not be ascertained due to high heterogeneity and few available studies.

Delamination of Layered Double Hydroxide in Ionic Liquids under Ambient Conditions.

Liquid phase delamination of layered materials into single- or few-layer nanosheets leads to stable nanoscale dispersions of 2D materials. The delamination of layered double hydroxide (LDH) to double hydroxide nanosheets was studied in two ionic liquids (ILs): ethylammonium nitrate (EAN) and 1-butyl-3-methylimidazolium thiocyanate (BMIMSCN). The as-prepared lamellar structure of LDH disappeared upon dispersing it in ILs due to delamination into 2D nanosheets confirmed by X-ray scattering and diffraction techniques and further evaluated by height profile assessment of the nanoparticles by atomic force microscopy. The results showed that both the thickness and lateral size of the dispersed particles decreased in the IL-based samples, indicating that cleavage of the LDH materials can be observed in addition to delamination. The findings prove the concept of delamination of layered materials by ILs under ambient conditions─an excellent way to prepare 2D double hydroxide nanosheet dispersions in one step using nonvolatile green solvents.