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Impact of Heavy Metals on Growth and Biosynthesis of Important Secondary Metabolites from Mucuna Pruiens (L.) DC and Withania Somnifera (L). DUNAL
Herbal medicine has a long history of utilizing medicinal plants to treat various newlineailments for a long time. However, heavy metal toxicity in herbal medicines has been newlinedocumented. The occurrence of heavy metals in medicinal plants is a consequence of exposure to tainted agricultural sources. The consumption of medicinal plants newlinecontaminated with heavy metals has caused detrimental health implications. On the newlineother hand, plants when subjected to heavy metal stress exhibit changes in secondary newlinemetabolite production. Thus, the assessment of heavy metal stress on plant growth, newlinesecondary metabolite production, and its bioaccumulation must be worked on. The newlinepresent study investigates the effect of heavy metals such as lead, cadmium and newlinemercury on germination, growth, biochemical variations, heavy metal accumulation, newlineand biosynthesis of secondary metabolites in two of the most valuables ayurvedic newlinemedicinal plants Mucuna pruriens (L.) DC and Withania somnifera (L). Dunal. The M. pruriens seeds were exposed to 25 -250 ppm Cd and Hg and 200-2000 ppm Pb and the seeds of W. somnifera were exposed to 20-200 ppm Cd, 10-100 ppm Hg and 100-1000 ppm Pb for 21 days to evaluate the LD50 value. M. pruriens showed 50% germination at 150 ppm Cd, 175 ppm Hg, and 1200 ppm Pb. W. somnifera showed newline50% germination at 70 ppm of Hg, 140 ppm Cd and 400 ppm Pb. The LD50 value obtained was used to select the appropriate Cd concentrations for further studies to newlinebe carried out in the polyhouse. The seeds of M. pruriens were sown in soil pretreated newlinewith metals ranging from 50-200 ppm Cd, 25-225 ppm Hg and 400- 1600 ppm Pb, newlinewhereas the two months old W. somnifera were exposed to 40-200 ppm Cd, 20-100 ppm Hg and 200-1000 ppm Pb. The heavy metals impacted the growth of plants and significantly varied biochemical parameters, such as carbohydrate, chlorophyll, flavonoid, protein, proline, phenol, MDA content, metabolite content, and newlineantioxidant activity. -
Machine Learning Based recommendation system Using User-Item Interaction
Electronic commerce, or e-commerce, is the activity of trading services and commodities through the internet. Identifying the item that the consumer may buy from the enormous number of possibilities accessible to solve this difficulty is now one of the key difficulties encountered by most E-commerce businesses. Recommender systems have been implemented. Recommender systems (RS) are systems that collect information from users about their preferences and allow them to make decisions from the available options. Today, various recommender systems are growing with the advent of web-based information. As you can see from various articles, such recommender systems are used in a variety of industries, from simple objects to more sophisticated objects.RS has gained popularity in the previous decade, particularly in the realm of E-Commerce and related sectors. This report aims to identify recent developments as well as their potential for improvement. It is intended to elaborate on a number of points. And also work more on user-item based recommendation. These types of user-item based recommendation will be more effective in fashion area. 2022 IEEE. -
Electrochemical sensing of vitamin B12 deficiency marker methylmalonic acid using PdAu-PPy tailored carbon fiber paper electrode
Vitamin B12 is very important for human metabolism and its deficiency can cause anemia and the production of large red blood cells. An increased concentration of methylmalonic acid (MMA) is detected much before the transformation of blood cells, which thereby is an early indicator for mild or serious Vitamin B12 deficiency. A simple electrochemical sensor based on PalladiumGold (PdAu) was developed by electrodeposition of PdAu nanoparticles on Polypyrrole (PPy) modified carbon fiber paper (CFP) electrode. The modified electrodes were characterized by High resolution transmission electron microscopy (HRTEM), Field emission scanning electron microscopy (FESEM) with energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electroanalytical techniques. Differential Pulse Voltammetric (DPV) studies have established that under optimum conditions, the developed sensor exhibits a broad linear dynamic range (4.01 pM - 52.5 nM) with a very low detection limit (1.32 pM). The proposed method was effectively applied in the non-enzymatic determination of MMA at an ultralow level in human blood serum and urine samples. The method displayed high selectivity toward MMA in the presence of other interfering substances. 2020 Elsevier B.V. -
Non-enzymatic electrochemical determination of progesterone using carbon nanospheres from onion peels coated on carbon fiber paper
A simple electrochemical sensor was developed by coating Onion peel wastes derived carbon nanospheres on carbon fiber paper (CFP) electrode. Carbon nanospheres (CNS) were prepared from Onion peels utilizing an environmentally benign and cost-effective strategy. In the present investigation, the obtained carbon nanospheres were coated on carbon fiber paper and the modified electrodes were physicochemically characterized by Field emission scanning electron microscopy (FESEM) with energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) spectroscopy and X-ray photoelectron spectroscopy (XPS) techniques. Electrochemical characterizations of the modified electrodes were done by Cyclic voltammetry (CV) and Electrochemical impedance spectroscopy (EIS). CNS modified CFP electrode was successfully used in the determination of Progesterone, an important steroid hormone at an ultra-nanomolar level with superior detection limit of 0.012 nM. The developed electrochemical sensor was effectively utilized for the determination of Progesterone in pharmaceutical Progesterone injections, human blood serum samples and cow milk samples. 2019 The Electrochemical Society. -
Trace level determination of Hg 2+ ions in environmental samples with a mercaptotriazole-functionalized TiO 2 nanostructure-based fluorescent probe
A highly selective and sensitive fluorescent probe for the determination of Hg 2+ ions is reported using substituted mercaptotriazole functionalized TiO 2 nanoparticles (MMT@TiO 2 ). The functionalized TiO 2 nanoparticles were characterized by UV-vis spectrophotometric, spectrofluorometric, FT-IR, FT-Raman, XPS, TEM, SEM, EDAX and P-XRD analyses. The interaction of Hg 2+ ions with functionalized MMT@TiO 2 induced aggregation of nanoparticles causing chelation enhanced fluorescence. The limit of detection and limit of quantitation for the determination of Hg 2+ ions were found to be 2.18 10 -10 M and 6.61 10 -10 M, respectively. The method developed was successfully applied for the determination of Hg 2+ ions in environmental samples. 2019 The Royal Society of Chemistry. -
Synthesis and photophysical properties of a novel phthalimide derivative using solvatochromic shift method for the estimation of ground and singlet excited state dipole moments
A novel phthalimide derivative, 2-{4-[(1H-1,2,4-triazol-1-yl)methyl]phenyl}-1Hisoindole-1,3(2H)-dione (TMPID) containing an isoindole moiety was synthesized by the cyclisation of 2-({4-[(1H-1,2,4-triazol-1-yl)methyl]phenyl}carbamoyl)benzoic acid (TMPCB). The absorbance and fluorescence spectra of the derivative were recorded in fifteen different solvents to investigate their solvatochromic behaviour and dipole moments. Different solvent correlation methods, like the BilotKawski, LippertMataga, Bakhshiev, KawskiChammaViallet and Reichardt methods were employed to estimate the singlet excited and ground state dipole moments. Using multiple regression analysis, solute-solvent, specific and non-specific interactions were analyzed by means of Kamlet-Abboud-Taft and Catalan parameters. Computational studies were performed using time dependent density functional theory (TD-DFT) in order to calculate ground state dipole moment, atomic charges and frontier molecular orbital energies in solvent phase. Experimental and computational studies indicate that the singlet excited state dipole moment of TMPID is greater than the ground state dipole moment. The chemical stability of the derivative was determined by means of chemical hardness (?) using HOMOLUMO energies. From TD-DFT computational analysis, reactive centres in the molecule were evaluated based on molecular electrostatic potential (MESP) 3D plots. 2016 Elsevier B.V. -
Amorphous Ru-Pi nanoclusters coated on polypyrrole modified carbon fiber paper for non-enzymatic electrochemical determination of cholesterol
A facile electrochemical sensor based on Ruthenium-Phosphate (Ru-Pi) was developed by electrodeposition of Ru-Pi on Polypyrrole (PPy) modified carbon fiber paper (CFP) electrode. Phosphate buffer solutions of neutral pH containing RuCl3 was used for voltammetric deposition of Ru-Pi on PPy/CFP electrode. The modified electrodes were characterized by High resolution transmission electron microscopy (HRTEM), High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), Field emission scanning electron microscopy (FESEM) with energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and electroanalytical techniques. A significant amount of phosphate (Pi) and Ru centers in higher oxidation states were present on Ru-Pi film deposited on PPy/CFP substrate. Pi plays a significant role during catalyst deposition and in its activity toward determination of Cholesterol. DPV studies demonstrated that under optimum conditions, the developed sensor has displayed a wide linear dynamic range between 0.16 nM and 20.0 nM with a superior detection limit of 0.54 10-10 M. The proposed method was effectively applied in the nonenzymatic determination of cholesterol at an ultralow level in human blood serum samples. The method displayed high selectivity toward cholesterol in the presence of other interfering substances. 2019 The Electrochemical Society. -
Electrocatalytic oxidation of morin on electrodeposited Ir-PEDOT nanograins
Nanoclusters of Ir were electrochemically deposited on carbon fiber paper (CFP) substrate modified with poly(3,4-ethylenedioxythiophene) (PEDOT), a conducting polymer between the potential range 0.0 V and 0.6 V at 0.05 V/s scan rate. The electrocatalytic activity of IrPEDOT/CFP electrode towards oxidation of morin, a flavonoid was significantly greater than that of PEDOT/CFP and bare CFP electrodes. Factors affecting the anodic peak of morin namely, effect of pH, scan rate and number of cycles were optimized. The electrochemical route involved adsorption controlled and irreversible processes. Under optimal conditions, the linear dynamic range for the determination of morin was found to be 0.12 nM2.80 nM. The significantly low detection limit (42.18 pM) demonstrates the ultrasensitivity of the proposed method. The reliability of the method was evaluated for the quantification of morin present in mulberry leaves, guava leaves and grape wine. 2018 Elsevier Ltd -
Study on Photophysical Properties of N-Arylphthalamic Acid Derivative Containing 1, 2, 4-Triazole Scaffold
A novel N-arylphthalamic acid derivative, 2-({4-[(1H-1,2,4-triazol-1-yl)methyl]phenyl}carbamoyl)benzoic acid (TMPCB) was synthesized and their absorption and emission spectra were recorded in fifteen different solvents of varying polarities at room temperature. Ground state dipole moment of the derivative was calculated experimentally by Guggenheim method and solvatochromic approach proposed by Bilot-Kawski. The singlet excited state dipole moment of TMPCB were calculated experimentally based on different approaches of solvent polarity function proposed by LippertMataga, Bakhshiev, Kawskii-Chamma-Viallet, Reichardt and Bilot-Kawski. Singlet excited state dipole moment was greater than ground state dipole moment in all the approaches which could be attributed to considerable ?- electron density redistribution. Multiple Linear Regression (MLR) analysis based on Kamlet-Abboud-Taft and Catalan parameters were also studied to correlate solvatochromism and influence of solvents with absorbance and emission spectra. Ground and singlet excited state optimizations of the molecule were also performed using Gaussian 09W software. HOMO-LUMO energies of the phthalamic acid derivative have been obtained using TD-DFT/PCM (B3LYP/6-31G (d, p)) computations and experimentally by using cyclic voltammetry. Mulliken charges and molecular electrostatic potential plot have also been generated from DFT calculations to identify nucleophilic and electrophilic sites of TMPCB. 2017, Springer Science+Business Media, LLC. -
PEDOT decorated with PTIR nanoclusters on carbon fiber paper toward electrocatalytic reduction of a hypertensive drug olmesartan medoxomil
A facile electrochemical sensor was developed by electrochemical deposition of PtIr nanoparticles on poly(3,4ethylenedioxythiophene) (PEDOT) modified carbon fiber paper electrode (CFP). The modified electrodes were characterized by Field emission scanning electron microscopy (FESEM) with energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), RAMAN spectroscopy, Fourier transform infrared spectroscopy (FTIR) and electroanalytical techniques. PtIr-PEDOT modified CFP electrode was used successfully in the determination of an anti-hypertensive prodrug Olmesartan medoxomil (OM) at femtomolar (fM) level for the first time. Under optimal conditions, the prepared electrochemical sensor has shown broad linear range between 0.001 pM and 0.220 pM and superior detection limit of 3.42 fM was observed based on Differential pulse voltammetric (DPV) study. In addition, the designed electrochemical sensor was successfully demonstrated as a novel platform in the electrochemical determination of OM in human urine and pharmaceutical samples. 2018 The Electrochemical Society. -
Components of the diffuse ultraviolet radiation at high latitudes
We have used data from the Galaxy Evolution Explorer to study the different components of the diffuse ultraviolet background in the region between the Galactic latitudes 70?-80?. We find an offset at zero dust column density (E(B ? V) = 0) of 240 18 photon units in the FUV (1539 and 394 37 photon units in the NUV (2316 . This is approximately half of the total observed radiation with the remainder divided between an extragalactic component of 114 18 photon units in the FUV and 194 37 photon units in the NUV and starlight scattered by Galactic dust at high latitudes. The optical constants of the dust grains were found to be a = 0.4 0.1 and g = 0.8 0.1 (FUV) and a = 0.4 0.1 and g = 0.5 0.1 (NUV). We cannot differentiate between a Galactic or extragalactic origin for the zero-offset but can affirm that it is not from any known source. 2019 Oxford University Press. All rights reserved. -
The Diffuse Radiation Field at High Galactic Latitudes
We have used GALEX observations of the north and south Galactic poles to study the diffuse ultraviolet background at locations where the Galactic light is expected to be at a minimum. We find offsets of 230-290 photon units in the far-UV (1531 and 480-580 photon units in the near-UV (2361 . Of this, approximately 120 photon units can be ascribed to dust-scattered light and another 110 photon units (190 in the near-UV) to extragalactic radiation. The remaining radiation is, as yet, unidentified and amounts to 120-180 photon units in the far-UV and 300-400 photon units in the near-UV. We find that molecular hydrogen fluorescence contributes to the far-UV when the 100 ?m surface brightness is greater than 1.08 MJy sr-1. 2018. The American Astronomical Society. All rights reserved. -
Design and development of cognitive improvement through virtual reality based treatment using mathematical model
Virtual reality (VR) used in rehabilitation has the potential to enhance the quality of life for individuals with various medical conditions. As a result of this novel approach, there has been an increase in the number of individuals who are now giving their attention and actively engaging in rehabilitation programmes. This study aims to assess the effectiveness and advantages of virtual reality-based rehabilitation programmes in comparison to traditional educational methods for enhancing and strengthening talents. The creative capacity of VR was assessed through a study involving 50 participants who are going through regular traditional therepy methods. Virtual reality therapy enhances cognitive functions. As a result of the changes, there was a 30-40% increase in growth using proposed mathamatical model compared to traditional methods. The study revealed that the use of virtual reality-based personalised rehabilitation resulted in enhanced cognitive function and improved retention of knowledge among the participants. 2024, Taru Publications. All rights reserved. -
A hybrid deep learning and quantum computing approach for optimized encryption algorithms in secure communications
As online dangers get worse, there is a greater need for strong encryption methods to protect private conversations. Utilizing the strengths of both deep learning and quantum computing, this study suggests a new mixed method for improving the security of communication systems by making encryption algorithms work better. When it comes to keeping up with new online threats, traditional security methods often fall behind. Deep learning techniques could be a good way to improve encryption algorithms because they let the system learn and change to new attack methods. In the meantime, quantum computing offers unmatched computing power that can completely change how cryptography works by using quantum events like superposition and entanglement. Our suggested method combines the flexibility of deep learning with the computing power of quantum computing to get around the problems with current encryption methods. This will make safe communication systems more resistant to attacks from smart people. Through tests and models, we show that our mixed approach works better and more effectively than current encryption methods. This shows that it has the ability to solve the growing safety problems in a world that is becoming more and more linked. 2024, Taru Publications. All rights reserved. -
Comprehensive evaluation and performance analysis of machine learning in heart disease prediction
Heart disease is a leading cause of mortality on a global scale. Accurately predicting cardiovascular disease poses a significant challenge within clinical data analysis. The present study introduces a prediction model that utilizes various combinations of information and employs multiple established classification approaches. The proposed technique combines the genetic algorithm (GA) and the recursive feature elimination method (RFEM) to select relevant features, thus enhancing the models robustness. Techniques like the under sampling clustering oversampling method (USCOM) address the issue of data imbalance, thereby improving the models predictive capabilities. The classification challenge employs a multilayer deep convolutional neural network (MLDCNN), trained using the adaptive elephant herd optimization method (AEHOM). The proposed machine learning-based heart disease prediction method (ML-HDPM) demonstrates outstanding performance across various crucial evaluation parameters, as indicated by its comprehensive assessment. During the training process, the ML-HDPM model exhibits a high level of performance, achieving an accuracy rate of 95.5% and a precision rate of 94.8%. The systems sensitivity (recall) performs with a high accuracy rate of 96.2%, while the F-score highlights its well-balanced performance, measuring 91.5%. It is worth noting that the specificity of ML-HDPM is recorded at a remarkable 89.7%. The findings underscore the potential of ML-HDPM to transform the prediction of heart disease and aid healthcare practitioners in providing precise diagnoses, exerting a substantial influence on patient care outcomes. The Author(s) 2024. -
Synthesis and Multifaceted Exploration of 4-Phenylpiperidin-4-ol Substituted Pyrazole: Photophysical Insights with Biological Activity
In this study, we successfully synthesized a pyrazole derivative, specifically 4-phenylpiperidin-4-ol substituted pyrazole (CHP), through the reaction of Grignard reagents in combination with pyrazole. This newly synthesized molecule was subjected to a comprehensive evaluation for both its photophysical and biological applications. Notably, CHP exhibited promising invitro antifungal and antibacterial activities, primarily attributed to the presence of the 4-phenylpiperidin-4-ol moiety and resulting component contributed to an enhanced absorption rate of lipids, thereby improving the pharmacological activity of CHP. This correlation between structure and function was further supported by the outcomes of structure-activity relationship studies. Additionally, we conducted in silico studies to examine the molecular interactions of the synthesized molecule with key proteins, including DNA Gyrase, Lanosterol 14 ?-demethylase, and KEAP1-NRF2. The results unveiled robust binding interactions at specific sites within these proteins, indicating potential therapeutic relevance. Furthermore, the photophysical properties of the synthesized compounds were thoroughly investigated using the ab-initio technique. This involved the determination of ground state optimization and HOMO-LUMO energy levels, all calculated with the DFT-B3LYP-6-31G(d) basis set. The assessment of the theoretically estimated HOMO-LUMO value provided insights into the global chemical reactivity descriptors, revealing that the synthesized molecule boasts a highly electronegative and electrophilic index. Taken together, our findings suggest that pyrazole derivatives with 4-phenylpiperidin-4-ol substitutions exhibit promising applications in both photophysical and biological contexts. 2024 Ghaferah H. Al-Hazmi et al., published by Sciendo. -
Studies on Photophysical and Biological Activity of Newly Synthesized of 4-Methylpiperidin-4-ol Substituted Pyrazole Derivatives
The in vitro antifungal, antibacterial, and antioxidant activities of a substituted pyrazole derivative (FHM) have been evaluated in the current work. The addition of 4-methylpiperidin-4-ol, which increases the molecules lipid solubility and speeds up absorption by increasing its rate of absorption, gives the molecule strong in vitro antifungal and antibacterial properties. Additionally, it is clear from the findings of structure-activity relationship (SAR) investigations. Additionally, the ab-intio technique was used to theoretically evaluate the photophysical characteristics of produced substances. Using the DFT-B3LYP-6-31G(d) basis set, the ground state optimization and HOMO-LUMO energy levels are computed. Global chemical reactivity and descriptive characteristics are evaluated using theoretically estimated HOMO-LUMO values, and the results demonstrate that the synthesized molecule possesses a high electrophilicity and electronegative index. Overall findings indicate that substituting a 4-methylpiperidin-4-ol substituted pyrazole derivative shows good photophysical and in vitro biological applications. 2024, HARD Publishing Company. All rights reserved. -
Essential Oil from Coriandrum sativum: A review on Its Phytochemistry and Biological Activity
Essential oils are hydrophobic liquids produced as secondary metabolites by specialized secretory tissues in the leaves, seeds, flowers, bark and wood of the plant, and they play an important ecological role in plants. Essential oils have been used in various traditional healing systems due to their pharmaceutical properties, and are reported to be a suitable replacement for chemical and synthetic drugs that come with adverse side effects. Thus, currently, various plant sources for essential oil production have been explored. Coriander essential oil, obtained from the leaf and seed oil of Coriandrum sativum, has been reported to have various biological activities. Apart from its application in food preservation, the oil has many pharmacological properties, including allelopathic properties. The present review discusses the phytochemical composition of the seed and leaf oil of coriander and the variation of the essential oil across various germplasms, accessions, at different growth stages and across various regions. Furthermore, the study explores various extraction and quantification methods for coriander essential oils. The study also provides detailed information on various pharmacological properties of essential oils, such as antimicrobial, anthelmintic, insecticidal, allelopathic, antioxidant, antidiabetic, anticonvulsive, antidepressant, and hepatoprotective properties, as well as playing a major role in maintaining good digestive health. Coriander essential oil is one of the most promising alternatives in the food and pharmaceutical industries. 2023 by the authors. -
Cadmium toxicity in medicinal plants: An overview of the tolerance strategies, biotechnological and omics approaches to alleviate metal stress
Medicinal plants, an important source of herbal medicine, are gaining more demand with the growing human needs in recent times. However, these medicinal plants have been recognized as one of the possible sources of heavy metal toxicity in humans as these medicinal plants are exposed to cadmium-rich soil and water because of extensive industrial and agricultural operations. Cadmium (Cd) is an extremely hazardous metal that has a deleterious impact on plant development and productivity. These plants uptake Cd by symplastic, apoplastic, or via specialized transporters such as HMA, MTPs, NRAMP, ZIP, and ZRT-IRT-like proteins. Cd exerts its effect by producing reactive oxygen species (ROS) and interfere with a range of metabolic and physiological pathways. Studies have shown that it has detrimental effects on various plant growth stages like germination, vegetative and reproductive stages by analyzing the anatomical, morphological and biochemical changes (changes in photosynthetic machinery and membrane permeability). Also, plants respond to Cd toxicity by using various enzymatic and non-enzymatic antioxidant systems. Furthermore, the ROS generated due to the heavy metal stress alters the genes that are actively involved in signal transduction. Thus, the biosynthetic pathway of the important secondary metabolite is altered thereby affecting the synthesis of secondary metabolites either by enhancing or suppressing the metabolite production. The present review discusses the abundance of Cd and its incorporation, accumulation and translocation by plants, phytotoxic implications, and morphological, physiological, biochemical and molecular responses of medicinal plants to Cd toxicity. It explains the Cd detoxification mechanisms exhibited by the medicinal plants and further discusses the omics and biotechnological strategies such as genetic engineering and gene editing CRISPR- Cas 9 approach to ameliorate the Cd stress. Copyright 2023 Al-Khayri, Banadka, Rashmi, Nagella, Alessa and Almaghasla. -
In Silico Identification of 1-DTP Inhibitors of Corynebacterium diphtheriae Using Phytochemicals from Andrographis paniculata
A number of phytochemicals have been identified as promising drug molecules against a variety of diseases using an in-silico approach. The current research uses this approach to identify the phyto-derived drugs from Andrographis paniculata (Burm. f.) Wall. ex Nees (AP) for the treatment of diphtheria. In the present study, 18 bioactive molecules from Andrographis paniculata (obtained from the PubChem database) were docked against the diphtheria toxin using the AutoDock vina tool. Visualization of the top four molecules with the best dockscore, namely bisandrographolide (?10.4), andrographiside (?9.5), isoandrographolide (?9.4), and neoandrographolide (?9.1), helps gain a better understanding of the molecular interactions. Further screening using molecular dynamics simulation studies led to the identification of bisandrographolide and andrographiside as hit compounds. Investigation of pharmacokinetic properties, mainly ADMET, along with Lipinskis rule and binding affinity considerations, narrowed down the search for a potent drug to bisandrographolide, which was the only molecule to be negative for AMES toxicity. Thus, further modification of this compound followed by in vitro and in vivo studies can be used to examine itseffectiveness against diphtheria. 2023 by the authors.