A new potential energy surface for forming glycine in the gas phase, starting from association of aminoacetonitrile (NH2CH2CN) with OH followed by subsequent hydrolysis, was determined using CBS-QB3 calculation. The overall activation energy was 90 kJ mol−1 or 0 without or with catalytic H2O, respectively. Alanine or serine was formed from 2-aminopropionitrile (CH3CH(NH2)CN) or 2-amino-3-hydrxypropionitrile (HOCH2CH(NH2)CN) instead of aminoacetonitrile with the overall activation energies of 89 or 49 kJ mol−1, respectively. When an additional H2O was involved in each reaction as a catalyst, barrierless reaction pathways were obtained. These results suggest that it is possible for investigated reactions to occur in interstellar ices along the proposed pathways, taking kinetic aspects into account.
{"title":"Mechanisms of interstellar synthesis of glycine, alanine, and serine from aminonitriles, OH, and H2O","authors":"Joong Chul Choe","doi":"10.1002/bkcs.12844","DOIUrl":"10.1002/bkcs.12844","url":null,"abstract":"<p>A new potential energy surface for forming glycine in the gas phase, starting from association of aminoacetonitrile (NH<sub>2</sub>CH<sub>2</sub>CN) with OH followed by subsequent hydrolysis, was determined using CBS-QB3 calculation. The overall activation energy was 90 kJ mol<sup>−1</sup> or 0 without or with catalytic H<sub>2</sub>O, respectively. Alanine or serine was formed from 2-aminopropionitrile (CH<sub>3</sub>CH(NH<sub>2</sub>)CN) or 2-amino-3-hydrxypropionitrile (HOCH<sub>2</sub>CH(NH<sub>2</sub>)CN) instead of aminoacetonitrile with the overall activation energies of 89 or 49 kJ mol<sup>−1</sup>, respectively. When an additional H<sub>2</sub>O was involved in each reaction as a catalyst, barrierless reaction pathways were obtained. These results suggest that it is possible for investigated reactions to occur in interstellar ices along the proposed pathways, taking kinetic aspects into account.</p>","PeriodicalId":54252,"journal":{"name":"Bulletin of the Korean Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-05-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/bkcs.12844","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141014023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Gajendra Gupta, Yena Choe, Suhyun Kim, Junseong Lee, Jiwon Bang, Chang Yeon Lee
Two new monopyridyl-based Anthracene and Pyrene ligands were synthesized and employed to design Ruthenium-coordinated organometallic complexes, RuAnthra and RuPyrene, respectively. The ligands and their metal complexes were fully characterized by different analytical techniques, including multinuclear 1D- and 2D-NMR, electrospray ionization-mass spectrometry, UV–Vis, fluorescence spectroscopy, and elemental analysis. Furthermore, their photophysical properties were studied in different solvents with increasing polarity using UV–Vis and fluorescence spectroscopy, showing less or no significant solvolysis effect. The average emission lifetimes of the complexes were further determined using time-resolved emission spectroscopy. Additionally, the ligands and their metal complexes showed excellent ability to generate singlet oxygen and can be useful for several important potential applications.
{"title":"Organometallic ruthenium complexes derived from anthracene and pyrene chromophores: Synthesis and photophysical properties","authors":"Gajendra Gupta, Yena Choe, Suhyun Kim, Junseong Lee, Jiwon Bang, Chang Yeon Lee","doi":"10.1002/bkcs.12841","DOIUrl":"10.1002/bkcs.12841","url":null,"abstract":"<p>Two new monopyridyl-based Anthracene and Pyrene ligands were synthesized and employed to design Ruthenium-coordinated organometallic complexes, <b>RuAnthra</b> and <b>RuPyrene</b>, respectively. The ligands and their metal complexes were fully characterized by different analytical techniques, including multinuclear 1D- and 2D-NMR, electrospray ionization-mass spectrometry, UV–Vis, fluorescence spectroscopy, and elemental analysis. Furthermore, their photophysical properties were studied in different solvents with increasing polarity using UV–Vis and fluorescence spectroscopy, showing less or no significant solvolysis effect. The average emission lifetimes of the complexes were further determined using time-resolved emission spectroscopy. Additionally, the ligands and their metal complexes showed excellent ability to generate singlet oxygen and can be useful for several important potential applications.</p>","PeriodicalId":54252,"journal":{"name":"Bulletin of the Korean Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141020014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sunghee Lee, Soyun Lee, Soojin Hwang, So-Jung Park
Plasmonic nanoparticles exhibit dramatic changes in optical properties depending on their spatial organization. Therefore, the ability to precisely control their assembly structure is important for both fundamental understanding and practical applications. In this personal account, we describe a templated surfactant-assisted seed-growth method to synthesize core–shell-type gold nanoparticle assemblies with controllable surface morphologies and optical properties. This approach provides a simple procedure for simultaneous growth and assembly of metal nanoparticles on polymer templates, producing well-defined nanostructures such as spiky nanoshells and raspberry-like metamolecules with useful and interesting optical properties, such as strong and uniform surface-enhanced Raman scattering and metamaterial properties. We discuss the factors that control the morphology and collective properties, describe the design rules acquired from the system, and suggest future directions of this research area.
{"title":"Gold nanoshells with varying morphologies through templated surfactant-assisted seed-growth method","authors":"Sunghee Lee, Soyun Lee, Soojin Hwang, So-Jung Park","doi":"10.1002/bkcs.12845","DOIUrl":"https://doi.org/10.1002/bkcs.12845","url":null,"abstract":"<p>Plasmonic nanoparticles exhibit dramatic changes in optical properties depending on their spatial organization. Therefore, the ability to precisely control their assembly structure is important for both fundamental understanding and practical applications. In this personal account, we describe a templated surfactant-assisted seed-growth method to synthesize core–shell-type gold nanoparticle assemblies with controllable surface morphologies and optical properties. This approach provides a simple procedure for simultaneous growth and assembly of metal nanoparticles on polymer templates, producing well-defined nanostructures such as spiky nanoshells and raspberry-like metamolecules with useful and interesting optical properties, such as strong and uniform surface-enhanced Raman scattering and metamaterial properties. We discuss the factors that control the morphology and collective properties, describe the design rules acquired from the system, and suggest future directions of this research area.</p>","PeriodicalId":54252,"journal":{"name":"Bulletin of the Korean Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/bkcs.12845","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430324","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The tumor-suppressing phosphorylation cascade is primarily regulated by transcriptional enhanced associate domain (TEAD) transcription factors, and the overexpression of these factors is associated with tumorigenesis and cancer progression. The central pocket of TEAD protein can be targeted by noncovalent inhibitors, and therefore, investigating the interaction patterns for TEAD and its available inhibitors seems essential. In this regard, molecular dynamics simulations were conducted to identify the most potent TEAD3 noncovalent inhibitors and to study TEAD3–inhibitor interaction patterns. We developed a 3D-quantitative structure–activity relationship model to investigate the structure–activity correlation for the available TEAD3 inhibitors. Our results indicated the role of Tyr230, Val317, Thr333, Met367, Cys368, Met371, Phe394, Ile396, Gln398, and Phe416 residues in TEAD3–inhibitor interactions. Dihydropyrazolo pyrimidines and compound 2 were identified as the most potent TEAD3 noncovalent inhibitors. The Comparative Molecular Field Analysis model analysis identified the hydrophobic-favored regions around the pyrazolo[1,5-a]pyrimidin-7(4H)-one ring and the unfavored steric regions around cyclohexane and phenyl groups of dihydropyrazolo pyrimidines.
{"title":"Computational basis of TEAD-3 protein noncovalent inhibition: 3D-QSAR modeling and molecular dynamics simulation","authors":"Bita Kaviani, Marzieh Ghani Dehkordi, Hamed Haghshenas","doi":"10.1002/bkcs.12843","DOIUrl":"10.1002/bkcs.12843","url":null,"abstract":"<p>The tumor-suppressing phosphorylation cascade is primarily regulated by transcriptional enhanced associate domain (TEAD) transcription factors, and the overexpression of these factors is associated with tumorigenesis and cancer progression. The central pocket of TEAD protein can be targeted by noncovalent inhibitors, and therefore, investigating the interaction patterns for TEAD and its available inhibitors seems essential. In this regard, molecular dynamics simulations were conducted to identify the most potent TEAD3 noncovalent inhibitors and to study TEAD3–inhibitor interaction patterns. We developed a 3D-quantitative structure–activity relationship model to investigate the structure–activity correlation for the available TEAD3 inhibitors. Our results indicated the role of Tyr230, Val317, Thr333, Met367, Cys368, Met371, Phe394, Ile396, Gln398, and Phe416 residues in TEAD3–inhibitor interactions. Dihydropyrazolo pyrimidines and compound 2 were identified as the most potent TEAD3 noncovalent inhibitors. The Comparative Molecular Field Analysis model analysis identified the hydrophobic-favored regions around the pyrazolo[1,5-a]pyrimidin-7(4H)-one ring and the unfavored steric regions around cyclohexane and phenyl groups of dihydropyrazolo pyrimidines.</p>","PeriodicalId":54252,"journal":{"name":"Bulletin of the Korean Chemical Society","volume":null,"pages":null},"PeriodicalIF":1.7,"publicationDate":"2024-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140690420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The cover picture illustrates metal-organic frameworks (MOFs) being used as fluorescent probes to detect biomarkers in human urine. MOF-based fluorescent probes facilitate the diagnosis of diseases, including pheochromocytoma, toluene exposure, vitamin deficiencies, gout, hyperuricemia, cancers, various body disorders, and teratogenic effects, with low detection limits. Unlike conventional disease diagnosis methods such as biopsies or blood collection, detecting pathogenic biomarkers in human urine is non-invasive and carries less risk. More details are available in the article by Seyeon Jeong and Hoi Ri Moon.