Pub Date : 2024-11-04DOI: 10.1021/acsomega.4c0287610.1021/acsomega.4c02876
Mariana C. Santoro*, Bashir M. Ghanim, Witold Kwapinski, James J. Leahy and Jair C. C. Freitas,
Poultry litter (PL) hydrochars obtained at different temperatures and charring times were characterized by solid-state 1H, 13C and 31P nuclear magnetic resonance (NMR) spectroscopy. 13C NMR spectra obtained with cross polarization (CP) and magic-angle spinning evidenced the chemical and structural changes suffered by PL during its transformation into hydrochar; these changes were particularly dependent on the production temperature rather than the residence time. The hydrochars were essentially composed of aromatic and alkyl domains at the temperature of 250 °C. 31P NMR observations were conducted using single-pulse excitation (SPE) and CP sequences to distinguish between phosphorus far from protons and protonated phosphate species. Results showed that water-soluble phosphorus was the only form detected in hydrochars through the CP sequence. In contrast, the stable phosphorus species formed during hydrothermal carbonization (HTC) exhibited broad signals, detected exclusively using the SPE sequence. This indicates that unprotonated orthophosphates were the dominant form. These NMR results offer a deeper understanding of hydrochar formation from PL, shedding light on the chemical and structural changes caused by the HTC process at the atomic scale.
{"title":"Solid-State NMR Study of Hydrochars Produced from Hydrothermal Carbonization of Poultry Litter","authors":"Mariana C. Santoro*, Bashir M. Ghanim, Witold Kwapinski, James J. Leahy and Jair C. C. Freitas, ","doi":"10.1021/acsomega.4c0287610.1021/acsomega.4c02876","DOIUrl":"https://doi.org/10.1021/acsomega.4c02876https://doi.org/10.1021/acsomega.4c02876","url":null,"abstract":"<p >Poultry litter (PL) hydrochars obtained at different temperatures and charring times were characterized by solid-state <sup>1</sup>H, <sup>13</sup>C and <sup>31</sup>P nuclear magnetic resonance (NMR) spectroscopy. <sup>13</sup>C NMR spectra obtained with cross polarization (CP) and magic-angle spinning evidenced the chemical and structural changes suffered by PL during its transformation into hydrochar; these changes were particularly dependent on the production temperature rather than the residence time. The hydrochars were essentially composed of aromatic and alkyl domains at the temperature of 250 °C. <sup>31</sup>P NMR observations were conducted using single-pulse excitation (SPE) and CP sequences to distinguish between phosphorus far from protons and protonated phosphate species. Results showed that water-soluble phosphorus was the only form detected in hydrochars through the CP sequence. In contrast, the stable phosphorus species formed during hydrothermal carbonization (HTC) exhibited broad signals, detected exclusively using the SPE sequence. This indicates that unprotonated orthophosphates were the dominant form. These NMR results offer a deeper understanding of hydrochar formation from PL, shedding light on the chemical and structural changes caused by the HTC process at the atomic scale.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 46","pages":"45759–45773 45759–45773"},"PeriodicalIF":3.7,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsomega.4c02876","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671507","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-03eCollection Date: 2024-11-12DOI: 10.1021/acsomega.4c07463
Zhongyi Zhang, Yunliang He, Mei Zhao, Xin He, Zubing Zhou, Yuanyuan Yue, Tao Shen, Juncheng Liu, Gan Zhang, Yong Zhang
Background: Qinglian Hongqu decoction (QLHQD), a traditional Chinese herbal remedy, shows potential in alleviating metabolic issues related to nonalcoholic fatty liver disease (NAFLD). However, its precise mode of action remains uncertain. Objective: This study aims to evaluate the efficacy and mechanisms of QLHQD in treating NAFLD. Methods: This study utilized a NAFLD mouse model to assess the effects of QLHQD on lipid metabolism, including blood lipids and hepatic steatosis, as well as glucose metabolism, including blood glucose levels, OGTT results, and serum insulin. Network pharmacology, bioinformatics, and molecular docking were used to explore how QLHQD may improve NAFLD treatment. Key proteins involved in these mechanisms were validated via WB and immunohistochemistry. Additionally, the expression of downstream pathway targets was examined to further validate the insulin resistance mechanism by which QLHQD improves NAFLD. Results: Animal studies demonstrated that QLHQD alleviated lipid abnormalities, hepatic steatosis, blood glucose levels, the insulin resistance index, and the OGTT results in NAFLD mice (P < 0.05 or 0.01). Network pharmacology and bioinformatics analyses indicated that the effects of QLHQD on NAFLD might involve bile acid secretion pathways. Subsequent validation through Western blotting, immunohistochemistry, and qPCR demonstrated that QLHQD may influence fat metabolism and insulin sensitivity in NAFLD mice via the FXR/TGR5/GLP-1 signaling pathway. Conclusion: QLHQD significantly alleviates glucose and lipid metabolism disorders in a high-fat diet-induced NAFLD mouse model. Its mechanism of action may involve the activation of the FXR/TGR5/GLP-1 signaling pathway in the gut, which reduces lipid accumulation and insulin resistance.
{"title":"Qinlian Hongqu Decoction Modulates FXR/TGR5/GLP-1 Pathway to Improve Insulin Resistance in NAFLD Mice: Bioinformatics and Experimental Study.","authors":"Zhongyi Zhang, Yunliang He, Mei Zhao, Xin He, Zubing Zhou, Yuanyuan Yue, Tao Shen, Juncheng Liu, Gan Zhang, Yong Zhang","doi":"10.1021/acsomega.4c07463","DOIUrl":"10.1021/acsomega.4c07463","url":null,"abstract":"<p><p><b>Background:</b> Qinglian Hongqu decoction (QLHQD), a traditional Chinese herbal remedy, shows potential in alleviating metabolic issues related to nonalcoholic fatty liver disease (NAFLD). However, its precise mode of action remains uncertain. <b>Objective:</b> This study aims to evaluate the efficacy and mechanisms of QLHQD in treating NAFLD. <b>Methods:</b> This study utilized a NAFLD mouse model to assess the effects of QLHQD on lipid metabolism, including blood lipids and hepatic steatosis, as well as glucose metabolism, including blood glucose levels, OGTT results, and serum insulin. Network pharmacology, bioinformatics, and molecular docking were used to explore how QLHQD may improve NAFLD treatment. Key proteins involved in these mechanisms were validated via WB and immunohistochemistry. Additionally, the expression of downstream pathway targets was examined to further validate the insulin resistance mechanism by which QLHQD improves NAFLD. <b>Results:</b> Animal studies demonstrated that QLHQD alleviated lipid abnormalities, hepatic steatosis, blood glucose levels, the insulin resistance index, and the OGTT results in NAFLD mice (<i>P</i> < 0.05 or 0.01). Network pharmacology and bioinformatics analyses indicated that the effects of QLHQD on NAFLD might involve bile acid secretion pathways. Subsequent validation through Western blotting, immunohistochemistry, and qPCR demonstrated that QLHQD may influence fat metabolism and insulin sensitivity in NAFLD mice via the FXR/TGR5/GLP-1 signaling pathway. <b>Conclusion:</b> QLHQD significantly alleviates glucose and lipid metabolism disorders in a high-fat diet-induced NAFLD mouse model. Its mechanism of action may involve the activation of the FXR/TGR5/GLP-1 signaling pathway in the gut, which reduces lipid accumulation and insulin resistance.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 45","pages":"45447-45466"},"PeriodicalIF":3.7,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11561767/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142645971","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The analysis of data-independent acquisition (DIA) mass spectrometry data is crucial for comprehensive proteomics studies. However, traditional single-run methods often fall short in terms of identification depth and consistency. We present HFDiscrim, a specialized multirun DIA analysis tool aimed at enhancing the depth and consistency of reliable peptide identifications of DIA analysis tools. HFDiscrim was extensively benchmarked on multiple data sets, including the MCB data set, the ccRCC data set, and a three-species benchmark mixture. Compared to PyProphet, HFDiscrim identified 22.04% more precursors, 19.1% more peptides, and 13.2% more proteins while maintaining a controllable false discovery rate. Furthermore, HFDiscrim demonstrated higher identification rates and improved reproducibility across multiple runs. HFDiscrim is publicly available at https://github.com/yachliu/HFDiscrim.
{"title":"Cross-Run Hybrid Features Improve the Identification of Data-Independent Acquisition Proteomics","authors":"Yachen Liu, Longfei Mei, Chenyu Liang, Chuan-Qi Zhong, Mengsha Tong* and Rongshan Yu*, ","doi":"10.1021/acsomega.4c0739810.1021/acsomega.4c07398","DOIUrl":"https://doi.org/10.1021/acsomega.4c07398https://doi.org/10.1021/acsomega.4c07398","url":null,"abstract":"<p >The analysis of data-independent acquisition (DIA) mass spectrometry data is crucial for comprehensive proteomics studies. However, traditional single-run methods often fall short in terms of identification depth and consistency. We present HFDiscrim, a specialized multirun DIA analysis tool aimed at enhancing the depth and consistency of reliable peptide identifications of DIA analysis tools. HFDiscrim was extensively benchmarked on multiple data sets, including the MCB data set, the ccRCC data set, and a three-species benchmark mixture. Compared to PyProphet, HFDiscrim identified 22.04% more precursors, 19.1% more peptides, and 13.2% more proteins while maintaining a controllable false discovery rate. Furthermore, HFDiscrim demonstrated higher identification rates and improved reproducibility across multiple runs. HFDiscrim is publicly available at https://github.com/yachliu/HFDiscrim.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 46","pages":"46362–46372 46362–46372"},"PeriodicalIF":3.7,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsomega.4c07398","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671254","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-03DOI: 10.1021/acsomega.4c0890410.1021/acsomega.4c08904
Yang Li*,
As a fragile topological state lacking spin–orbit coupling (SOC) and possessing space–time inversion (PT) symmetry, the Stiefel–Whitney (SW) insulator has received much attention. Up until now, the identification of SW insulators has been extensively suggested for 2D phononic systems but has been rarely considered for 3D phononic systems. 3D carbon allotrope 43T57-CA has the capability to achieve nontrivial phononic SW topology, which can be distinguished by a nontrivial second SW number. Moreover, 3D 43T57-CA can host hinge vibrational modes, which are protected by PT.
{"title":"Phononic Stiefel–Whitney Topology with Hinge Vibrational Modes in 3D Carbon Allotrope 43T57-CA","authors":"Yang Li*, ","doi":"10.1021/acsomega.4c0890410.1021/acsomega.4c08904","DOIUrl":"https://doi.org/10.1021/acsomega.4c08904https://doi.org/10.1021/acsomega.4c08904","url":null,"abstract":"<p >As a fragile topological state lacking spin–orbit coupling (SOC) and possessing space–time inversion (<i>PT</i>) symmetry, the Stiefel–Whitney (SW) insulator has received much attention. Up until now, the identification of SW insulators has been extensively suggested for 2D phononic systems but has been rarely considered for 3D phononic systems. 3D carbon allotrope 4<sup>3</sup>T57-CA has the capability to achieve nontrivial phononic SW topology, which can be distinguished by a nontrivial second SW number. Moreover, 3D 4<sup>3</sup>T57-CA can host hinge vibrational modes, which are protected by <i>PT</i>.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 46","pages":"46610–46614 46610–46614"},"PeriodicalIF":3.7,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsomega.4c08904","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-03DOI: 10.1021/acsomega.4c0673510.1021/acsomega.4c06735
Gege Tang, Rui Jia*, Huilan He, Yiming Li and Xiaolin Li,
Understanding the effect of clay on the mechanical properties and strength criteria of hydrate-bearing sediments (HBS) is essential for evaluating the safety of clay-rich reservoirs. In this study, a series of triaxial shear tests were conducted to investigate the impacts of clay type and content on the mechanical behavior of I-HBS (hydrate-bearing sediments containing illite) and M-HBS (hydrate-bearing sediments containing montmorillonite). The findings reveal that M-HBS exhibit greater susceptibility to strain hardening compared to I-HBS, accompanied by more extensive volume deformation, and both strain hardening and shear shrinkage intensify with increasing clay content. Moreover, the results demonstrate higher failure strength and Young’s modulus in I-HBS than M-HBS. The failure strength of sediments is affected by both the clay content and effective confining pressure, with an established relationship between the failure strength and these two factors. Additionally, the cohesion and internal friction angle of sediments exhibit distinct linear correlations with clay content due to variations in the clay type. The Mohr–Coulomb strength criterion incorporating the clay content is established, enabling the prediction of shear strength in clay-rich hydrate reservoirs. The clay type and content are the cause for different strengths and shear mechanisms of sediments. This research holds significant implications for the safe mining of natural gas clay-rich hydrate reservoirs.
{"title":"Mechanical Properties and Strength Criteria of Hydrate-Bearing Sediments Considering Clay Minerals","authors":"Gege Tang, Rui Jia*, Huilan He, Yiming Li and Xiaolin Li, ","doi":"10.1021/acsomega.4c0673510.1021/acsomega.4c06735","DOIUrl":"https://doi.org/10.1021/acsomega.4c06735https://doi.org/10.1021/acsomega.4c06735","url":null,"abstract":"<p >Understanding the effect of clay on the mechanical properties and strength criteria of hydrate-bearing sediments (HBS) is essential for evaluating the safety of clay-rich reservoirs. In this study, a series of triaxial shear tests were conducted to investigate the impacts of clay type and content on the mechanical behavior of I-HBS (hydrate-bearing sediments containing illite) and M-HBS (hydrate-bearing sediments containing montmorillonite). The findings reveal that M-HBS exhibit greater susceptibility to strain hardening compared to I-HBS, accompanied by more extensive volume deformation, and both strain hardening and shear shrinkage intensify with increasing clay content. Moreover, the results demonstrate higher failure strength and Young’s modulus in I-HBS than M-HBS. The failure strength of sediments is affected by both the clay content and effective confining pressure, with an established relationship between the failure strength and these two factors. Additionally, the cohesion and internal friction angle of sediments exhibit distinct linear correlations with clay content due to variations in the clay type. The Mohr–Coulomb strength criterion incorporating the clay content is established, enabling the prediction of shear strength in clay-rich hydrate reservoirs. The clay type and content are the cause for different strengths and shear mechanisms of sediments. This research holds significant implications for the safe mining of natural gas clay-rich hydrate reservoirs.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 46","pages":"46192–46203 46192–46203"},"PeriodicalIF":3.7,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsomega.4c06735","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142671163","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bauxite residue (or red mud) is a highly alkaline waste generated during the extraction of alumina. As a result of the substantial accumulation of bauxite residue in tailings facilities, there is a growing interest in exploring the potential for reusing this material for other purposes. The main objective of this study is to evaluate the use of activated bauxite residue (ABR) for remediating oil sands process-affected water (OSPW) and as a supplement to municipal wastewater treatment through bench-scale, proof-of-concept studies. The ABR is produced through a reduction roasting process that alters the physicochemical properties of bauxite residue, resulting in the generation of potentially effective adsorbent media. The treatment performance via chemical and biological activity removals (cytotoxicity, estrogenicity, and mutagenicity) was also assessed. For OSPW, ABR treatment resulted in the effective removal of recalcitrant acid-extractable organics (AEOs), with kinetics following the pseudo-second-order and comparable adsorption capacity to other waste materials (e.g., petroleum coke). ABR also effectively reduced the estrogenicity and mutagenicity of OSPW, albeit cytotoxicity increased at higher dosages, possibly due to some components leaching out of the material (e.g., metals). For municipal wastewater, ABR treatment reduced fecal coliform concentrations (>99%), total phosphorus (up to 98%), total ammonia-nitrogen (63%), estrogenicity (nondetectable), and mutagenicity (nondetectable), especially in the primary effluent. The ultimate end use of ABR is for the recovery of valuable metals (especially iron) and as a construction material, but additional work is needed to optimize the dosage (currently in the g/L range) and maximize the use of ABR as an adsorbent prior to its subsequent uses.
{"title":"Treating Waste with Waste: Activated Bauxite Residue (ABR) as a Potential Wastewater Treatment.","authors":"Fei Cheng, Jingya Pang, Scott Berggren, Himanshu Tanvar, Brajendra Mishra, Maricor J Arlos","doi":"10.1021/acsomega.4c06699","DOIUrl":"10.1021/acsomega.4c06699","url":null,"abstract":"<p><p>Bauxite residue (or red mud) is a highly alkaline waste generated during the extraction of alumina. As a result of the substantial accumulation of bauxite residue in tailings facilities, there is a growing interest in exploring the potential for reusing this material for other purposes. The main objective of this study is to evaluate the use of activated bauxite residue (ABR) for remediating oil sands process-affected water (OSPW) and as a supplement to municipal wastewater treatment through bench-scale, proof-of-concept studies. The ABR is produced through a reduction roasting process that alters the physicochemical properties of bauxite residue, resulting in the generation of potentially effective adsorbent media. The treatment performance via chemical and biological activity removals (cytotoxicity, estrogenicity, and mutagenicity) was also assessed. For OSPW, ABR treatment resulted in the effective removal of recalcitrant acid-extractable organics (AEOs), with kinetics following the pseudo-second-order and comparable adsorption capacity to other waste materials (e.g., petroleum coke). ABR also effectively reduced the estrogenicity and mutagenicity of OSPW, albeit cytotoxicity increased at higher dosages, possibly due to some components leaching out of the material (e.g., metals). For municipal wastewater, ABR treatment reduced fecal coliform concentrations (>99%), total phosphorus (up to 98%), total ammonia-nitrogen (63%), estrogenicity (nondetectable), and mutagenicity (nondetectable), especially in the primary effluent. The ultimate end use of ABR is for the recovery of valuable metals (especially iron) and as a construction material, but additional work is needed to optimize the dosage (currently in the g/L range) and maximize the use of ABR as an adsorbent prior to its subsequent uses.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 45","pages":"45251-45262"},"PeriodicalIF":3.7,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11561612/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
<p><p>X-ray structural elucidation, supramolecular self-assembly, and energetics of existential noncovalent interactions for a triad comprising α-diketone, α-ketoimine, and an imidorhenium complex are highlighted in this report. Molecular packing reveals a self-assembled 2D network stabilized by the C-H···O H-bonds for the α-diketone (benzil), and the first structural report of Brown and Sadanaga stressing on the prevalence of <i>only the van der Waals forces</i> seems to be an oversimplified conjecture. In the α-ketoimine, the imine nitrogen atom undergoes intramolecular N···H interaction to render itself inert toward intermolecular C-H···N interaction and exhibits two types of C-H···O H-bonds in consequence to generate a self-assembled 2D molecular architecture. The imidorhenium complex features a self-aggregated 3D packing engendered by the interplay of C-H···Cl H-bonds along with the ancillary C-H···π, C···C, and C···Cl contacts. To the best of our knowledge, in rhenium chemistry, this imidorhenium complex unravels the first example of self-associated 3D molecular packing constructed by the directional hydrogen bonds of C-H···Cl type. The presence of characteristic supramolecular synthons, viz., R<sub>2</sub> <sup>2</sup>(12), R<sub>2</sub> <sup>2</sup>(16), and R<sub>2</sub> <sup>2</sup>(14), in the α-diketone, α-ketoimine, and imidorhenium complex, respectively, has prompted us to delve into the energetics of noncovalent interactions. Symmetry-adapted perturbation theory analysis has authenticated a stability order: R<sub>2</sub> <sup>2</sup>(14) > R<sub>2</sub> <sup>2</sup>(12) > R<sub>2</sub> <sup>2</sup>(16) based on the interaction energy values of -25.97, -9.93, and -4.98 kcal/mol, respectively. The respective average contributions of the long-range dispersion, electrostatic, and induction forces are 58.5, 32.8, and 8.7%, respectively, for the intermolecular C-H···O interactions. The C-H···Cl interactions experience comparable contribution from the dispersion force (57.9% on average), although the electrostatic and induction forces contribute much less, 28.0 and 14.1%, respectively, on average. The natural energy decomposition analysis has further attested that the short-range, interfragment charge transfer occurring via the lp(O/Cl) → σ*(C-H) routes contributes 17-25% of the total attractive force for the C-H···O and C-H···Cl interactions. Quantum theory of atoms in molecules analysis unfolds a first-order exponential decay relation (<i>y</i> = 8.1043<i>e</i> <sup>-<i>x</i>/0.4095</sup>) between the electron density at the bond critical point and the distance of noncovalent interactions. The distances of noncovalent interactions in the lattices are internally governed by the individual packing patterns rather than the chemical nature of the H-bond donors and acceptors. Intrinsic bond strength index analysis shows promise to correlate the electron density at BCP with the SAPT-derived interaction energy for the noncovalent interactions.
{"title":"Diverse Self-Assembled Molecular Architectures Promoted by C-H···O and C-H···Cl Hydrogen Bonds in a Triad of α-Diketone, α-Ketoimine, and an Imidorhenium Complex: A Unified Analysis Based on XRD, NEDA, SAPT, QTAIM, and IBSI Studies.","authors":"Ankita Sinha, Suphal Sen, Tejender Singh, Aniruddha Ghosh, Satyen Saha, Krishanu Bandyopadhyay, Arindam Dey, Suparna Banerjee, Jaydip Gangopadhyay","doi":"10.1021/acsomega.4c07702","DOIUrl":"10.1021/acsomega.4c07702","url":null,"abstract":"<p><p>X-ray structural elucidation, supramolecular self-assembly, and energetics of existential noncovalent interactions for a triad comprising α-diketone, α-ketoimine, and an imidorhenium complex are highlighted in this report. Molecular packing reveals a self-assembled 2D network stabilized by the C-H···O H-bonds for the α-diketone (benzil), and the first structural report of Brown and Sadanaga stressing on the prevalence of <i>only the van der Waals forces</i> seems to be an oversimplified conjecture. In the α-ketoimine, the imine nitrogen atom undergoes intramolecular N···H interaction to render itself inert toward intermolecular C-H···N interaction and exhibits two types of C-H···O H-bonds in consequence to generate a self-assembled 2D molecular architecture. The imidorhenium complex features a self-aggregated 3D packing engendered by the interplay of C-H···Cl H-bonds along with the ancillary C-H···π, C···C, and C···Cl contacts. To the best of our knowledge, in rhenium chemistry, this imidorhenium complex unravels the first example of self-associated 3D molecular packing constructed by the directional hydrogen bonds of C-H···Cl type. The presence of characteristic supramolecular synthons, viz., R<sub>2</sub> <sup>2</sup>(12), R<sub>2</sub> <sup>2</sup>(16), and R<sub>2</sub> <sup>2</sup>(14), in the α-diketone, α-ketoimine, and imidorhenium complex, respectively, has prompted us to delve into the energetics of noncovalent interactions. Symmetry-adapted perturbation theory analysis has authenticated a stability order: R<sub>2</sub> <sup>2</sup>(14) > R<sub>2</sub> <sup>2</sup>(12) > R<sub>2</sub> <sup>2</sup>(16) based on the interaction energy values of -25.97, -9.93, and -4.98 kcal/mol, respectively. The respective average contributions of the long-range dispersion, electrostatic, and induction forces are 58.5, 32.8, and 8.7%, respectively, for the intermolecular C-H···O interactions. The C-H···Cl interactions experience comparable contribution from the dispersion force (57.9% on average), although the electrostatic and induction forces contribute much less, 28.0 and 14.1%, respectively, on average. The natural energy decomposition analysis has further attested that the short-range, interfragment charge transfer occurring via the lp(O/Cl) → σ*(C-H) routes contributes 17-25% of the total attractive force for the C-H···O and C-H···Cl interactions. Quantum theory of atoms in molecules analysis unfolds a first-order exponential decay relation (<i>y</i> = 8.1043<i>e</i> <sup>-<i>x</i>/0.4095</sup>) between the electron density at the bond critical point and the distance of noncovalent interactions. The distances of noncovalent interactions in the lattices are internally governed by the individual packing patterns rather than the chemical nature of the H-bond donors and acceptors. Intrinsic bond strength index analysis shows promise to correlate the electron density at BCP with the SAPT-derived interaction energy for the noncovalent interactions.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 45","pages":"45518-45536"},"PeriodicalIF":3.7,"publicationDate":"2024-11-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11561771/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.1021/acsomega.4c02251
Nouf N. Mahmoud, Salma Hamad, Sawsan Shraim
A diabetic wound exemplifies the challenge of chronic, nonhealing wounds. Elevated blood sugar levels in diabetes profoundly disrupt macrophage function, impairing crucial activities such as phagocytosis, immune response, cell migration, and blood vessel formation, all essential for effective wound healing. Moreover, the persistent presence of pro-inflammatory cytokines and reactive oxygen species, coupled with a decrease in anti-inflammatory factors, exacerbates the delay in wound healing associated with diabetes. This review emphasizes the dysfunctional inflammatory responses underlying diabetic wounds and explores preclinical studies of inflammation-modulating bioactives and biomaterials that show promise in expediting diabetic wound healing. Additionally, this review provides an overview of selected clinical studies employing biomaterials and bioactive molecules, shedding light on the gap between extensive preclinical research and limited clinical studies in this field.
{"title":"Inflammation-Modulating Biomedical Interventions for Diabetic Wound Healing: An Overview of Preclinical and Clinical Studies","authors":"Nouf N. Mahmoud, Salma Hamad, Sawsan Shraim","doi":"10.1021/acsomega.4c02251","DOIUrl":"https://doi.org/10.1021/acsomega.4c02251","url":null,"abstract":"A diabetic wound exemplifies the challenge of chronic, nonhealing wounds. Elevated blood sugar levels in diabetes profoundly disrupt macrophage function, impairing crucial activities such as phagocytosis, immune response, cell migration, and blood vessel formation, all essential for effective wound healing. Moreover, the persistent presence of pro-inflammatory cytokines and reactive oxygen species, coupled with a decrease in anti-inflammatory factors, exacerbates the delay in wound healing associated with diabetes. This review emphasizes the dysfunctional inflammatory responses underlying diabetic wounds and explores preclinical studies of inflammation-modulating bioactives and biomaterials that show promise in expediting diabetic wound healing. Additionally, this review provides an overview of selected clinical studies employing biomaterials and bioactive molecules, shedding light on the gap between extensive preclinical research and limited clinical studies in this field.","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"6 1","pages":""},"PeriodicalIF":4.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01eCollection Date: 2024-11-12DOI: 10.1021/acsomega.4c09053
Mikel Dolz, Dianelis T Monterrey, Felice Quartinello, Patricia Gomez de Santos, Ivan Mateljak, Alessandro Pellis, Georg Guebitz, Javier Viña-González, Miguel Alcalde
Plastic waste is a major threat in our industrialized world and is driving research into bioplastics. The success of biobased polyethylene furanoate (PEF) as a viable alternative to polyethylene terephthalate (PET) of fossil origin will depend on designing effective enzymes to break it down, aiding its recycling. Here, a panel of fungal and bacterial cutinases were functionally expressed in a tandem yeast expression system based on Saccharomyces cerevisiae and Pichia pastoris. The activity of the enzyme panel was tested with soluble PEF model scaffolds, observing a correlation with the degradation of real PEF powder. A high-throughput colorimetric screening assay based on the PEF scaffold diethyl furan-2,5-dicarboxylate was developed, establishing the basis for future directed evolution campaigns of PEFases.
{"title":"Enzyme Benchmarking with Polyethylene Furanoate Soluble Scaffolds for Directed Evolution of PEFases.","authors":"Mikel Dolz, Dianelis T Monterrey, Felice Quartinello, Patricia Gomez de Santos, Ivan Mateljak, Alessandro Pellis, Georg Guebitz, Javier Viña-González, Miguel Alcalde","doi":"10.1021/acsomega.4c09053","DOIUrl":"10.1021/acsomega.4c09053","url":null,"abstract":"<p><p>Plastic waste is a major threat in our industrialized world and is driving research into bioplastics. The success of biobased polyethylene furanoate (PEF) as a viable alternative to polyethylene terephthalate (PET) of fossil origin will depend on designing effective enzymes to break it down, aiding its recycling. Here, a panel of fungal and bacterial cutinases were functionally expressed in a tandem yeast expression system based on <i>Saccharomyces cerevisiae</i> and <i>Pichia pastoris</i>. The activity of the enzyme panel was tested with soluble PEF model scaffolds, observing a correlation with the degradation of real PEF powder. A high-throughput colorimetric screening assay based on the PEF scaffold diethyl furan-2,5-dicarboxylate was developed, establishing the basis for future directed evolution campaigns of PEFases.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 45","pages":"45633-45640"},"PeriodicalIF":3.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11561765/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The use of nucleic acid-based detection tools for microorganisms and fungi has become a gold standard. This is particularly the case for wood-decaying fungi like Serpula lacrymans, which are hard to discriminate based on macroscopic and microscopic observations. This dry rot is important to detect as it is particularly destructive in an infested building, which requires immediate action to prevent spreading and significant damage to structural elements. Through the development and optimization of loop-mediated isothermal amplification against S. lacrymans-specific rDNA internal transcribed spacer region, we demonstrate that it is possible to achieve rapid and specific amplification without nonspecific self-amplification in a similar range as real-time quantitative PCR without any necessary DNA isolation using a colorimetric detection assay. Through a combined set of self-amplification minimization along with hand-held sample homogenization, the LAMP assay was optimized to provide a femtogram-range assay capable of confirming identification in a real field sample either predominantly composed of S. lacrymans or containing the fungus while remaining negative when tested on different types of fungi found in basement-collected samples.
{"title":"Conception and Optimization of Extraction-Free Loop-Mediated Isothermal Amplification Detection of Dry Rot Fungus <i>Serpula lacrymans</i>.","authors":"Vanessa Lapointe, Myriam Roy, Stéphanie Rose, Yvan Boutin, Frédéric Couture","doi":"10.1021/acsomega.4c05509","DOIUrl":"10.1021/acsomega.4c05509","url":null,"abstract":"<p><p>The use of nucleic acid-based detection tools for microorganisms and fungi has become a gold standard. This is particularly the case for wood-decaying fungi like <i>Serpula lacrymans,</i> which are hard to discriminate based on macroscopic and microscopic observations. This dry rot is important to detect as it is particularly destructive in an infested building, which requires immediate action to prevent spreading and significant damage to structural elements. Through the development and optimization of loop-mediated isothermal amplification against <i>S. lacrymans</i>-specific rDNA internal transcribed spacer region, we demonstrate that it is possible to achieve rapid and specific amplification without nonspecific self-amplification in a similar range as real-time quantitative PCR without any necessary DNA isolation using a colorimetric detection assay. Through a combined set of self-amplification minimization along with hand-held sample homogenization, the LAMP assay was optimized to provide a femtogram-range assay capable of confirming identification in a real field sample either predominantly composed of <i>S. lacrymans</i> or containing the fungus while remaining negative when tested on different types of fungi found in basement-collected samples.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"9 45","pages":"45080-45089"},"PeriodicalIF":3.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11561609/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}