Biochemical Processes Research Articles

ИЗУЧЕНИЕ ПРОЦЕССОВ КОМПЛЕКСООБРАЗОВАНИЯ В ПОЛИМЕРНЫХ БИОДЕГРАДИРУЕМЫХ КОМПОЗИЦИЯХ

One of the possible directions of the development of targeted substance delivery systems is the creation and introduction of biodegradable polymers into production. Their distinctive feature is that they are capable of spontaneously gradually degradation in the body due to natural biochemical processes. There is an increasing spread pharmaceutical form, which use similar excipients in their technology – medicinal ocular insert. Modified cellulose, gums and rare-cross-linked acrylic polymers are used to create a biodegradable matrix base. In terms of development approach, ocular inserts can be divided into two groups according to the principle of matrix biodegradation. In non-biodegradable composites, the effect of prolongation of the therapeutic effect is observed due to the release of the active substance from the non-decomposing matrix. This fact can be confirmed by both pharmacopoeial and non-pharmacopoeial methods. The classic tests regulated by the Pharmacopoeia of the XV edition include the "Dissolution" test (GPM.1.4.2.0014 "Dissolution of solid pharmaceutical dose forms"), and for non–pharmacopoeial ones – dialysis through a semipermeable membrane according to Kruvchinsky or using Franz's dialysis cells. The analysis of the kinetics of dissolution helps to determine and select the most suitable matrix-forming agent to be used in the composition with other substances in the composition of ocular insert. Ocular inserts with a biodegradable matrix have a second factor that affects the release of active substances – the formation of complexes or associates between parts of the matrix and the active ingredient molecules. These intermolecular compounds can indirectly prolong the effect of the drug. All features must be taken into account in the development of ocular inserts, since they, among other things, help to model fundamentally new ways of targeted delivery of substances. In this case, it is necessary to develop a test for the second modified release factor, which would reliably determine the presence of complexation processes within the selected ocular inserts model.

A Foam Line Position Detection Algorithm for A/O Pool Based on YOLOv5

During the biochemical pretreatment process of leachate in urban landfill sites, if the foam in the A/O pool is not promptly addressed, it can lead to overflow, posing hazards to the surrounding environment and personnel. Therefore, a real-time foam line detection algorithm based on YOLOv5x was proposed, which enhances feature information and improves anchor box regression prediction to accurately detect the position of foam lines. Firstly, in the preprocessing stage, employing a rectangular box to simultaneously label the foam line and the edge of the A/O pool within the same region, enhances the feature information of the foam line. Then, the C3NAM module was proposed, which applies weight sparse penalties to attention modules in the feature extraction section, to enhance the capability of extracting foam line features. Subsequently, a B-SPPCSPC module was proposed to enhance the fusion of shallow and deep feature information, addressing the issue of susceptibility to background interference during foam line detection. Next, the Focal_EIOU was introduced to ameliorate the issue of class imbalance in detection, providing more accurate bounding box predictions. Lastly, optimizing the detection layer scale improves the detection performance for smaller targets. The experimental results demonstrate that the accuracy of this algorithm reaches 98.9%, and the recall reaches 88.1%, with a detection frame rate of 26.2 frames per second, which can meet the actual detection requirements of real-world application scenarios.

Advanced Dressings for Chronic Wound Management.

Wound healing, particularly for chronic wounds, presents a considerable difficulty due to differences in biochemical and cellular processes that occur in different types of wounds. Recent technological breakthroughs have notably advanced the understanding of diagnostic and therapeutic approaches to wound healing. The evolution in wound care has seen a transition from traditional textile dressings to a variety of advanced alternatives, including self-healing hydrogels, hydrofibers, foams, hydrocolloids, environment responsive dressings, growth factor-based therapy, bioengineered skin substitutes, and stem cell and gene therapy. Technological advancements, such as 3D printing and electronic skin (e-skin) therapy, contribute to the customization of wound healing. Despite these advancements, effectively managing chronic wounds remains challenging. This necessitates the development of treatments that consider performance, risk-benefit balance, and cost-effectiveness. This review discusses innovative strategies for the healing of chronic wounds. Incorporating biomarkers into advanced dressings, coupled with corresponding biosensors and drug delivery formulations, enables the theranostic approach to the treatment of chronic wounds. Furthermore, integrating advanced dressings with power sources and user interfaces like near-field communication, radio frequency identification, and Bluetooth enhances real-time monitoring and on-demand drug delivery. It also provides a thorough evaluation of the advantages, patient compliance, costs, and durability of advanced dressings, emphasizing smart formulations and their preparation methods.

The role of reduced graphene oxide on mitigation of lead phytotoxicity in Triticum aestivum L.plants at morphological and physiological levels

Rapid global industrialization and an increase in population have enhanced the risk of heavy metals accumulation in plant bodies to disrupt the morphological, biochemical, and physiological processes of plants. To cope with this situation, reduced graphene oxide (rGO) NPs were used first time to mitigate abiotic stresses caused in plant. In this study, rGO NPs were synthesized and reduced with Tecoma stans plant leave extract through modified Hummer's methods. The well prepared rGO NPs were characterized by ultra-violet visible spectroscopy (UV–Vis), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Zeta potential, and scanning electron microscopy (SEM). However, pot experiment was conducted with four different concentrations (15, 30, 60, 120 mg/L) of rGO NPs and three different concentrations (300, 500,700 mg/L) of lead (Pb) stress were applied. To observe the mitigative effects of rGO NPs, 30 mg/L of rGO NPs and 700 mg/L of Pb were used in combination. Changes in morphological and biochemical characteristics of wheat plants were observed for both Pb stress and rGO NPs treatments. Pb was found to inhibit the morphological and biochemical characteristics of plants. rGO NPs alone as well as in combination with Pb was found to increase the chlorophyll content of wheat plants. Under Pb stress conditions and rGO NPs treatments, antioxidant enzyme activities like ascorbate peroxidases (APX), superoxide dismutase (SOD), peroxidase (POD) and catalase (CAT) were observed. Current findings revealed that greenly reduced graphene oxide NPs can effectively promote growth in wheat plants under Pb stress by elevating chlorophyll content of leaves, reducing the Pb uptake, and suppressing ROS produced due to Pb toxicity.

Promoting Circular Economy of the Building Industry by the Use of Straw Bales: A Review

Over the past decade, the concept of a circular economy has increasingly gained attention as a framework for guiding businesses and policymakers. Given its significant environmental impact, the building industry plays a pivotal role in the transition toward a circular economy. To address this, our review proposes a bio-based building material, specifically straw bale, which elaborates on the circularity of bio-based buildings based on the 3R principles of a circular economy: reduce, reuse, and recycle. In terms of the “reduce” principle, straw-bale buildings can reduce construction waste, the environmental impact, energy requirements, and carbon emissions. Regarding the “reuse” principle, straw-bale buildings utilize agricultural waste resources and are easily disassembled due to their prefabrication. As for the “recycle” principle, straw-bale buildings can undergo physical, biological, and biochemical conversion processes (thermochemical conversion), yielding both wooden composite boards and potential biogas and biomass fuels for electricity and heating. This study evaluates the contribution of straw packaging construction and the use of straw as a raw material, using the 3R principles to determine future research opportunities for the construction industry to achieve a circular economy. The results of this study offer circular economy solutions and interdisciplinary research insights for researchers and practitioners interested in the building environment.

Lipid mediators in neutrophil biology: inflammation, resolution and beyond.

Acute inflammation is the body's first defense in response to pathogens or injury. Failure to efficiently resolve the inflammatory insult can severely affect tissue homeostasis, leading to chronic inflammation. Neutrophils play a pivotal role in eradicating infectious pathogens, orchestrating the initiation and resolution of acute inflammation, and maintaining physiological functions. The resolution of inflammation is a highly orchestrated biochemical process, partially modulated by a novel class of endogenous lipid mediators known as specialized pro-resolving mediators (SPMs). SPMs mediate their potent bioactions via activating specific cell-surface G protein-coupled receptors (GPCR). This review focuses on recent advances in understanding the multifaceted functions of SPMs, detailing their roles in expediting neutrophil apoptosis, promoting clearance by macrophages, regulating their excessive infiltration at inflammation sites, orchestrating bone marrow deployment, also enhances neutrophil phagocytosis and tissue repair mechanisms under both physiological and pathological conditions. We also focus on the novel role of SPMs in regulating bone marrow neutrophil functions, differentiation, and highlight open questions about SPMs' functions in neutrophil heterogeneity. SPMs play a pivotal role in mitigating excessive neutrophil infiltration and hyperactivity within pathological milieus, notably in conditions such as sepsis, cardiovascular disease, ischemic events, and cancer. This significant function highlights SPMs as promising therapeutic agents in the management of both acute and chronic inflammatory disorders.

Comparison of Various Extraction Approaches for Optimized Preparation of Intracellular Metabolites from Human Mesenchymal Stem Cells and Fibroblasts for NMR-Based Study

Metabolomics has proven to be a sensitive tool for monitoring biochemical processes in cell culture. It enables multi-analysis, clarifying the correlation between numerous metabolic pathways. Together with other analysis, it thus provides a global view of a cell’s physiological state. A comprehensive analysis of molecular changes is also required in the case of mesenchymal stem cells (MSCs), which currently represent an essential portion of cells used in regenerative medicine. Reproducibility and correct measurement are closely connected to careful metabolite extraction, and sample preparation is always a critical point. Our study aimed to compare the efficiencies of four harvesting and six extraction methods. Several organic reagents (methanol, ethanol, acetonitrile, methanol–chloroform, MTBE) and harvesting approaches (trypsinization vs. scraping) were tested. We used untargeted nuclear magnetic resonance spectroscopy (NMR) to determine the most efficient method for the extraction of metabolites from human adherent cells, specifically human dermal fibroblasts adult (HDFa) and dental pulp stem cells (DPSCs). A comprehensive dataset of 29 identified and quantified metabolites were determined to possess statistically significant differences in the abundances of several metabolites when the cells were detached mechanically to organic solvent compared to when applying enzymes mainly in the classes of amino acids and peptides for both types of cells. Direct scraping to organic solvent is a method that yields higher abundances of determined metabolites. Extraction with the use of different polar reagents, 50% and 80% methanol, or acetonitrile, mostly showed the same quality. For both HDFa and DPSC cells, the MTBE method, methanol–chloroform, and 80% ethanol extractions showed higher extraction efficiency for the most identified and quantified metabolites Thus, preparation procedures provided a cell sample processing protocol that focuses on maximizing extraction yield. Our approach may be useful for large-scale comparative metabolomic studies of human mesenchymal stem cell samples.

Histology, fatty acid composition, antioxidant and glycolipid metabolism, and transcriptome analyses of the acute cold stress response in Phoxinus lagowskii

Water temperature is a crucial environmental factor that significantly affects the physiological and biochemical processes of fish. Due to the occurrence of cold events in aquaculture, it is imperative to investigate how fish respond to cold stress. This study aims to uncover the mechanisms responds to acute cold stress by conducting a comprehensive analysis of the histomorphology, glycolipid metabolic and antioxidant enzymes, fatty acid composition and transcriptome at three temperatures (16 °C, 10 °C and 4 °C) in Phoxinus lagowskii. Our results showed that cold stress not damaged muscle microstructure but caused autophagy (at 10 °C). In addition, serum glucose (Glu) and triglycerides (TG) increased during cold stress. The activities of reactive oxygen species (ROS), superoxide dismutase (SOD), catalase (CAT), fructose phosphokinase (PFK), hexokinase (HK), pyruvate kinase (PK), and malondialdehyde (MDA) content in muscle were measured and analyzed. During cold stress, superoxide dismutase and catalase activities increased, reactive oxygen species content decreased. No significant difference in Glutathione peroxidase (GPx) activity, malondialdehyde and total cholesterol (T-CHO) contents among groups. Phosphokinase and pyruvate kinase activities decreased, and HK activity increased during cold stress. Our study resulted in the identification of a total of 25,400 genes, with 2524 genes showing differential expression across different temperature treatments. Furthermore, KEGG pathway indicated that some pathways upregulated during light cold stress (at 10 °C, including autophagy, and AMP-activated protein kinase (AMPK) signaling pathway. Additionally, circadian rhythm is among the most enriched pathways in genes up-regulated during severe cold stress (at 4 °C). Our findings offer valuable insights into how cold-water fish respond to cold stress.

Implication of system xc− in neuroinflammation during the onset and maintenance of neuropathic pain

BackgroundDespite the high prevalence of neuropathic pain, treating this neurological disease remains challenging, given the limited efficacy and numerous side effects associated with current therapies. The complexity in patient management is largely attributed to an incomplete understanding of the underlying pathological mechanisms. Central sensitization, that refers to the adaptation of the central nervous system to persistent inflammation and heightened excitatory transmission within pain pathways, stands as a significant contributor to persistent pain. Considering the role of the cystine/glutamate exchanger (also designated as system xc−) in modulating glutamate transmission and in supporting neuroinflammatory responses, we investigated the contribution of this exchanger in the development of neuropathic pain.MethodsWe examined the implication of system xc− by evaluating changes in the expression/activity of this exchanger in the dorsal spinal cord of mice after unilateral partial sciatic nerve ligation. In this surgical model of neuropathic pain, we also examined the consequence of the genetic suppression of system xc− (using mice lacking the system xc− specific subunit xCT) or its pharmacological manipulation (using the pharmacological inhibitor sulfasalazine) on the pain-associated behavioral responses. Finally, we assessed the glial activation and the inflammatory response in the spinal cord by measuring mRNA and protein levels of GFAP and selected M1 and M2 microglial markers.ResultsThe sciatic nerve lesion was found to upregulate system xc− at the spinal level. The genetic deletion of xCT attenuated both the amplitude and the duration of the pain sensitization after nerve surgery, as evidenced by reduced responses to mechanical and thermal stimuli, and this was accompanied by reduced glial activation. Consistently, pharmacological inhibition of system xc− had an analgesic effect in lesioned mice.ConclusionTogether, these observations provide evidence for a role of system xc− in the biochemical processes underlying central sensitization. We propose that the reduced hypersensitivity observed in the transgenic mice lacking xCT or in sulfasalazine-treated mice is mediated by a reduced gliosis in the lumbar spinal cord and/or a shift in microglial M1/M2 polarization towards an anti-inflammatory phenotype in the absence of system xc−. These findings suggest that drugs targeting system xc− could contribute to prevent or reduce neuropathic pain.

Exploring the physicochemical properties of the integration of Tristearoyl uridine in Langmuir monolayers: An approach to cell membrane modeling for prodrugs

Understanding the mechanisms by which drugs interact with cell membranes is crucial for unraveling the underlying biochemical and biophysical processes that occur on the surface of these membranes. Our research focused on studying the interaction between an ester-type derivative of tristearoyl uridine and model cell membranes composed of lipid monolayers at the air-water interface. For that, we selected a specific lipid to simulate nontumorigenic cell membranes, namely 1,2-dihexadecanoyl-sn-glycero-3-phospho-l-serine. We noted significant changes in the surface pressure-area isotherms, with a noticeable shift towards larger areas, which was lower than expected for ideal mixtures, indicating monolayer condensation. Furthermore, the viscoelastic properties of the interfacial film demonstrated an increase in both the elastic and viscous parameters for the mixed film. We also observed structural alterations using vibrational spectroscopy, which revealed an increase in the all-trans to gauche conformers ratio. This confirmed the stiffening effect of the prodrug on the lipid monolayer. In summary, this study indicates that this lipophilic prodrug significantly impacts the lipid monolayer's thermodynamic, rheological, electrical, and molecular characteristics. This information is crucial for understanding how the drug interacts with specific sites on the cellular membrane. It also has implications for drug delivery, as the drug's passage into the cytosol may involve traversing the lipid bilayer.

Biomarkers of Alzheimer's Disease Associated with Programmed Cell Death Reveal Four Repurposed Drugs.

Alzheimer's disease (AD) is a neurodegenerative disorder and the most common cause of dementia. Programmed cell death (PCD) is mainly characterized by unique morphological features and energy-dependent biochemical processes. The predominant pathway leading to cell death in AD has not been thoroughly analyzed, although there is evidence of neuron loss in AD and numerous pathways of PCD have been associated with this process. A better understanding of the systems biology underlying the relationship between AD and PCD could lead to the development of new therapeutic approaches. To this end, publicly available transcriptome data were examined using bioinformatic methods such as differential gene expression and weighted gene coexpression network analysis (WGCNA) to find PCD-related AD biomarkers. The diagnostic significance of these biomarkers was evaluated using a logistic regression-based predictive model. Using these biomarkers, a multifactorial regulatory network was developed. Last, a drug repositioning study was conducted to propose new drugs for the treatment of AD targeting PCD. The development of 3PM (predictive, preventive, and personalized) drugs for the treatment of AD would be enabled by additional research on the effects of these drugs on this disease.

A mathematical model for the role of dopamine-D2 self-regulation in the production of ultradian rhythms.

Many self-motivated and goal-directed behaviours display highly flexible, approximately 4 hour ultradian (shorter than a day) oscillations. Despite lacking direct correspondence to physical cycles in the environment, these ultradian rhythms may be involved in optimizing functional interactions with the environment and reflect intrinsic neural dynamics. Current evidence supports a role of mesostriatal dopamine (DA) in the expression and propagation of ultradian rhythmicity, however, the biochemical processes underpinning these oscillations remain to be identified. Here, we use a mathematical model to investigate D2 autoreceptor-dependent DA self-regulation as the source of ultradian behavioural rhythms. DA concentration at the midbrain-striatal synapses is governed through a dual-negative feedback-loop structure, which naturally gives rise to rhythmicity. This model shows the propensity of striatal DA to produce an ultradian oscillation characterized by a flexible period that is highly sensitive to parameter variations. Circadian (approximately 24 hour) regulation consolidates the ultradian oscillations and alters their response to the phase-dependent, rapid-resetting effect of a transient excitatory stimulus. Within a circadian framework, the ultradian rhythm orchestrates behavioural activity and enhances responsiveness to an external stimulus. This suggests a role for the circadian-ultradian timekeeping hierarchy in governing organized behaviour and shaping daily experience through coordinating the motivation to engage in recurring, albeit not highly predictable events, such as social interactions.

Genome-wide identification, characterization and functional prediction of the SRS gene family in sesame (Sesamum indicum L.)

Sesame (Sesamum indicum L.) is an ancient oilseed crop of the Pedaliaceae family with high oil content and potential health benefits. SHI RELATED SEQUENCE (SRS) proteins are the transcription factors (TFs) specific to plants that contain RING-like zinc figure domain and are associated with the regulation of several physiological and biochemical processes. They also play vital roles in plant growth and development such as root formation, leaf development, floral development, hormone biosynthesis, signal transduction, and biotic and abiotic stress responses. Nevertheless, the SRS gene family was not reported in sesame. In this study, identification, molecular characterization, phylogenetic relationship, cis-acting regulatory elements, protein-protein interaction, syntenic relationship, duplication events and expression pattern of SRS genes were analyzed in S. indicum. We identified total six SiSRS genes on seven different linkage groups in the S. indicum genome by comparing the other species, including the model plant Arabidopsis thaliana. The SiSRS genes showed variation in their structure like 2-5 exons and 1-4 introns. Like other species, SiSRS proteins also contained ‘RING-like zinc figure’ and ‘LRP1’ domains. Then, the SiSRS genes were clustered into subclasses via phylogenetic analysis with proteins of S. indicum, A. thaliana, and some other plant species. The cis-acting regulatory elements analysis revealed that the promoter region of SiSRS4 (SIN_1011561) showed the highest 13 and 16 elements for light- and phytohormone-responses whereas, SiSRS1 (SIN_1015187) showed the highest 15 elements for stress-response. The ABREs, or ABA-responsive elements, were found in a maximum of 8 copies in the SiSRS3 (SIN 1009100). Moreover, the available RNA-seq based expression of SiSRS genes revealed variation in expression patterns between stress-treated and non-treated samples, especially in drought and salinity conditions in. S. indicum. Two SiSRS genes like SiSRS1 (SIN_1015187) and SiSRS5 (SIN_1021065), also exhibited variable expression patterns between control vs PEG-treated sesame root samples and three SiSRS genes, including SiSRS1 (SIN_1015187), SiSRS2 (SIN_1003328) and SiSRS5 (SIN_1021065) were responsive to salinity treatments. The present outcomes will encourage more research into the gene expression and functionality analysis of SiSRS genes in S. indicum and other related species.

Nitric oxide alleviates programmed cell death induced by cadmium in Solanum lycopersicum seedlings through protein S-nitrosylation

Cadmium (Cd), as a non-essential and toxic heavy metal in plants, has deleterious effects on plant physiological and biochemical processes. Nitric oxide (NO) is one of the most important signaling molecules for plants to response diverse stresses. Here, we found that Cd-induced programmed cell death (PCD) was accompanied by NO bursts, which exacerbated cell death when NO was removed and vice versa. Proteomic analysis of S-nitrosylated proteins showed that the differential proteins in Cd-induced PCD and in NO-alleviated PCD mainly exist together in carbohydrate metabolism and amino acid metabolism, while some of the differential proteins exist alone in metabolism of cofactors and vitamins and lipid metabolism. Meanwhile, S-nitrosylation of proteins in porphyrin and chlorophyll metabolism and starch and sucrose metabolism could explain the leaf chlorosis induced by PCD. Moreover, protein transport protein SEC23, ubiquitinyl hydrolase 1 and pathogenesis-related protein 1 were identified to be S-nitrosylated in vivo, and their expressions were increased in Cd-induced PCD while decreased in NO treatment. Similar results were obtained in tomato seedlings with higher S-nitrosylation. Taken together, our results indicate that NO might be involved in the regulation of Cd-induced PCD through protein S-nitrosylation, especially proteins involved in PCD response.

THE CELL AS A SEMIOTIC SYSTEM THAT REALIZES CLOSURE TO EFFICIENT CAUSATION: THE SEMIOTIC (M, R) SYSTEM

Robert Rosen defines organisms as material systems closed to efficient causation, and proposes the replicative (M, R) system as a model for them. Vega (2023) proposes a cell model that realizes Rosen’s formal model, based on Hofmeyr's (2017) analysis of the functional organization of cell biochemistry and on Rosen's construction of the replication function. In this article we propose a cell model that, starting from the same biochemical processes, replaces the replication function with a set of semiotic relations between some of the elements that participate in cellular processes. The result is a cell model that constitutes a semiotic system that realizes closure to efficient causation: a semiotic (M, R) system. We compare the models of closure that correspond to the replicative (M, R) system and the semiotic (M, R) system. Additionally, we discuss the role that the genetic code and protein synthesis play in the semiotic closure to efficient causation. Finally, we outline the method to extend this analysis to more complex organisms.

LncRNA FTH1P3: A New Biomarker for Cancer-Related Therapeutic Development.

Cancer is a persistent and urgent health problem that affects the entire world. Not long ago, regulatory biomolecules referred to as long noncoding RNAs (lncRNAs) might have value for their innate abundance and stability. These single-stranded RNAs potentially interfere with several physiological and biochemical cellular processes involved in many human pathological situations, particularly cancer diseases. Ferritin heavy chain1 pseudogene 3 (FTH1P3), a lncRNA that is ubiquitously transcribed and belongs to the ferritin heavy chain (FHC) family, represents a novel class of lncRNAs primarily found in oral squamous cell carcinoma. Further research has shown that FTH1P3 is involved in other malignancies such as uveal melanoma, glioma, esophageal squamous cell carcinoma, non-small cell lung cancer, breast cancer, laryngeal squamous cell carcinoma, and cervical cancer. Accordingly, FTH1P3 significantly enhances cancer symptoms, including cell proliferation, invasion, metastasis, chemoresistance, and inhibition of apoptosis through many specific mechanisms. Notably, the clinical data significantly demonstrated the association of FTH1P3 overexpression with poor prognosis and poor overall survival within the examined samples. Here, we summarize all the research published to date (13 articles) on FTH1P3, focusing on the biological function underlying the regulatory mechanism and its possible clinical relevance.

Magnetic Modulation of Biochemical Synthesis in Synthetic Cells.

Synthetic cells can be constructed from diverse molecular components, without the design constraints associated with modifying 'living' biological systems. This can be exploited to generate cells with abiotic components, creating functionalities absent in biology. One example is magnetic responsiveness, the activation and modulation of encapsulated biochemical processes using a magnetic field, which is absent from existing synthetic cell designs. This is a critical oversight, as magnetic fields are uniquely bio-orthogonal, noninvasive, and highly penetrative. Here, we address this by producing artificial magneto-responsive organelles by coupling thermoresponsive membranes with hyperthermic Fe3O4 nanoparticles and embedding them in synthetic cells. Combining these systems enables synthetic cell microreactors to be built using a nested vesicle architecture, which can respond to alternating magnetic fields through in situ enzymatic catalysis. We also demonstrate the modulation of biochemical reactions by using different magnetic field strengths and the potential to tune the system using different lipid compositions. This platform could unlock a wide range of applications for synthetic cells as programmable micromachines in biomedicine and biotechnology.

Eco-Synthesis of Gold Nanoparticles Using Vigna unguiculata Seed Extract: A Leap in the Direction of Antiglycation Remedies

Eco-Synthesis of Gold Nanoparticles Using <i>Vigna unguiculata</i> Seed Extract: A Leap in the Direction of Antiglycation Remedies

Combined effects of three insecticides with different modes of action on biochemical responses of the solitary bee Osmia bicornis

Bees are simultaneously exposed to a variety of pesticides, which are often applied in mixtures and can cause lethal and sublethal effects. The combined effects of pesticides, however, are not measured in the current risk assessment schemes. Additionally, the sublethal effects of pesticides on a variety of physiological processes are poorly recognized in bees, especially in non-Apis solitary bees. In this study, we used a full-factorial design to examine the main and interactive effects of three insecticide formulations with different modes of action (Mospilan 20 SP, Sherpa 100 EC, and Dursban 480 EC) on bee biochemical processes. We measured acetylcholinesterase (AChE), glutathione S-transferase (GST) and esterase (EST) activities, as well as a nonenzymatic biomarker associated with energy metabolism, i.e., ATP level. All studied endpoints were affected by Sherpa 100 EC, and the activities of AChE and EST as well as ATP levels were affected by Dursban 480 EC. Moreover, complex interactions between all three insecticides affected ATP levels, showing outcomes that cannot be predicted when testing each insecticide separately. The results indicate that even if interactive effects are sometimes difficult to interpret, there is a need to study such interactions if laboratory-generated toxicity data are to be extrapolated to field conditions.

Coordination Variations within Binuclear Copper Dioxygen-Derived (Hydro)Peroxo and Superoxo Species; Influences upon Thermodynamic and Electronic Properties.

Copper ion is a versatile and ubiquitous facilitator of redox chemical and biochemical processes. These include the binding of molecular oxygen to copper(I) complexes where it undergoes stepwise reduction-protonation. A detailed understanding of thermodynamic relationships between such reduced/protonated states is key to elucidate the fundamentals of the chemical/biochemical processes involved. The dicopper(I) complex [CuI2(BPMPO-)]1+ {BPMPOH = 2,6-bis{[(bis(2-pyridylmethyl)amino]methyl}-4-methylphenol)} undergoes cryogenic dioxygen addition; further manipulations in 2-methyltetrahydrofuran generate dicopper(II) peroxo [CuII2(BPMPO-)(O22-)]1+, hydroperoxo [CuII2(BPMPO-)(-OOH)]2+, and superoxo [CuII2(BPMPO-)(O2•-)]2+ species, characterized by UV-vis, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies, and cold spray ionization mass spectrometry. An unexpected EPR spectrum for [CuII2(BPMPO-)(O2•-)]2+ is explained by the analysis of its exchange-coupled three-spin frustrated system and DFT calculations. A redox equilibrium, [CuII2(BPMPO-)(O22-)]1+ ⇄ [CuII2(BPMPO-)(O2•-)]2+, is established utilizing Me8Fc+/Cr(η6-C6H6)2, allowing for [CuII2(BPMPO-)(O2•-)]2+/[CuII2(BPMPO-)(O22-)]1+ reduction potential calculation, E°' = -0.44 ± 0.01 V vs Fc+/0, also confirmed by cryoelectrochemical measurements (E°' = -0.40 ± 0.01 V). 2,6-Lutidinium triflate addition to [CuII2(BPMPO-)(O22-)]1+ produces [CuII2(BPMPO-)(-OOH)]2+; using a phosphazene base, an acid-base equilibrium was achieved, pKa = 22.3 ± 0.7 for [CuII2(BPMPO-)(-OOH)]2+. The BDFEOO-H = 80.3 ± 1.2 kcal/mol, as calculated for [CuII2(BPMPO-)(-OOH)]2+; this is further substantiated by H atom abstraction from O-H substrates by [CuII2(BPMPO-)(O2•-)]2+ forming [CuII2(BPMPO-)(-OOH)]2+. In comparison to known analogues, the thermodynamic and spectroscopic properties of [CuII2(BPMPO-)] O2-derived adducts can be accounted for based on chelate ring size variations built into the BPMPO- framework and the resulting enhanced CuII-ion Lewis acidity.