Reactions In Biological Systems Research Articles

The covalent reactivity of functionalized 5-hydroxy-butyrolactams is the basis for targeting of fatty acid binding protein 5 (FABP5) by the neurotrophic agent MT-21.

Covalently acting compounds experience a strong interest within chemical biology both as molecular probes in studies of fundamental biological mechanisms and/or as novel drug candidates. In this context, the identification of new classes of reactive groups is particularly important as these can expose novel reactivity modes and, consequently, expand the ligandable proteome. Here, we investigated the electrophilic reactivity of the 3-acyl-5-hydroxy-1,5-dihydro-2H-pyrrole-2-one (AHPO) scaffold, a heterocyclic motif that is e.g. present in various bioactive natural products. Our investigations were focused on the compound MT-21 - a simplified structural analogue of the natural product epolactaene - which is known to have both neurotrophic activity and ability to trigger apoptotic cell death. We found that the central N-acyl hemiaminal group of MT-21 can function as an electrophilic centre enabling divergent reactivity with both amine- and thiol-based nucleophiles, which furthermore translated to reactivity with proteins in both cell lysates and live cells. We found that in live cells MT-21 strongly engaged the lipid transport protein fatty acid-binding protein 5 (FABP5) by direct binding to a cysteine residue in the bottom of the ligand binding pocket. Through preparation of a series of MT-21 derivatives, we probed the specificity of this interaction which was found to be strongly dependent on subtle structural changes. Our study suggests that MT-21 may be employed as a tool compound in future studies of the biology of FABP5, which remains incompletely understood. Furthermore, our study has also made clear that other natural products containing the AHPO-motif may likewise possess covalent reactivity and that this property may underlie their biological activity.

Development of a PFAS reaction library: identifying plausible transformation pathways in environmental and biological systems.

Perfluoroalkyl and polyfluoroalkyl substances (PFAS) are used in many consumer applications due to their stain repellency, surfactant properties, ability to form water-proof coatings and use in fire suppression. The production, application, transport, use and disposal of PFAS and PFAS-treated products have resulted in their wide-spread occurrence in environmental and biological systems. Concern over exposure to PFAS and their transformation products and metabolites has necessitated the development of tools to predict the transformation of PFAS in environmental systems and metabolism in biological systems. We have developed reaction libraries for predicting transformation products and metabolites in a variety of environmental and biological reaction systems. These reaction libraries are based on generalized reaction schemes that encode the process science of PFAS reported in the peer-reviewed literature. The PFAS reaction libraries will be executed through the Chemical Transformation Simulator, a web-based tool that is available to the public. These reaction libraries are intended for predicting the environmental transformation and metabolism of PFAS only.

Regulation and Functional Complexity of the Chlorophyll-Binding Protein IsiA.

As the oldest known lineage of oxygen-releasing photosynthetic organisms, cyanobacteria play the key roles in helping shaping the ecology of Earth. Iron is an ideal transition metal for redox reactions in biological systems. Cyanobacteria frequently encounter iron deficiency due to the environmental oxidation of ferrous ions to ferric ions, which are highly insoluble at physiological pH. A series of responses, including architectural changes to the photosynthetic membranes, allow cyanobacteria to withstand this condition and maintain photosynthesis. Iron-stress-induced protein A (IsiA) is homologous to the cyanobacterial chlorophyll (Chl)-binding protein, photosystem II core antenna protein CP43. IsiA is the major Chl-containing protein in iron-starved cyanobacteria, binding up to 50% of the Chl in these cells, and this Chl can be released from IsiA for the reconstruction of photosystems during the recovery from iron limitation. The pigment–protein complex (CPVI-4) encoded by isiA was identified and found to be expressed under iron-deficient conditions nearly 30years ago. However, its precise function is unknown, partially due to its complex regulation; isiA expression is induced by various types of stresses and abnormal physiological states besides iron deficiency. Furthermore, IsiA forms a range of complexes that perform different functions. In this article, we describe progress in understanding the regulation and functions of IsiA based on laboratory research using model cyanobacteria.

Characterization And Screening Of Protease, Amylase, And Cellulase From Phylloplane Fungi Isolates Of Avicennia marina (Forssk.) Vierh.

Mangrove (Avicennia marina) is an important mangrove species, because it has many benefits for human life, including in the ecological scope as a source of food and medicine. These plants can also be used as a source of symbiont mold isolates which can be developed as an alternative to produce bioactive compounds, one of which is enzymes. Enzymes are protein compounds that can catalyze all chemical reactions in biological systems. This study aims to determine whether mangrove symbiont fungi (A. marina) can produce amylase, protease and cellulase enzymes. This research was conducted using a method based on enzyme activity, namely amylase activity with lugol iodine staining, protease activity and cellulase activity with congo red staining. on agar media enriched with 1% skim milk, 1% starch and 1% CMC. The results showed that 4 isolates were able to show potential enzymatic activity to be developed as agents for enzyme production.

Synthesis, characterization and catalytic activity of a mononuclear nonheme copper(II)-iodosylbenzene adduct

Iodosylbenzene (PhIO) and its derivatives have attracted significant attention due to their various applications in organic synthesis and biomimetic studies. For example, PhIO has been extensively used for generating high-valent metal-oxo species that have been regarded as key intermediates in diverse oxidative reactions in biological system. However, recent studies have shown that metal-iodosylbenzene adduct, known as a precursor of metal-oxo species, plays an important role in transition metal-catalyzed oxidation reactions. During last few decades, extensive investigations have been conducted on the synthesis and reactivity studies of metal-iodosylbenzene adducts with early and middle transition metals including manganese, iron, cobalt. Nevertheless, metal-iodosylbenzene adducts with late transition metals such as nickel, copper and zinc, still remains elusive. Herein, we report a novel copper(II)-iodosylbenzene adduct bearing a linear ligand composed of two pyridine rings and an ethoxyethanol side-chain, [Cu(OIPh)(HN3O2)]2+ (1). The copper(II)-iodosylbenzene adduct was characterized by several spectroscopic methods including UV–vis spectroscopy, electrospray ionization mass spectrometer (ESI MS), and electron paramagnetic resonance (EPR) combined with theoretical calculations. Interestingly, 1 can carry out the catalytic sulfoxidation reaction. In sulfoxidation reaction with thioanisole under catalytic reaction condition, not only two-electron but also four-electron oxidized products such sulfoxide and sulfone were yielded, respectively. However, 1 was not an efficient oxidant towards CH bond activation and epoxidation reactions due to the steric hindrance created by the intramolecular H-bonding interaction between HN3O2 ligand and iodosylbenzene moiety.

Type-specific impacts of silver on the protein profile of tomato (Lycopersicon esculentum L.)

Silver nanoparticles (AgNPs) are particularly among the widely used nanomaterials in medicine, industry, and agriculture. The small size and large surface area of AgNPs and other nanomaterials result in their high reactivity in biological systems. To better understand the effects of AgNPs on plants at the molecular level, tomato (Lycopersicon esculentum L.) seedlings were exposed to 30 mg/L silver in the form of nanoparticle (AgNPs), ionic (AgNO3), or bulk (Ag0) in 50% Hoagland media for 7 days. The effects of silver on the expression of plant membrane transporters H+-ATPase, vacuolar type H+-ATPase (V-ATPase), and enzymes isocitrate dehydrogenase (IDH), and catalase in roots was assessed using RT-qPCR and immunofluorescence-confocal microscopy. We observed significantly higher expression of catalase in plants exposed to AgNPs (Fold of expression 1.1) and AgNO3 (Fold of expression 1.2) than the control group. The immunofluorescence imaging of the proteins confirmed the gene expression data; the expression of the enzyme catalase was upregulated 41, 216, and 770% higher than the control group in plants exposed to AgNPs, Ag0, and AgNO3, respectively. Exposure to AgnO3 resulted in the upregulation (fold of expression 1.2) of H+-ATPase and downregulation (fold of expression 0.7) of V-ATPase. A significant reduction in the expression of the redox-sensitive tricarboxylic cycle (TCA) enzyme mitochondrial IDH was observed in plants exposed to AgNPs (38%), AgNO3 (48%), or Ag0 (77%) compared to the control. This study shows that exposure to silver affects the expression of genes and protein involved in membrane transportation and oxidative response. The ionic form of silver had the most significant effect on the expression of genes and proteins compared to other forms of silver. The results from this study improve our understanding about the molecular effects of different forms of silver on important crop species. Novelty statement Silver nanoparticles released into the environment can be oxidized and be transformed into ionic form. Both the particulate and ionic forms of silver can be taken by plants and affect plants physiological and molecular responses. Despite the extensive research in this area, there is a scarce of information about the effects of silver nanoparticles on the expression of membrane transporters especially H+-ATPase involved in regulating cells' electrochemical charge, and the activity of enzymes involved in oxidative stress responses. This is a unique study that evaluates the expression of cellular proton transporters and enzymes of redox balance and energy metabolisms such as membrane transporters, H+-ATPase, and V-ATPases, and enzymes catalase and IDH. The results provide us valuable information about the impact of silver on plants at the molecular level by evaluating the expression of genes and proteins. Key Message The exposure of plants to silver as an environmental stressor affects the expression of genes and proteins involved in maintaining cell’s electrochemical gradient (H+-ATPase, V-ATPase) and redox potential (IDH, catalase).

Palladium Probe Consisting of Naphthalimide and Ethylenediamine for Selective Turn-On Sensing of CO and Cell Imaging.

An assay to detect carbon monoxide (CO), one of the gaseous signaling molecules, has been prepared using a new palladium complex probe. The ethylenediamine group linked to the naphthalimide fluorophore coordinates to Pd(II) which intramolecularly quenches the emission. Upon treatment with CO, the absorbance of the turn-on fluorescent sensor changes due to the formation of a complex between Pd(II) and CO at room temperature in a phosphate buffer. As the concentration of CO increases, the probe peak emission intensity at 527 nm gradually increases. Other analyte controls, such as K+, Mg2+, Al3+, Zn2+, Cr3+, Hg2+, Fe3+, alanine, glycine, leucine, lysine, serine, threonine, tyrosine, F-, Cl-, Br-, NO, NO2-, NO3-, HCO3-, CH3COO-, H2O2, •OH, and tBuOO•, exhibit no significant effect on emission intensity. The response time of the probe to CO was quite fast because of the relatively weak coordination of Pd(II) to the pendent ethylenediamine group. The Pd probe is capable of detecting CO in aqueous buffer as well as in living cells with high selectivity and stability, providing a potential real-time indicator for studying CO-involved reactions in biological systems.

Photogenerated Radical Pair between Flavin and a Tryptophan-Containing Transmembrane-Type Peptide in a Large Unilamellar Vesicle.

Electron-transfer (ET) reactions in biological systems, such as those with magnetic sensors based on flavoproteins and electron transport at biomembrane interfaces, are interesting and important issues that require understanding. As a model system of flavoproteins in biomimetic environments, we report the dynamics of the radical pair generated by photoinduced ET between riboflavin tetrabutylate (RFTB) and tryptophan (Trp) residues in a transmembrane-type polypeptide, both of which are distributed in a large unilamellar vesicle of 1,2-dimyristoyl-sn-glycero-3-phosphocholine. The Trp residues locate near the hydrophilic membrane interface, as confirmed by a dual-fluorescence quenching assay. The fluorescence and transient absorption upon photoexcitation of RFTB indicate that ET from both the singlet and triplet excited states occurs at the hydrophilic interface, whereas the RFTB in the hydrophobic region does not contribute to ET. The ET efficiency and the magnetic field effect (MFE) on the RFTB anion increase significantly above the gel-to-liquid crystal phase transition temperature due to a decrease in microviscosity. The MFE analysis indicates that the radical pair generated from the triplet ET channel exhibits a long lifetime as those in micellar systems due to the strong cage effect of the vesicle.

Antimicrobial Photodynamic Therapy: Molecular Cell Mechanisms and Prospects for Use in Dentistry

The article touches upon general issues of the course of photochemical reactions in biological systems and the mechanisms of such reactions during laser photodynamic therapy in dentistry. The properties and role of singlet oxygen, features of the response to photodynamic effects of gram-positive and gram-negative microorganisms, the spectrum and stages of the emergence of modern photosensitizers, and their disadvantages are reflected. On the basis of the information provided, as a conclusion, the main directions of the development of antimicrobial photodynamic therapy are formulated today.

Mass Spectrometry-based Metabolomics in Translational Research.

Metabolomics is the systematic study of metabolite profiles of complex biological systems, and involves the systematic identification and quantification of metabolites. Metabolism is integrated with all biochemical reactions in biological systems; thus metabolite profiles provide collective information on biochemical processes induced by genetic or environmental perturbations. Transcriptomes or proteomes may not be functionally active and not always reflect phenotypic variations. The metabolome, however, consists of the biomolecules closest to the phenotype of living organisms, and is often called the molecular phenotype of biological systems. Thus, metabolome alterations can easily result in disease states, providing important clues to understand pathophysiological mechanisms contributing to various biomedical symptoms. The metabolome and metabolomics have been emphasized in translational research related to biomarker discovery, drug target discovery, drug responses, and disease mechanisms. This review describes the basic concepts, workflows, and applications of mass spectrometry-based metabolomics in translational research.

Exploring the Use of Gas Chromatography Coupled to Chemical Ionization Mass Spectrometry (GC-CI-MS) for Stable Isotope Labeling in Metabolomics.

Isotopic-labeling experiments have been valuable to monitor the flux of metabolic reactions in biological systems, which is crucial to understand homeostatic alterations with disease. Experimental determination of metabolic fluxes can be inferred from a characteristic rearrangement of stable isotope tracers (e.g., 13C or 15N) that can be detected by mass spectrometry (MS). Metabolites measured are generally members of well-known metabolic pathways, and most of them can be detected using both gas chromatography (GC)-MS and liquid chromatography (LC)-MS. In here, we show that GC methods coupled to chemical ionization (CI) MS have a clear advantage over alternative methodologies due to GC's superior chromatography separation efficiency and the fact that CI is a soft ionization technique that yields identifiable protonated molecular ion peaks. We tested diverse GC-CI-MS setups, including methane and isobutane reagent gases, triple quadrupole (QqQ) MS in SIM mode, or selected ion clusters using optimized narrow windows (∼10 Da) in scan mode, and standard full scan methods using high resolution GC-(q)TOF and GC-Orbitrap systems. Isobutane as a reagent gas in combination with both low-resolution (LR) and high-resolution (HR) MS showed the best performance, enabling precise detection of isotopologues in most metabolic intermediates of central carbon metabolism. Finally, with the aim of overcoming manual operations, we developed an R-based tool called isoSCAN that automatically quantifies all isotopologues of intermediate metabolites of glycolysis, TCA cycle, amino acids, pentose phosphate pathway, and urea cycle, from LRMS and HRMS data.

Gordon Henry Dixon. 25 March 1930—24 July 2016

Gordon H. Dixon was a highly influential scientist who excelled in all the stages of his career and in each laboratory of every institution at which he was a member. Gordon began his graduate career at the University of Cambridge and completed his studies at the University of Toronto on the subject of transpeptidation reactions in biological systems. At an early stage of his career, he developed the technique of starch gel electrophoresis with Oliver Smithies and made important discoveries on the structure of human haptoglobins. Subsequently, Gordon contributed to the determination of the structure and active sites and mechanisms of action of trypsin and chymotrypsin and made seminal discoveries related to understanding the structure of the protein hormone insulin. However, he is best known for his later studies on the regulation of protamine genes and chromatin transitions in spermatogenesis. He is often considered to be the father of the protamine molecular biology underlying this gene system and his research is continually cited to this day. Gordon contributed to the identification and sequencing of the protamine genes, the discovery that methionine was required for initiation of protamine synthesis, understanding the roles of histone hyperacetylation and protamine phosphorylation, and the generation of the highly compact nucleoprotamine structure present in sperm, primarily using trout as a model system. Gordon is fondly remembered as a brilliant and very generous scientist by all his mentees, representing all levels from undergraduates to PhD and postdoctoral fellows, who provided a scientifically stimulating atmosphere in which they could develop their careers. From a more personal perspective, he also had a fun side and was devoted to his family. Gordon was a person who, owing to his legacy of great science and his fundamental humanity, still lives in the memory of many people.

ATP synthase: Evolution, energetics, and membrane interactions.

The synthesis of ATP, life's "universal energy currency," is the most prevalent chemical reaction in biological systems and is responsible for fueling nearly all cellular processes, from nerve impulse propagation to DNA synthesis. ATP synthases, the family of enzymes that carry out this endless task, are nearly as ubiquitous as the energy-laden molecule they are responsible for making. The F-type ATP synthase (F-ATPase) is found in every domain of life and has facilitated the survival of organisms in a wide range of habitats, ranging from the deep-sea thermal vents to the human intestine. Accordingly, there has been a large amount of work dedicated toward understanding the structural and functional details of ATP synthases in a wide range of species. Less attention, however, has been paid toward integrating these advances in ATP synthase molecular biology within the context of its evolutionary history. In this review, we present an overview of several structural and functional features of the F-type ATPases that vary across taxa and are purported to be adaptive or otherwise evolutionarily significant: ion channel selectivity, rotor ring size and stoichiometry, ATPase dimeric structure and localization in the mitochondrial inner membrane, and interactions with membrane lipids. We emphasize the importance of studying these features within the context of the enzyme's particular lipid environment. Just as the interactions between an organism and its physical environment shape its evolutionary trajectory, ATPases are impacted by the membranes within which they reside. We argue that a comprehensive understanding of the structure, function, and evolution of membrane proteins-including ATP synthase-requires such an integrative approach.

Engineered glyphosate oxidase coupled to spore-based chemiluminescence system for glyphosate detection

The extensive and intensive utilization of glyphosate (Glyp) caused public concerns on the potential risk of environment and health resulted from the chemical residues. Therefore, the development of a high-selective, low-cost and easy-operation Glyp detection methods is highly desired. Screening highly selective enzymes by directed evolution is important in practical applications. Herein, a glyphosate oxidase (GlypO) preferring substrate Glyp to produce H2O2 was obtained via directed evolution from glycine oxidase obtained from Bacillus cereus (BceGO). The catalytic efficiency, specificity constant, and affinity enhancement factor of GlypO toward Glyp were increased by 2.85 × 103-fold; 2.25 × 105-fold; and 9.64 × 104-fold, respectively, compared with those of BceGO. The catalytic efficiency toward glycine decreased by 78.60-fold. The spores of Bacillus subtilis (B. subtilis) effectively catalyzed luminol-H2O2 reaction to create excellent chemiluminescence (CL) signal because CotA-laccase exists on their surface. Based on these findings, a new CL biosensor via coupling to biological reaction system was presented for Glyp detection. The CL biosensor exhibited several advantages, such as eco-friendliness, low cost, high selectivity and sensitivity, and good practical application prospects for environmental pollution control.

Pooled analysis of genotoxicity markers in relation to exposure in the Flemish Environment and Health Studies (FLEHS) between 1999 and 2018

BackgroundThe Flemish Environment and Health Studies (FLEHS) are human biomonitoring surveys running in Flanders since 1999. Additionally to biomarkers of exposure, markers of genotoxicity and oxidative stress have been measured, including the alkaline comet and micronucleus assay in peripheral whole blood cells, and urinary concentrations of 8-oxo-2′-deoxyguanosine (8-oxodG). AimExposure-effect associations were explored in a pooled dataset of nine different cross-sectional FLEHS surveys. Data of adolescents collected in a time frame of about 20 years (1999–2018) were compiled. The aim of the study was to examine whether increased variation in exposure, lifestyle and environmental factors would lead to more powerful and robust exposure-effect associations. Materials & methodsThe biomarkers were measured in 2283 adolescents in the age range of 14–18 years. Exposure to polycyclic aromatic hydrocarbons [1-hydroxypyrene (1-OHP)], benzene (tt’-muconic acid), metals (arsenic, cadmium, copper, nickel, thallium, lead, chromium), persistent organochlorines and phthalates were assessed in blood or urine. Furthermore, outdoor air levels of particulate matter (PM10 and PM2.5) at the residences of the youngsters were calculated. Pooled statistical analysis was done using mixed models. Study-specific differences in the genotoxicity markers and in the strength/direction of the association were accounted for. This was done by incorporating the random factor ‘study’ and a random study slope (if possible). The exposure markers were centered around the study-specific mean in order to correct for protocol changes over time. ResultsA significant association was observed for the urinary oxidative stress marker 8-oxodG, which was positively associated with 1-OHP (5% increase for doubling of 1-OHP levels, p = 0.001), and with urinary copper (26% increase for doubling of copper levels, p = 0.001), a metal involved in the Fenton reaction in biological systems. 8-oxodG was also associated with the sum of the metabolites of the phthalate di(2-ethylhexyl) phthalate (DEHP) (3% increase for doubling of the DEHP levels, p = 0.02). For those associations, data pooling increased the statistical power. However, some of the associations in the individual surveys, were not confirmed in the pooled analysis (such as comet assay and 8-oxodG vs. atmospheric PM; and 8-oxodG vs. urinary nickel). This may be due to inconsistencies in exposure-effect relations and/or variations in the pollutant mix over time and regions. ConclusionPooled analysis including a large population of 2283 Flemish adolescents showed that 8-oxodG, a marker of oxidative DNA damage is a valuable marker to assess impact of daily life pollutants, such as PAHs, Cu and the phthalate DEHP.

Cooperative Binding of 1-Phenylimidazole to Cobalt(II) Octaethylporphyrin on Graphite: A Quantitative Imaging and Computational Study at Molecular Resolution

Cooperative interactions play a critical role in the stability and reactivity of biological systems and an increasingly important consideration in the synthesis of functional materials, but quantit...

Impact of Natural Antioxidants on Biological Systems

ABSTRACT:Free radicals are the unstable electron-deficient species that reacts with different molecules to gain stability and to eliminate their unpaired condition. Antioxidant molecules neutralizes the free radicals by donating their electrons and inhibits the unwanted oxidative reactions in biological system. The imbalance between antioxidants and free radicals generated oxidative stress which leads to severe impairment of the biological systems. The purpose of the present review is to highlight the beneficial role of naturally occurring antioxidant systems in minimizing the damage and maintaining the homeostasis in the biological system. Enzymatic and non-enzymatic antioxidants are the major classes of natural antioxidants which executes diverse functions in the biological system to provide defense against the destructive accumulating effects of ROS/RNS. Superoxide dismutase (SOD) are responsible for providing first line of defense to thebiological system, by converting the superoxide anion radical (O oˉ) into hydrogen 2 peroxide (H O ) which eventually converted into water and oxygen. Non-enzymatic 2 2 antioxidants either endogenous or exogenous provides numerous crucial mechanisms to quench the ROS/RNS in the biological system. Endogenous antioxidants inhibits lipid peroxidation in the cellular membranes while the exogenous antioxidants acts as chain breakers and terminates the oxidative chain reaction. It is significant to sustain the level of exogenous antioxidants in the body through diet so that the normal biological processes can be maintained at optimal levels.

Effects of nonequilibrium fluctuations on ultrafast short-range electron transfer dynamics

A variety of electron transfer (ET) reactions in biological systems occurs at short distances and is ultrafast. Many of them show behaviors that deviate from the predictions of the classic Marcus theory. Here, we show that these ultrafast ET dynamics highly depend on the coupling between environmental fluctuations and ET reactions. We introduce a dynamic factor, γ (0 ≤ γ ≤ 1), to describe such coupling, with 0 referring to the system without coupling to a “frozen” environment, and 1 referring to the system’s complete coupling with the environment. Significantly, this system’s coupling with the environment modifies the reaction free energy, ΔGγ, and the reorganization energy, λγ, both of which become smaller. This new model explains the recent ultrafast dynamics in flavodoxin and elucidates the fundamental mechanism of nonequilibrium ET dynamics, which is critical to uncovering the molecular nature of many biological functions.

Enhanced Stability of Enzyme Immobilized in Rationally Designed Amphiphilic Aerogel and Its Application for Sensitive Glucose Detection.

Natural enzyme complex with the subunits cooperating with each other could catalyze cascade reactions in biological system but, just like the limitation of free-floating natural enzymes, usually suffer from deactivation in harsh environment such as high temperature. In this study, a purpose-driven design of amphiphilic aerogel working as the enzymes-immobilization substrate to form the multienzyme complex (MEC) was demonstrated. The aerogel was synthesized only by a single polymer poly(vinyl alcohol) (PVA) as well as a surface modulator maleic acid (MA), the incorporation of which tunes the surface wettability. The usage of the amphiphilic aerogel may do favor for multienzyme immobilization, conserving the enzyme conformation as well as stabilizing the enzymes in high temperature. As a typical example, glucose oxidase and hemin were firmly coimmobilized in the aerogel matrix and actively catalyze the cascade reactions of (i) glucose to gluconic acid and (ii) 3,3,5,5-tetramethylbenzidine (TMB) to its oxidized state. The enzymes could resist the degradation under high temperature (70-100 °C) which is witnessed by the rate of decrease in activity was progressively slackened. Taking the advantage of the chromogenic reaction of TMB, a glucose sensor based on aerogel-enzyme composite for glucose detection in whole blood and sweat was established, exhibiting reliable results and satisfactory recovery. The modified aerogel could also withstand multiple physical deformation meantime maintaining good adsorption capacity as well as catalytic performance. The enzymes-loading aerogel model may hopefully contribute to composing sensors based on other analytes.

A macroscopic theory for predicting catastrophic phenomena in both biological and mechanical chemical reactions

A possibility for predicting the time-dependent pattern of sickness of human beings, i.e., biological catastrophe, has been shown by proposal of a nonlinear ordinary differential equation, describing temporal features of six macroscopic molecular groups chemically interacting in living beings, (Naitoh in Jpn J Ind Appl Math 28:15–26, 2011; Naitoh and Inoue in J Artif Life Robot 18:127–132, 2013). Logically, we also find that, six is minimum and essential as the number of macroscopic molecular groups for describing living systems. Then, along with the number theory applied for the differential equation, we derive critical mathematical conditions for predicting the premonition just before sickness (discrepancy from a healthy condition), which agree with an important knowledge revealed by the linear analysis proposed by Chen (Dynamical network biomarkers for identifying early-warning signals of complex diseases, Beppu, Oita Japan, 2015). In the present report, we first show that computational several time-histories of sickness obtained by solving the nonlinear differential equation with various parameters describing polymorphism agree well with actual time-dependent patterns of sickness for human beings, which is further evidence of usefulness of the nonlinear differential equation and its critical mathematical conditions. Thus, to examine the boundary between biological and abiological chemical reaction systems, which is related to the origin of living systems, we next check whether or not the nonlinear equation can also predict such abiological catastrophic phenomenon as misfire in artifacts including mechanical combustion engines.