Chemical Structure Research Articles

Antibacterial mechanism of Malaysian Carey clay against food-borne Staphylococcus aureus.

Depending on their chemical structure and geochemistry, clay minerals can display potent antibacterial properties against a range of bacterial pathogens. Malaysian Carey clay was evaluated for its antibacterial activity against food-borne Staphylococcus aureus ATCC 13565 strains. The minimum inhibitory concentration (MIC) and minimum bactericidal activity (MBC) of both Carey clay leachates and suspension were 125 mg/mL and 250 mg/mL, respectively. Time-kill assay revealed that 2x MIC and 4x MIC Carey clay in both leachate and suspension forms resulted in complete killing of S. aureus. Antibacterial mechanism was investigated through imaging of bacterial morphology using TEM and determination of reactive oxygen species (ROS) using NBT assay. Imaging of bacterial morphology using TEM showed abnormalities, including disrupted cell walls following exposure to Carey clay, and the antibacterial activity was associated with generation of ROS. Our study suggests that Carey clay displays promising functionality as a natural antibacterial agent in the food industry.

Actinomycetes are a natural resource for sustainable pest control and safeguarding agriculture.

Actinomycetes, a diverse group of bacteria with filamentous growth characteristics, have long captivated researchers and biochemists for their prolific production of secondary metabolites. Among the myriad roles played by actinomycete secondary metabolites, their historical significance in the field of biocontrol stands out prominently. The fascinating journey begins with the discovery of antibiotics, where renowned compounds like streptomycin, tetracycline, and erythromycin revolutionized medicine and agriculture. The history of biocontrol traces its roots back to the early twentieth century, when scientists recognized the potential of naturally occurring agents to combat pests and diseases. The emergence of synthetic pesticides in the mid-twentieth century temporarily overshadowed interest in biocontrol. However, with growing environmental concerns and the realization of the negative ecological impacts of chemical pesticides, the pendulum swung back towards exploring sustainable alternatives. Beyond their historical role as antibiotics, actinomycete-produced secondary metabolites encompass a rich repertoire with biopesticide potential. The classification of these compounds based on chemical structure and mode of action is highlighted, demonstrating their versatility against both plant pathogens and insect pests. Additionally, this review provides in-depth insights into how endophytic actinomycete strains play a pivotal role in biocontrol strategies. Case studies elucidate their effectiveness in inhibiting Spodoptera spp. and nematodes through the production of bioactive compounds. By unraveling the multifunctional roles of endophytic actinomycetes, this review contributes compelling narrative knowledge to the field of sustainable agriculture, emphasizing the potential of these microbial allies in crafting effective, environmentally friendly biocontrol strategies for combating agricultural pests.

The relationship between polysaccharide structure and its antioxidant activity needs to be systematically elucidated.

Polysaccharides have a wide range of applications due to their excellent antioxidant activity. However, the low purity and unclear structure of polysaccharides have led some researchers to be skeptical about the antioxidant activity of polysaccharides. The current reports on the structure-activity relationship of polysaccharides are sporadic, so there is an urgent need to systematically summarize the antioxidant effects of polysaccharides with clear structures and the relationships between the structures to provide a scientific basis for the development and application of polysaccharides. This paper will systematically elucidate the structure-activity relationship of antioxidant polysaccharides, including the molecular weight, monosaccharide composition, glycosidic linkage, degree of branching, advanced conformation and chemical modification. For the first time, the antioxidant activity of polysaccharides is related to their chemical structure through histogram and radar map, and further studies using principal component analysis and cluster analysis. We critically discussed how the source, chemical structure and chemically modified groups of polysaccharides significantly contribute to their antioxidant activity and summarized the current research status and shortcomings of the structure-activity relationship of antioxidant polysaccharides. This review provides a theoretical basis and new perspective for further research on the structure-activity relationship of antioxidant polysaccharides and the development of natural antioxidants.

Quantitative Non-targeted Screening to Profile Micropollutants in Sewage Sludge Used for Agricultural Field Amendments.

A considerable number of micropollutants from human activities enter the wastewater network for removal. However, at the wastewater treatment plant (WWTP), some proportion of these compounds is retained in the sewage sludge (biosolids), and due to its high content of nutrients, sludge is widely applied as an agricultural fertilizer and becomes a means for the micropollutants to be introduced to the environment. Accordingly, a holistic semiquantitative nontarget screening was performed on sewage sludges from five different WWTPs using nanoflow liquid chromatography coupled to high-resolution Orbitrap mass spectrometry. Sixty-one inorganic elements were measured using inductively coupled plasma mass spectrometry. Across all sludges, the nontarget analysis workflow annotated >21,000 features with chemical structures, and after strict prioritization and filtering, 120 organic micropollutants with diverse chemical structures and applications such as pharmaceuticals, pesticides, flame retardants, and industrial and natural compounds were identified. None of the tested sludges were free from organic micropollutants. Pharmaceuticals contributed the largest share followed by pesticides and natural products. The predicted concentration of identified contaminants ranged between 0.2 and 10,881 ng/g dry matter. Through quantitative nontarget analysis, this study comprehensively demonstrated the occurrence of cocktails of micropollutants in sewage sludges.

Sex-Dimorphic Effects of Hypoglycemia on Metabolic Sensor mRNA Expression in Ventromedial Hypothalamic Nucleus-Dorsomedial Division (VMNdm) Growth Hormone-Releasing Hormone Neurons.

Growth hormone-releasing hormone (Ghrh) neurons in the dorsomedial ventromedial hypothalamic nucleus (VMNdm) express the metabolic transcription factor steroidogenic factor-1 and hypoglycemia-sensitive neurochemicals of diverse chemical structures, transmission modes, and temporal signaling profiles. Ghrh imposes neuromodulatory control of coexpressed transmitters. Multiple metabolic sensory mechanisms are employed in the brain, including screening of the critical nutrient glucose or the energy currency ATP. Here, combinatory laser-catapult-microdissection/single-cell multiplex qPCR tools were used to investigate whether these neurons possess molecular machinery for monitoring cellular metabolic status and if these biomarkers exhibit sex-specific sensitivity to insulin-induced hypoglycemia. Data show that hypoglycemia up- (male) or downregulated (female) Ghrh neuron glucokinase (Gck) mRNA; Ghrh gene silencing decreased baseline and hypoglycemic patterns of Gck gene expression in each sex. Ghrh neuron glucokinase regulatory protein (Gckr) transcript levels were respectively diminished or augmented in hypoglycemic male vs female rats; this mRNA profile was decreased by Ghrh siRNA in both sexes. Gene transcripts encoding catalytic alpha subunits of the energy monitor 5-AMP-activated protein kinase (AMPK), i.e., Prkaa1 and 2, were increased by hypoglycemia in males, yet only the former mRNA was hypoglycemia-sensitive in females. Ghrh siRNA downregulated baseline and hypoglycemia-associated Prkaa subunit mRNAs in males but elicited divergent changes in Prkaa2 transcripts in eu- vs hypoglycemic females. Results provide unique evidence that VMNdm Ghrh neurons express the characterized metabolic sensor biomarkers glucokinase and AMPK and that the corresponding gene profiles exhibit distinctive sex-dimorphic transcriptional responses to hypoglycemia. Data further document Ghrh neuromodulation of baseline and hypoglycemic transcription patterns of these metabolic gene profiles.

Characterization, components, and chemical structure of a novel natural pigments derived from Streptomyces tauricus

Characterization, components, and chemical structure of a novel natural pigments derived from Streptomyces tauricus

Properties and release behavior of sodium alginate-based nanocomposite active films: Effects of particle size of IRMOF-3.

Nanoparticles are used as fillers to improve the properties of biopolymers, and their particle size is an important parameter. This work aims to investigate the effect of particle size of isoreticular metal-organic framework-3 (IRMOF-3) on the mechanical, physical, and release properties of sodium alginate (SA)-based composite active film. In our study, IRMOF-3 with six different particle sizes was synthesized by introducing additives. IRMOF-3 loading with carvacrol (IRMOF-3/CA nanoparticles) was incorporated into the SA matrix to prepare the composite film. The characterization and testing results of films showed that the particle size of nanoparticles affected the physical morphology and chemical structure of the film. Especially smaller nanoparticles uniformly dispersed into the SA matrix more easily, forming a denser and more stable spatial network structure with SA, which could more significantly improve the tensile strength, water vapor barrier, and hydrophobic properties of the film (P < 0.05). In addition, the CA release rate from the active film could be significantly reduced by about 33.90 % even when the smallest particle size of the IRMOF-3/CA nanoparticles was added. Therefore, when IRMOF-3/CA is used as the nano-filler to develop SA-based active film, its particle size has a potential influence on the properties of the film.

Fast computational approach with prior dimension reduction for three-dimensional chemical component analysis using CT data of spectral imaging.

Spectral image (SI) measurement techniques, such as X-ray absorption fine structure (XAFS) imaging and scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS) or electron energy loss spectroscopy (EELS), are useful for identifying chemical structures in composite materials. Machine-learning techniques have been developed for automatic analysis of SI data, and their usefulness has been proven. Recently, an extended measurement technique combining SI with a computed tomography (CT) technique (CT-SI), such as CT-XAFS and STEM-EDS/EELS tomography, was developed to identify the three-dimensional (3D) structures of chemical components. CT-SI analysis can be conducted by combining CT reconstruction algorithms and chemical component analysis based on machine learning techniques. However, this analysis incurs high computational costs owing to the size of the CT-SI datasets. To address this problem, this study proposed a fast computational approach for 3D chemical component analysis in an unsupervised learning setting. The primary idea for reducing the computational cost involved compressing the CT-SI data prior to CT computation and performing 3D reconstruction and chemical component analysis on the compressed data. The proposed approach significantly reduced the computational cost without losing information about the 3D structure and chemical components. We experimentally evaluated the proposed approach using synthetic and real CT-XAFS data, which demonstrated that our approach achieved a significantly faster computational speed than the conventional approach while maintaining analysis performance. As the proposed procedure can be implemented with any CT algorithm, it is expected to accelerate 3D analyses with sparse regularized CT algorithms in noisy and sparse CT-SI datasets.

Tributelosides A-D: Four Undescribed Spirostan Glycosides Isolated from the Branches and Leaves of Tribulus terrestris with Their NO Production Inhibitory Activity in LPS Activated RAW 264.7 Cells.

Four undescribed spirostan glycosides, (25S)-5α-spirostan-12-one-2α,3β-diol-3-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside (1), (25S)-5α-spirostan-12-one-2α,3β-diol-3-O-β-D-galatopyranosyl-(1→2)-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside (2), (25S)-5α-spirostan-12-one-2α,3β-diol-3-O-β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)]-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside (3), and hecogenin 3-O-β-D-glucopyranosyl-(1→3)-[β-D-xylopyranosyl-(1→2)]-β-D-glucopyranosyl-(1→4)-[α-L-rhamnopyranosyl-(1→2)]-β-D-galactopyranoside (4), together with eleven known compounds (5-15) were isolated from the branches and leaves of Tribulus terrestris. Their chemical structures were established through spectroscopic methods. including HR-ESI-MS, 1D-, and 2D-NMR spectra. Preliminary biological evaluation on NO production inhibitory activity in LPS activated RAW 264.7 cells showed that compounds 1-3, 5, and 6 had significant inhibitory effects with IC50 values ranging from 2.4 to 18.3 µM, compared to that of the positive control compound, dexamethazone (IC50 13.6 µM).

Modulating Nonlinear Acoustic Response of Phospholipid-Coated Microbubbles with pH for Ultrasound Imaging.

Activatable microbubble contrast agents for contrast-enhanced ultrasound have a potential role for measuring physiologic and pathologic states in deep tissues, including tumor acidosis. In this study, we describe a novel observation of increased harmonic oscillation of phosphatidylcholine microbubbles (PC-MBs) in response to lower ambient pH using a clinical ultrasound scanner. MB echogenicity and nonlinear echoes were monitored at neutral and acidic pH using B-mode and Cadence contrast pulse sequencing (CPS), a harmonic imaging technique at 7.0 and 1.5 MHz. A 3-fold increase in harmonic signal intensity was observed when the pH of PC-MB suspensions was decreased from 7.4 to 5.5 to mimic normal and pathophysiological levels that can be encountered in vivo. This pH-mediated activation is tunable based on the chemical structure and length of phospholipids composing the MB shell. It is also reliant on the presence of phosphate groups, as the use of lipids without phosphate instead of phospholipids completely abrogated this phenomenon. The increased harmonic signal likely is the result of increased MB oscillation caused by a decrease of the interfacial tension induced at a lower pH, altering the lipid conformation. While relative signal changes are interpreted clinically as mostly related to blood flow, pH effects could be significant contributors, particularly when imaging tumors. While our observation can be used clinically, it requires further research to isolate the effect of pH from other variables. These findings could pave the way toward for the development of new smart ultrasound contrast agents that expand the clinical utility of contrast-enhanced ultrasound.

Food Plants and Environmental Contamination: An Update

Food plants are the basis of human nutrition, but, in contaminated places, they can uptake contaminants. Environmental contamination and climate change can modify food quality; generally, they have a negative impact on and imply risks to human health. Heavy metals, like lead, arsenic, cadmium, and chromium, can be present at various environmental levels (soil, water, and atmosphere), and they are widely distributed in the world. Food plants can carry out heavy metal bioaccumulation, a defense pathway for plants, which is different for every plant species. Accumulation is frequent in the roots and the leaves, and heavy metals can be present in fruits and seeds; As and Cd are always present. In addition, other contaminants can bioaccumulate in food plants, including emerging contaminants, like persistent organic pollutants (POPs), pesticides, and microplastics. In food plants, these are present in the roots but also in the leaves and fruits, depending on their chemical structure. The literature published in recent years was examined to understand the distribution of contaminants among food plants. In the literature, old agronomical practices and new integrated technology to clean the water, control the soil, and monitor the crops have been proposed to mitigate contamination and produce high food quality and high food safety.

Polyhydroxylated Sirostanol Saponins from the Rhizomes of Paris dulongensis.

Three new polyhydroxylated spirostanol steroidal saponins, dulongenosides B-D (2-4), along with 14 known compounds, dulongenoside A (1), padelaoside B (5), parisyunnanoside G (6), polyphyllin D (7), ophiopogonin C' (8), formosanin C (9), dioscin (10), paris saponin VII (11), paris H (12), parisyunnanoside I (13), protodioscin (14), proprotogracillin (15), crustecdysone (16), and stigmasterol-3-O-β-d-glucopyranoside (17), were isolated from the rhizomes of Paris dulongensis (Melanthiaceae). Their chemical structures were elucidated based on extensive analyses of NMR and MS data and acidic hydrolyses. The isolates were evaluated for their cytotoxicity to five human cancer cell lines (HL-60, SW480, MDA-MB-231, A549, and A549/Taxol) and the normal human bronchial epithelial cell line BEAS-2B by the MTS test. Compounds 7-12 and 14 showed cytotoxic activity, with IC50 values ranging from 0.20 to 4.35 μM. Proprogracillin selectively inhibited A549(IC50 = 0.58 μM) and A549/Taxol (IC50 = 0.74 μM) cells, with no significant cytotoxic activity against HL-60, SW480, MDA-MB-231, or BEAS-2B cells, with IC50 values greater than 40 μM.

Molecular Symmetry and Art: Visualizing the Near‐Symmetry of Molecules in Piet Mondrian's De Stijl

AbstractSymmetry and shape are essential aspects of molecular structure and how we interpret molecules and their properties. We, as chemists, are comfortable with pictorial representations of structure, in which some nuance is lost—investigating molecular shape numerically by looking at how closely it fits a reference, such as a plane, or a set of vectors or coordinates, is informative, though far from engaging. Often relationships between chemical structure and derived values are obscured. Taking our inspiration from Piet Mondrian's Compositions, we have depicted the symmetry information encoded within 3D data as blocks of color, to show clearly how chemical arguments and resultant molecular distortion may contribute to symmetry. Great art gives us a new perspective on the world; as a pastiche, this art may allow us to look at familiar molecules, such as porphyrins, in a new light, understanding how their shape and properties are intertwined.

Chemical Annealing Restructures RNA for Nanopore Detection.

RNA is a key biochemical marker, yet its chemical instability and complex secondary structure hamper its integration into DNA nanotechnology-based sensing platforms. Relying on the denaturation of the native RNA structure using urea, we show that restructured DNA/RNA hybrids can readily be prepared at room temperature. Using solid-state nanopore sensing, we demonstrate that the structures of our DNA/RNA hybrids conform to the design at the single-molecule level. Employing this chemical annealing procedure, we mitigate RNA self-cleavage, enabling the direct detection of restructured RNA molecules for biosensing applications.

A comprehensive study on the identification and characterization of degradation products of lipoglycopeptide Dalbavancin using LC and LC-HRMS/MS.

Dalbavancin is the second-generation approved semisynthetic lipoglycopeptide by the United States Food and Drug Administration (USFDA) for the treatment of acute bacterial skin and skin-structure infections. Unlike other lipoglycopeptides, the stability behavior of Dalbavancin was least explored, which is a prerequisite. The current study endeavors to elucidate the oxidative and hydrolytic stability behavior of Dalbavancin by exposing the drug to oxidative, acidic, and basic stress conditions. A simple liquid chromatography (LC) method was developed, where significant resolution between Dalbavancin, its homologs, and the generated degradation products was achieved. Seven degradation products were identified under acidic, basic, and oxidative stress conditions. Using liquid chromatography and high-resolution mass spectrometry (LC-HRMS), MS/MS studies, the generated degradation products were identified and characterized. Formation of isomeric degradation products was identified especially upon exposure to basic stress conditions. The mechanistic fragmentation pathway for the seven degradation products was established, and the chemical structure for the identified degradation products was elucidated. The results strongly suggest that Dalbavancin is highly susceptible to degradation under oxidative and hydrolytic stress conditions. This study provides insights into the hydrolytic and oxidative stability of Dalbavancin, which can be employed during drug development and discovery in synthesizing relatively stable analogs.

Citrate-buffered Yamanaka medium allows to produce high-yield bacterial nanocellulose in static culture using Komagataeibacter strains isolated from apple cider vinegar

Bacterial nanocellulose (BNC) is a sustainable, renewable, and eco-friendly nanomaterial, which has gained great attentions in both academic and industrial fields. Two bacterial nanocellulose-producing strains (CVV and CVN) were isolated from apple vinegar sources, presenting high 16S rRNA gene sequence similarities (96%–98%) with Komagataeibacter species. The biofilm was characterized by scanning electron microscopy (SEM), revealing the presence of rod-shaped bacteria intricately embedded in the polymeric matrix composed of nanofibers of bacterial nanocellulose. FTIR spectrum and XRD pattern additionally confirmed the characteristic chemical structure associated with this material. The yields and productivities achieved during 10 days of fermentation were compared with Komagataeibacter xylinus ATCC 53524, resulting in low levels of BNC production. However, a remarkable increase in the BNC yield was achieved for CVV (690% increase) and CVN (750% increase) strains at day 6 of the fermentation upon adding 22 mM citrate buffer into the medium. This effect is mainly attributed to the buffering capacity of the modified Yakamana medium, which allowed to maintain pH close to 4.0 until day 6, though in combination with additional factors including stimulation of the gluconeogenesis pathway and citrate assimilation as a carbon source. In addition, the productivities determined for both isolated strains (0.850 and 0.917 g L−1 d−1) compare favorably to previous works, supporting current efforts to improve fermentation performance in static cultures and the feasibility of scaling-up BNC production in these systems.

Mechanistic insight into heteroatom removal from vacuum gas oil blended with PMMA or PET waste.

This work analyzes vacuum gas oil (VGO) and hydrocracking products of feed blended with polymethylmethacrylate (PMMA) or polyethylene terephthalate (PET) in depth to clarify the oxygen, nitrogen, and sulfur removal pathways in these complex mixtures. Hydrocracking reactions are conducted in a semi-batch reactor with a Pt-Pd/HY bifunctional catalyst at 400 °C and 80 bar for 300 min with 10 wt% waste plastic using 0.1 catalyst/feed weight ratio. The samples are analyzed using various techniques, including high-resolution mass spectrometry, providing an improved, more detailed analytical representation. The results demonstrate the synergistic effect of cofeeding oxygenated plastics to the VGO, altering the preferential reaction pathways of heteroatom-containing species in the following order: nitrogen, oxygen, and sulfur. We assess the chemical structures from the gathered data, establish plausible reaction mechanisms, and evaluate the catalyst's role.

Unveiling the Shadows: Overcoming Bottlenecks in Scaling Organic Photovoltaic Technology from Laboratory to Industry

AbstractOrganic photovoltaic (OPV) technology has recently achieved remarkable progress in academia, attaining power conversion efficiencies exceeding 19%, a breakthrough previously unimaginable. Despite these advancements, the translation of high‐efficiency OPV cells into the commercialization of OPV modules has been limited, impeding the market penetration of OPV technology. Upon careful examination, various challenges emerge, including disparities between laboratory research and industrial production in device architecture, influenced by considerations of cost and manufacturability. Additionally, the incorporation of high‐efficiency materials requires careful consideration not only of the compatibility between the photoactive layer and interface layers or transparent electrodes but also of the associated synthetic complexity of chemical structures and cost implications. While these issues are crucial, they may not be widely discussed in current mainstream research. In this article, the purpose is to identify bottlenecks from a material techniques perspective, with the aim of promoting increased resources in the research of pertinent module technologies. This effort is intended to propel OPV technology toward greater success and bring it into closer alignment with the goals of commercialization.

Structural and chemical study of complex silver patterns additively manufactured by multi-photon reduction.

Multi-photon reduction (MPR) based on femtosecond laser makes rapid prototyping and molding in micro-nano scale feasible, but is limited in material selectivity due to lack of the understanding of the reaction mechanism in MPR process. In this paper, additively manufacturing of complex silver-based patterns through MPR is demonstrated. The effects of laser parameters, including laser pulse energies and scanning speeds, on the structural and chemical characteristics of the printed structures are systematically investigated. The results show that the geometric size of printed cubes deviates from the designed size further by increasing laser pulse energies or decreasing scanning speeds. The reaction mechanism of MPR is revealed by studying the elemental composition and chemical structures of printed cubes. The evolution of Raman spectra upon the laser processing parameters suggests that the MPR process mainly includes two processes: reduction and decomposition. In the MPR process, silver ions are reduced and grow into particles by accepting the electrons from ethonal molecules; meanwhile carboxyl groups in polyvinylpyrrolidone are decomposed and form amorphous carbon that is attached on the surface of silver particles. The conductivity of silver wires fabricated by MPR reaches 2×105 S/m and stays relatively constant as varying their cross section area, suggesting excellent electrical conduction. The understanding of the MPR process would accelerate the development of MPR technology and the implementation of MPR in micro-electromechanical systems could therefore be envisioned.

Gonadotropin-Releasing Hormone (GnRH) and Its Agonists in Bovine Reproduction I: Structure, Biosynthesis, Physiological Effects, and Its Role in Estrous Synchronization

GnRH is essential for the regulation of mammalian reproductive processes. It regulates the production and release of pituitary gonadotropins, thereby influencing steroidogenesis and gametogenesis. While primarily produced in the hypothalamus, GnRH is also produced in peripheral organs, such as the gonads and placenta. GnRH analogs, including agonists and antagonists, have been synthesized for the reproductive management of animals and humans. This review focuses on the functions of hypothalamic GnRH in the reproductive processes of cattle. In addition to inducing the surge release of LH, the pulsatile secretion of GnRH stimulates the pituitary gland to release FSH and LH, thereby regulating gonadal function. Various GnRH-based products have been synthesized to increase their potency and efficacy in regulating reproductive functions. This review article describes the chemical structures of GnRH and its agonists. This discussion extends to the gene expression of GnRH in the hypothalamus, highlighting its pivotal role in regulating the reproductive process. Furthermore, GnRH is involved in regulating ovarian follicular development and luteal phase support, and estrus synchronization is involved. A comprehensive understanding of the role of GnRH and its analogs in the modulation of reproductive processes is essential for optimizing animal reproduction.