Organic Macromolecules Research Articles

Preparation of Microelectrolysis Filler Using Coal Slag for the Removal of Hazardous Substances in Contaminated Water.

Presently, the utilization of gasification slag in the context of wastewater treatment is constrained. Furthermore, the presence of dye wastewater and wastewater containing hazardous metals represents a significant threat to human health. Accordingly, the present study prepared a microelectrolytic filler (MF) from gasification slag via a high-temperature roasting method and evaluated its degradation performance in water containing organic matter and harmful metal ions. The impact of varying preparation conditions, including initial solution pH and MF dose, on the degradation process was examined. The removal of methyl blue was found to be 92.21% at an initial pH of 2, a reaction time of 300 min and a dosage of 40 g L-1. The removal of Cu(II), Cd(II), and Pb(II) metal ions was 97.32, 96.58, and 99.38%, respectively, at an initial pH of 4, a reaction time of 180 min, and a dosage of 10 g L-1. Following five cycles, the MF process demonstrated continued efficacy in the removal of dyes and heavy metals from the wastewater. A mechanistic analysis revealed that the water treatment process is not a single adsorption process. Instead, it was found that organic macromolecules undergo chain-breaking reactions, while heavy metal ions undergo redox reactions. The wastewater treatment process comprises a number of distinct strategies, including electrochemical reactions, adsorption, flocculation, and precipitation. These findings illustrate the potential of a gasification slag green recycling approach to treat waste with waste, in alignment with the principles of sustainable development.

A highly capacitive Graphene/Multiholed N‐CNTs hybrid evolved from black humate‐Co‐melamine precursor

Black humic acid (BA) is a black mixture of organic macromolecules isolated from humic acid, which has a greater potential for graphene transformation than fulvic acid and ulmic acid because of more and larger aromatic units and higher molecular weights exceeding 5000 Dalton. Here, chemically bonded BA‐Co‐Melamine precursors are initially constructed using different BA fractions as substrate, Co2+ as bridge bond and melamine as ligand. A series of Graphene/N‐CNTs hybrids (GNCs) is eventually synthesized after the precursor pyrolysis. Resultantly, Fraction Ⅰ, separated at a pH value of 4.16, plays a significant role on constructing the BA‐Co‐Melamine precursor and further producing multiholed GNCs. Due to abundant CNTs, rich mesopores, moderate nitrogen incorporation and a certain graphitized assembly structure, the prepared GNC‐Ⅰ‐b has high capacitance performances. The assembled AC//GNC‐Ⅰ‐b supercapacitor has high specific capacitance (147 F g‐1 at 0.5 A g‐1), rate capability, cycling stability and energy density (16.8 Wh kg‐1 at 14.4 KW kg‐1). The 2032 coin‐type Li//GNC‐Ⅰ‐b half‐cell has high initial discharge capacity (759 mAh g‐1 at 0.03 A g‐1), initial Coulombic efficiency (81.8%), rate performance and cycling stability. Hence, the GNC is a favorable high‐performance carbon material hopefully applied as electrode materials of supercapacitors and LIBs.

Dissolved organic matter (DOM) rather than warming and eutrophication directly affects partial pressure of CO2 (pCO2) in mesocosm systems

Environmental warming and eutrophication pose significant challenges to shallow lake systems, where dissolved organic matter (DOM) serves as a diverse and intricate mixture of organic macromolecules, playing a pivotal role in aquatic ecosystems. Despite its complexity, comprehending the interplay between environmental changes and DOM composition alterations and their subsequent impacts on aqueous CO2 partial pressure (pCO2) is essential for a better understanding of carbon cycling. Yet, our current understanding in this realm remains limited. To address this gap, mesocosm systems were established to investigate how elevated water temperature and eutrophication, alongside changes in DOM composition, influence pCO2 dynamics. Results indicate that while temperature and nutrient levels do not directly influence pCO2 fluctuations, they indirectly affect aqueous pCO2 through their modulation of DOM composition. Elevated temperature and nutrient concentrations notably enhance both the production and degradation of indigenous protein-like organic matter and increase the accumulation of humic-like organic compounds, with phosphorus released from sediment playing a particularly significant role. Furthermore, the degradation rate of protein-like organic matter significantly exceeds its accumulation rate. On the other hand, the impact of water eutrophication on DOM composition surpasses that of temporal temperature variations, with a 2∼4 °C temperature rise showing minimal effects on DOM composition. Notably, the degradation of protein-like organic matter markedly increases aqueous pCO2, while the rise in humic-like organic matter in water exerts minimal influence on pCO2 concentrations. A comprehensive understanding of carbon cycling processes under environmental changes will facilitate effective management of lake ecosystems and the advancement of carbon mitigation technologies.

The application of unsupervised machine learning for the elucidation of the burial effect of lignin in peatland: Case of TMAH thermochemolysis

Lignin is one of the major components of organic macromolecules in peatland. Analysis of lignin in sediments is considered as a valuable tool for understanding peat vegetation as well as carbon cycle. It provides valuable perspectives on different sides such as occurrence of various vegetation types and the extent of decay in terrestrial organic material. Thermochemolysis technique using tetramethyl ammonium hydroxide (TMAH) was used for lignin analysis, in an ombrotrophic peatland. It specifically breaks of O-aryl bonds followed by methylation of the lignin components yielding phenolic subunits. Several discrepancies exist between TMAH thermochemolysis findings and those obtained from previous investigations with CuO oxidation. This could be explained by the specific pool of aryl ether, specifically targeted by the thermochemolysis, with discarding of C-C bonds. Hence, this would show the capacity of TMAH thermochemolysis to cleave oxidised lignin leaving lignin of fresh and preserved organic matter intact. The TMAH thermochemolysis method's efficiency in molecular characterization and lignin degradation was evaluated using principal component analysis (PCA). PCA reduced dimensionality and redundancy of component contributions, with the first two principal components accounting for 70.33 % of the total variance. PCA has reinforced the selectively of the thermochemolytic approach in targeting O-aryl bonds while maintaining C-C bonding of polyphenolic sub-units. Hence, two distinct oxidation phases: recent (acrotelm and mesotelm) and older (catotelm) have been revealed. PCA was applied to diagenetic and source vegetation proxies, revealing strong agreement among variables which is supported by the use of molecular ratios as indicators of organic matter source and dynamics in a peat core.

Adsorption and desorption of phenanthrene and 1-hydroxyphenanthrene by goethite-coated polyvinyl chloride

Microplastics loaded with phenanthrene and derivatives are widely detected in aquatic environments, and the coating of natural minerals or organic macromolecules may change the environmental behavior of microplastics. In this study, three kinds of composites with different coverage were prepared by coating goethite on the surface of polyvinyl chloride microplastics to investigate the adsorption and desorption behavior of phenanthrene (PHE) and 1-hydroxyphenanthrene (1-OHPHE), and the effect of mucin on desorption was investigated. The results showed that goethite promoted the adsorption of PHE and 1-OHPHE by increasing the specific surface area of the composites. With the increase of the cover degree, the adsorption of PHE decreased because of the decrease in hydrophobicity; while the adsorption of 1-OHPHE initially increased and then decreased with the contributions of hydrophobic interaction and hydrogen bond. The adsorption of 1-OHPHE could be influenced by the pH and ionic strength primarily through electrostatic interactions and Ca2+ bridging. The goethite significantly increased the desorption hysteresis for two chemicals due to the complicated pore structures and increased adsorption affinity. Mucin promoted the desorption of PHE through competitive adsorption, and inhibit the desorption of 1-OHPHE through hydrophobic interaction, hydrogen bonding and Ca2+ bridging. This study elucidated the effects of natural minerals on the adsorption and desorption behavior of organic pollutants on microplastics, briefly discussed the effects of organic macromolecules on the desorption behavior of pollutants with different properties, and emphasized the different environmental behaviors of pollutants.

Eco-friendly sustainable fluorescent coal-based carbon dots as a highly selective probe for Cu2+detection

Carbon dots as fluorescent probes exhibit brilliant sensitivity and selectivity in copper ion detection, which greatly depends on their microstructure. Herein, a mild oxidation method was adopted to tailor the organic macromolecules of coal and its derivatives for preparing coal-based carbon dots. Such coal-based carbon dots comprise a carbonaceous center dominated by sp2 microcrystalline carbon, surface defects formed by sp3 amorphous carbon, and oxygen/nitrogen-containing functional groups. The coal-based humic acid-based carbon dots (HA-CDs) exhibit high dispersity (∼7.6 nm), high sp2 microcrystalline carbon (61.73 %), abundant carboxyl groups (2.09 %), hydroxy groups (8.93 %), and pyridinic nitrogen (1.06 %). Due to their unique microstructure, the HA-CDs in aqueous solutions exhibit prominent fluorescence stability under different pH conditions and show superior selectivity and sensitivity to Cu2+ even in the existence of other metal ions. Within the concentration range of 0–40 µmol/L, the fluorescence intensity of HA-CDs linearly correlates with the concentration of Cu2+. The limit of detection is 0.014 µmol/L, allowing for tracing the Cu2+ concentration in flowing water. This work affords a novel idea for the microstructure design of high-sensitivity carbon dots for Cu2+ detection in the water environment.

Mechanism and application of bacterial exopolysaccharides: An advanced approach for sustainable heavy metal abolition from soil

The escalation of heavy metal pollutants in soils and effluents, driven by industrialization and human activities, poses significant environmental and health risks. Conventional remediation methods are often costly and ineffective, prompting a shift towards sustainable alternatives such as biological treatments. Natural biosorbents, including microbial cells and their byproducts, have emerged as promising solutions. One such approach involves leveraging exopolysaccharides (EPS), complex high-molecular-weight biopolymers synthesized by microbes under environmental stress conditions. EPS are intricate organic macromolecules comprising proteins, polysaccharides, uronic acids, humic compounds, and lipids, either located within microbial cells or secreted into their surroundings. Their anionic functional groups enable efficient electrostatic binding of cationic heavy metals, making EPS effective biosorbents for soil remediation. This review thoroughly explores the pivotal role of bacterial EPS in the removal of heavy metals, focusing on EPS biosynthesis mechanisms, the dynamics of interaction with heavy metals, and case studies that illustrate their effectiveness in practical remediation strategies. By highlighting these aspects, the review underscores the innovation and practical implications of EPS-based bioremediation technologies, demonstrating their potential to address critical environmental challenges effectively while paving the way for sustainable environmental management practices. Key findings reveal that EPS exhibit robust metal-binding capacities, facilitated by their anionic functional groups, thereby offering a promising solution for mitigating metal pollution in diverse environmental matrices.

Separation of galena and pyrite via green organic macromolecules at low alkalinity: Flotation response and surface adsorption mechanisms

Pyrite must be separated from galena during the beneficiation stage because it releases toxic gases during pyrometallurgy. However, the separation of the two minerals presents a huge obstacle as they have comparable hydrophobicity. This work offers an environmentally friendly pyrite depressant, pullulan polysaccharide (PP), for concentrating galena. Single mineral flotation showed that the ability of PP to deteriorate floatability was significantly stronger for pyrite than for galena within the pH range of 6.00 − 12.00. PP preadsorption assisted in separating galena from pyrite in a low-alkalinity pulp. The recovery of galena was 71.20 % higher than that of pyrite in the binary mineral flotation system. Characterization results confirmed that the Fe sites of pyrite were more susceptible to forming a stable coordination with the O atoms of PP’s C−O−H group compared to the Pb sites of galena. PP can impede the sodium butyl xanthate (BX) sorption on the pyrite surface, thus effectively depressing the pyrite. By contrast, the sorption of BX onto the galena surface was unaffected by PP, and the galena remained floatable. Thus, PP could be considered as an alternative to conventional inorganic depressants in the galena–pyrite flotation system. This work provides a scientific reference for the green and sustainable exploitation of non-ferrous metal resources.

(Invited) Synthesis of Multi-Metallic Nanoparticles for Advanced Catalysts

Dendrimers are highly branched organic macromolecules with successive layers or “generations” of branch units surrounding a central core. Organic inorganic hybrid versions have also been produced, by trapping metal ions or metal clusters within the voids of the dendrimers. Their unusual, tree-like topology endows these nanometer-sized macromolecules with a gradient in branch density from the interior to the exterior, which can be exploited to direct the transfer of charge and energy from the dendrimer periphery to its core.We show that PtCl4, SnCl2, FeCl3, and so on complexes to the imines groups of a spherical polyphenylazomethine dendrimer in a stepwise fashion according to an electron gradient, with complexation in a more peripheral generation proceeding only after complexation in generations closer to the core has been completed. By attaching an electron-withdrawing group to the dendrimer core, we are able to change the complexation pattern, so that the core imines are complexed last. By further extending this strategy, it should be possible to control the number and location of metal ions incorporated into dendrimer structures, which might and uses as tailored catalysts, building blocks, or fine-controlled clusters for advanced materials. The metal-assembly in a discrete dendrimer molecule can be converted to a size-regulated metal particle with a size smaller than 1 nm as a molecular reactor. Due to the well-defined number of metal clusters in the subnanometer region, its property is much different from that of bulk or general metal nanoparticles. The chemistry of nanocatalysts on the sub-nanometer scale is not yet well understood because precise multi-metallic nanoparticles are difficult to synthesize with control over size and composition. The template synthesis of multi-metallic sub-nanocalaysts is achieved using a phenylazomethine dendrimer as a macromolecular template.

Characterization and subcellular localization of selenium in Limosilactobacillus fermentum Ln-9 obtained by intense pulsed light-ultraviolet combined mutagenesis

Lactic acid bacteria (LAB) can convert inorganic selenium (Se) to organic Se and elemental forms with low toxicity and high bioavailability, but a comprehensive Se analysis of Se-enriched LAB is lacking. In this study, Limosilactobacillus fermentum Ln-9 was obtained by intense pulsed light-ultraviolet combined mutagenesis, and its characteristics and subcellular localization of Se were analyzed. The results displayed that Ln-9 accumulated 3.03 times Se that of the original strain. Under optimal fermentation conditions, the total Se content of Se-enriched Ln-9 (SeLn-9) reached 12.16 mg/g with 96.34% contained in Se nanoparticles (SeNPs), which was much higher than that of organic macromolecules. Furthermore, SeNPs were mainly localized outside the cell, Se-proteins were in the membrane and cytoplasmic fractions, and Se-polysaccharides were in the membrane fraction. Besides, SeLn-9 maintained a good morphology and gastrointestinal tolerance and had an enhanced antioxidant capacity. These findings make Ln-9 promising for applications in the food industry.

Cobalt-Modified Biochar from Rape Straw as Persulfate Activator for Degradation of Antibiotic Metronidazole

A cobalt-loaded magnetic biochar (Co-MBC) catalyst was synthesized to enhance the removal of metronidazole (MNZ). Study explored the performance and mechanism of MNZ degradation by Co-MBC activated permonosulfate (PMS). Results showed that cobalt oxides were effectively deposited onto the biochar surface, new oxygen functional groups were added to the modified biochar, and the presence of the metallic element Co enhanced the efficiency of PMS activation in the composite. More than 90% of MNZ was removed after 60 min with a catalyst dosage of 0.2 g/L and a PS concentration of 1 mM. After four reuses, Co-MBC still showed excellent catalytic performance to degrade over 75% of MNZ. The reaction system performed well even in the presence of inorganic anions and organic macromolecules. However, the degradation rate was inhibited under alkaline conditions. The quenching experiment indicated that •SO4−, •OH, 1O2, and •O2− synergistically degraded MNZ, and that•SO4− played a dominant role. LC-MS was applied to assess intermediate degradation products, in which CO2, H2O, and NO3− were the final degradation products, and potential degradation pathways were suggested. In conclusion, Co-MBC was an efficient and stable catalytic material, and its ability to activate PMS was improved to effectively degrade antibiotics, a typical priority pollutant.

Multi-omics combined approach to analyze the mechanism of flavor evolution in sturgeon caviar (Acipenser gueldenstaedtii) during refrigeration storage

Multi-omics techniques were combined with microstructure, molecular sensory science and non-volatile matrices for the first time to investigate variations in organic macromolecules and flavor in caviar during preservation. After 4–6 weeks of storage, the peroxide value was 35.38 mg/g and the accumulation of thiobarbiturates was significant with caviar membranes exhibiting a decrease in elasticity and an increase in viscosity. Sixteen key volatile compounds were detected by GC–MS, while the volatile compounds that contributed to the differences in caviar flavor at different storage times were mainly tetradecane, (E)-2-hexenal, and heptanal. The pathways associated with flavor release during storage were mainly abundant in the linolenic acid metabolism, alanine metabolism, and glycerophospholipid metabolism pathways. The correlation of 11 differential proteins and 24 differential lipids with odorants was further explored, such as arginine, proline, alanine, PE (20:4/22:6), PE (16:1/18:2), and PE (20:5/18:2). Overall, Aspartate, glutamate, oleic acid, linoleic acid, and phospholipids enriched in C22:6 and C18:2 chains are potential metabolic markers. This study provides a basis from a multi-omics perspective for the investigation of the relationship between quality deterioration and precursor metabolism in caviar storage process.

Research progress on formation mechanism of pearl

Pearls are deeply cherished for their rich color and gorgeous luster, and their quality directly affects their value. Currently, the evaluation of pearl quality is mainly based on four aspects: color, shape, size and smoothness. The quality of pearls is influenced by a variety of factors, categorized into internal factors, such as the structural composition of the nacreous layer and genetic factors of the mussels, and external factors, including the aquaculture environment. Existing research results indicates that genetic factors are the dominant factor controlling the pearl quality. However, the macromolecules such as metal ions, organic pigments and various physical and chemical factors in the aquaculture water environment will also significantly impact pearl quality. Among these, matrix proteins are organic macromolecules found in the nacreous layer that play an important role in pearl quality. They participate in the deposition of calcium carbonate and the construction of the organic framework, affecting the pearls’ size and shape. The color of pearls is influenced by the deposition of metal ions, the transport of organic pigments and the regulation of microstructure.

Basic magnesium carbonate template assisted co-carbonization of potassium citrate toward hierarchical porous carbon for supercapacitors

Hierarchical porous carbon (HPC) as the ideal host material for supercapacitors has received extensive attention. However, traditional methods of fabricating HPC often rely on organic macromolecules and complex procedures. Herein, a simple and straightforward approach is developed for the synthesis of HPC through basic magnesium carbonate template assisted co-carbonization of potassium citrate. Potassium citrate can be effectively embedded and encapsulated with basic magnesium carbonate due to the large bulk density difference between them. In the pyrolysis process, the carbon-containing small molecules produced by the pyrolysis of potassium citrate are deposited on the surface of MgO surface obtained from the decomposition of basic magnesium carbonate, and the etching reaction of potassium salt, CO2 and primary carbon structure occurs. The competitive rate of carbon deposition reaction and etching reaction can be easily controlled by changing the ratio of potassium citrate and basic magnesium carbonate. The obtained carbon materials show the morphology changes of nanoparticle accumulations, discontinuous carbon frames and carbon planar blocks, and the hierarchical porous structure of carbon materials can also be controlled in a wide range. HPC-2 exhibits the morphology of nanoparticle accumulation and generates abundant meso-macropores, which accelerates the rapid transport of electrolytic ions. The micropores inside the nanoparticles provide an accessible room for ionic adsorption. Benefited from this unique microstructural framework, HPC-2 shares a high capacitance of 305.5 F g−1 at 0.5 A g−1 and 173.1 F g−1 at 50 A g−1. Furthermore, the assembled symmetric supercapacitors exhibit a high energy density and power density than YP-50 F throughout the test range. The versatility of this synthetic strategy provides an insight into directional tailoring fine pore structure and micro-morphology of carbon materials based on small molecule deposition.

A robust self-regenerating graphene-based adsorbent for pharmaceutical removal in various water environments

The presence of active pharmaceutical ingredients (APIs) in wastewater effluents and natural aquatic systems threatens ecological and human health. While activated carbon-based adsorbents, such as GAC and PAC, are widely used for API removal, they exhibit certain deficiencies, including reduced performance due to the presence of natural organic macromolecules (NOMs) and high regeneration costs. There is growing demand for a robust, stable, and self-regenerative adsorbent designed for API removal in various environments. In this study, we synthesized a self-generating metal oxide nano-composite (S-MGC) containing titanium dioxide (TiO2) and silicon dioxide (SiO2) combined with 3D graphene oxide (GO) to adsorb APIs and undergo regeneration via light illumination. We determined optimal TiO2:SiO2:GO compositions for the S-MGCs through experiments using a model contaminant, methylene blue. The physical and chemical properties of S-MGCs were characterized, and their adsorption and photodegradation capabilities were studied using five model APIs, including sulfamethoxazole, carbamazepine, ketoprofen, valsartan, and diclofenac, both in single-component and multi-component mixtures. In the absence of TiO2/SiO2, 3D graphene oxide (CGB) displayed better adsorption performance compared to GAC, and S-MGCs further improve CGB's adsorption capacity. This performance remained consistent in two complex water environments: aqueous solutions at varying NOM levels and artificial urine. TiO2 supported on the GO surface exhibits similar photocatalytic activity to suspended TiO2. In a continuous fixed-bed column test, S-MGCs demonstrated robust API adsorption performance that is maintained in the presence of NOM or urine, and can be regenerated through multiple cycles of adsorption and light illumination.

A facile electrospinning strategy to prepare cost-effective carbon fibers as a self-supporting anode for lithium-ion batteries

Carbon materials with fibrous morphology and enhanced mechanical properties have shown to be promising materials as self-supporting anode materials for lithium-ion batteries (LIBs). In this study, coal-based carbon fibers (CFs) with favorable flexibility and superior tensile strength were prepared from lignite and coal derivatives such as coal-based humic acid and coal tar pitch via electrospinning in the assistance of polyacrylonitrile. All these coal-based CFs have an 1D dense fibrous microstructure with controllable diameter and appreciable specific surface area with enriched in O/N-containing groups by rationally choosing the precursor type. The organic macromolecules enriched aromatic ring in lignite and coal derivatives cross-link with linear polyacrylonitrile molecular chains to form a more solid three-dimensional (3D) network framework under the conditions of electrospinning and carbonization. Such 3D microstructure not only can significantly improve the flexibility and tensile strength of coal-based CFs, but also can increase the content of graphite-like microcrystalline carbon (sp2 carbon) in carbon fibers, thereby improving the electrical conductivity. Due to the smaller molecular structure, coal tar pitch can be more easily combined with polyacrylonitrile by electrostatic force. The CFs derived from coal tar pitch (CTP-CFs) exhibited the largest average diameter (156.2 nm), a higher microporous surface area (2.6 m2·g−1), higher pyrrole nitrogen and contained reasonable proportions of amorphous carbon (sp3 carbon) and sp2 carbon. As a consequence, among the various derived coal-based CFs applied as self-supporting anode materials for LIBs, CTP-CFs showed the highest first reversible capacity (770.8 mAh·g−1 at 20 mA·g−1) and excellent cycling performance with capacity retention rate of 89.1 % after 200 cycles. This work paves a new strategy to prepare CFs as flexible self-supporting anodes for LIBs from low-cost carbon precursors that can be rationally chosen to further tune the property of the CFs.

An anchor-inspired interface for improving interfacial properties of carbon fiber-reinforced high-performance thermoplastic composites

Carbon fiber-reinforced thermoplastic composites are promising materials with many application prospects. However, surface inertness of CFs weakens the interfacial properties of these composites. Therefore, in this study, an anchor-inspired structure was designed and grafted onto CFs by using an anchor-inspired segmented copolymer, comprising of polyimide as the “chain” and polyhedral oligomeric silsesquioxane (POSS) as the “anchor”. In combination with atom transfer radical polymerization with the advantage of controllable molecular weight, degree of polymerization of the anchor-shaped structure with the best compatibility with poly (phthalazinone ether nitrile ketone) (PPENK) resin was pre-determined through molecular dynamics simulations, which reduced the experimental costs. The results of X-ray photoelectron spectroscopy indicated the successful connection of the numerous anchor-shaped structures to the CFs. Compared to composite made of origin fibers and PPENK, the interfacial shear strength at the microscopic level and interlaminar shear strength at the macroscopic level of grafted CF and PPENK composite increased by 184.9 % and 44.2 %, respectively. This is mainly attributed to the synergistic effect of mechanical interlocking and interfacial interaction between the anchor-shaped structure and the PPENK resin. This study serves as a feasible path to enhance the interfacial adhesion of composites by designing an anchor-shaped structure of organic macromolecules and inorganic nanoparticles on CFs.

Microscale analysis reveals nature of hydrophobic biopolymers in aragonite bivalve shells with crossed-lamellar architecture

Bivalve shells with crossed-lamellar architecture consist of random orientation of anisotropic crystallographic directions that adds to the optimization of the mechanical properties of shell biominerals. The source of these anisotropic distortions has been attributed to the organic macromolecules in the inorganic unit. However, very little is known about the organic macromolecules in shells with crossed-lamellar architecture because it is believed that the organics in this shell ultrastructure can hardly be characterized owing to its low content, about 1 wt%. Here, the shells of two bivalve species (Callista kingii and Anadara trapezia) with crossed-lamellar architecture, have been studied by microRaman spectroscopy, FTIR, and histochemical analysis. For the first time, organic macromolecules and inorganic components were simultaneously identified. Using spectroscopic techniques (microRaman and FTIR) and a confocal scanning fluorescence microscopy, the results herein demonstrated minor chitin in the studied samples and document structural protein, collagen-like matrix as the major organic component. The SEM observations revealed a morphological biopolymer meshwork composed of a polygonal network. Based on those combined evidence, this study suggests that the interactions between polysaccharide-based biomolecules and collagen-like matrix are crucial for the mechanical properties of crossed-lamellar layers in bivalve shells. This study highlights the importance of using in-situ approaches for these types of biomaterials and provides another source of biomaterials.

Evaluation the role of insulin signaling pathway in reproductive toxicity of dispersed diesel particulate extract under environmental conditions

Diesel particulate extract (DPE), which is a significant constituent of airborne particle pollution, has a strong association with the development of cancer and respiratory diseases. Fulvic acid (FA), a plentiful organic macromolecule found in water, has the capability to modify particle surface charge and adsorption capacity when combined with minerals. Nevertheless, there is a scarcity of data regarding the influence of their interaction on DPE toxicity. To examine the impact of environmental factor on the toxic effects of DPE, we used the Caenorhabditis elegans (C. elegans) model to investigate the reproductive toxicity of DPE and FA on insulin signaling pathway. C. elegans were subjected to a semi-fluid medium (NGG) containing different concentrations of DPE or DPE + FA in order to assess germline apoptosis and the expression of important genes in the insulin signaling pathway. Through several mutant strains, we found that daf-2, age-1, pdk-1, akt-1 and daf-16 were involved in DPE-induced apoptosis. Furthermore, and the expression levels of these genes significantly altered. The ratio of daf-16 translocation to nucleation, as well as the amount of reactive oxygen species (ROS), exhibited a dose-response relationship, however, the presence of FA could altered these effects. The results revealed that the insulin signaling pathway plays a vital role in mediating the harmful effects caused by DPE, whereas environmental factors have a substantial impact on its toxicity. Moreover, it was noted that semi-fluid medium could effectively replicate three-dimensional exposure circumstances closely resembling those observed in actual situations.

Infrared Spectroscopy of Neutral and Cationic Benzonitrile-Methanol Binary Clusters in Supersonic Jets.

The formation of nitrogen-containing organic interstellar molecules is of great importance to reveal chemical processes and the origin of life on Earth. Benzonitrile (BN) is one of the simplest nitrogen-containing aromatic molecules in the interstellar medium (ISM) that has been detected in recent years. Methanol (CH3OH) exists widely in interstellar space with high reactivity. Herein, we measured the infrared (IR) spectra of neutral and cationic BN-CH3OH clusters by vacuum ultraviolet (VUV) photoionization combined with time-of-flight mass spectrometry. Combining IR spectra with the density functional theory calculations, we reveal that the BN-CH3OH intends to form a cyclic H-bonded structure in neutral clusters. However, after the ionization of BN-CH3OH clusters, proton-shared N···H···O and N···H···C structures are confirmed to form between BN and CH3OH, with the minor coexistence of H-bond and O-π structures. The formation of the proton-shared structure expands our knowledge of the evolution of the life-related nitrogen-containing molecules in the universe and provides a possible pathway to the further study of biorelevant aromatic organic macromolecules.