{"title":"Effect of Noise Filtering in an Ultraviolet Detector of UHPLC on the Statistical Reliability of Chemometrically Evaluated Repeatability.","authors":"Akira Kotani, Koichi Machida, Ryo Watanabe, Hideki Hakamata","doi":"10.1248/cpb.c24-00393","DOIUrl":"https://doi.org/10.1248/cpb.c24-00393","url":null,"abstract":"<p><p>A noise filter, which is usually attached to a detector for chromatography, was applied for the improvement of a signal-to-noise ratio (S/N) on a chromatogram. The objective of this paper is to elucidate the effect of noise filtering in an UV detector of ultra HPLC (UHPLC) on the statistical reliability of chemometrically evaluated repeatability by the function of mutual information (FUMI) theory. To examine the statistical reliability of chemometrically evaluated repeatability in the UHPLC system associated with noise filtering, the standard deviation (SD) values of the area in baseline fluctuations with peak region k (s(k)) were obtained from six chromatograms with noise filtering. Further, the average of s(k) values (σ̂) was calculated from the s(k) values (n = 6) to be alternatively applied as the population SD. All s(k)/σ̂ values were within the 95% confidence intervals (CIs) at the freedom degree of 50, indicating the chemometrically estimated relative SD (RSD) of a peak area and RSD by repeated measurements of at least 50 times had equivalent reliability.</p>","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":"72 9","pages":"800-803"},"PeriodicalIF":1.5,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142131932","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"8-Iodoisoquinolinone, a Conformationally Rigid Highly Reactive 2-Iodobenzamide Catalyst for the Oxidation of Alcohols by Hypervalent Iodine.","authors":"Takayuki Yakura, Tomoya Fujiwara, Kanna Asakubo, Hema Naga Lakshmi Perumalla, Mitsuha Uzu, Takashi Okitsu, Kengo Kasama, Hisanori Nambu","doi":"10.1248/cpb.c23-00887","DOIUrl":"10.1248/cpb.c23-00887","url":null,"abstract":"<p><p>The first lactam-type 2-iodobenzamide catalysts, 8-iodoisoquinolinones 8 (IB-lactam) and 9 (MeO-IB-lactam), were developed. These catalysts have a conformationally rigid 6/6 bicyclic lactam structure and are more reactive than the previously reported catalysts 2-iodobenzamides 4 (IBamide) and 5 (MeO-IBamide) for the oxidation of alcohols. The lactam structure could form an efficient intramolecular I---O interaction, depending on the size of the lactam ring.</p>","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":"72 2","pages":"234-239"},"PeriodicalIF":1.7,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139989448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Study of Palladium-Catalyzed Site and Regioselective Reductive Heck Hydroarylation of Unactivated Alkene.","authors":"Takahiro Shirai, Ryo Nakajima, Takuya Kumamoto","doi":"10.1248/cpb.c24-00431","DOIUrl":"https://doi.org/10.1248/cpb.c24-00431","url":null,"abstract":"<p><p>We studied the reaction pathway of our reductive Heck hydroarylation using a palladium catalyst and a hydrosilane. A key question to verify the reaction mechanism was which active species, Ar-Pd<sup>II</sup>-I or Si-Pd<sup>II</sup>-H, first performs migratory insertion into the alkenes. Identifying this step is crucial to elucidate the reaction mechanism. To address this, we designed a substrate containing two trisubstituted alkenes and tested its product. The results suggest that the migratory insertion of Ar-Pd<sup>II</sup>-I into the alkene is the initial step of the reaction. Furthermore, this reaction can construct a quaternary carbon center and give high yields with high functional group tolerance.</p>","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":"72 10","pages":"890-893"},"PeriodicalIF":1.5,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142459118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Development of Methodologies toward the Unified Synthesis of Ellagitannins.","authors":"Kazutada Ikeuchi","doi":"10.1248/cpb.c23-00920","DOIUrl":"10.1248/cpb.c23-00920","url":null,"abstract":"<p><p>Ellagitannins, a class of polyphenols with divergent structures, have attracted considerable attention from synthetic organic chemists. The basic structures in ellagitannins contain esters of D-glucose with galloyl or hexahydroxyldiphenoyl groups, as well as diaryl ether structures. Thus, the synthesis methodologies of such components have been developed by various groups, including our group. This review describes the synthetic methods reported by our group during 2017-2023, aimed at increasing the number of ellagitannins that can be chemically synthesized. In addition, recent related reports are introduced.</p>","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":"72 4","pages":"349-359"},"PeriodicalIF":1.7,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140331560","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Triboelectrification of Active Pharmaceutical Ingredients: Amines and Their Hydrochloride Salts.","authors":"Kenta Fujinuma, Shota Okada, Kyu Hayashi, Masataka Ito, Hironori Suzuki, Kiyohiko Sugano, Shuji Noguchi","doi":"10.1248/cpb.c24-00303","DOIUrl":"10.1248/cpb.c24-00303","url":null,"abstract":"<p><p>The triboelectric properties of active pharmaceutical ingredients (APIs) contribute to problems during the manufacturing of pharmaceuticals. However, the triboelectric properties of APIs have not been comprehensively characterized. In this study, the effect of salt formulation on the triboelectric properties of APIs was investigated. The triboelectric properties of three groups of amines, namely tertiary amines, purine bases, and amino acids, and their hydrochlorides were evaluated using a suction-type Faraday cage meter. Most of the hydrochloride salts exhibited more negative charges than the corresponding free bases, and the degree by which the triboelectric property changed upon hydrochlorination depended on the structural groups of the compounds. In the case of tertiary amines, the change in the zero-charge margin upon hydrochlorination was negatively correlated with the zero-charge margin of the free base. In contrast, hydrochlorination of the amino acids led to a significant change in the zero-charge margin. In most cases, salt formation also affected the triboelectric properties of API powders. Controlling the triboelectric properties of APIs solves various problems caused by the electrification of raw material powders and granules during the production of pharmaceuticals, thereby increasing the quality of produced pharmaceuticals.</p>","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":"72 9","pages":"817-825"},"PeriodicalIF":1.5,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142307195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthesis of Novel Pseudo-Enantiomeric Phase-Transfer Catalysts from Cinchona Alkaloids and Application to the Hydrolytic Dynamic Kinetic Resolution of Racemic 3-Phenyl-2-oxetanone.","authors":"Midori Kawasaki, Takahiro Shirai, Kenji Yatsuzuka, Ryuichi Shirai","doi":"10.1248/cpb.c24-00406","DOIUrl":"https://doi.org/10.1248/cpb.c24-00406","url":null,"abstract":"<p><p>Naturally occurring Cinchona alkaloids such as quinidine (QD)/cinchonine (CN) and their diastereomers, quinine (QN)/cinchonidine (CD), have been recognized as pseudo-enantiomeric pairs. Utilizing these pseudo-enantiomeric alkaloids as chiral resources provides complementary enantioselectivity in many asymmetric reactions. During the screening of Cinchona alkaloid phase-transfer catalysts (PTCs) in the hydrolytic dynamic kinetic resolution of racemic 3-phenyl-2-oxetanone (1) to tropic acid (2), we found that the introduction of a 4-trifluoromethylphenyl group at the vinyl terminus of BnQN significantly reduced the enantioselectivity to 41% enantiomeric excess (ee). The optimized structure of tetrahedral intermediates (TI, PTC + 1 + OH<sup>-</sup>) of hydrolysis obtained by density functional theory (DFT) calculations shows that the orientation of the quinoline and benzene rings of QD class PTC are nearly parallel to each other and to construct a greatly extended π-electron cloud surface, allowing good π-π interaction with the benzene ring of 1.</p>","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":"72 10","pages":"913-916"},"PeriodicalIF":1.5,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142495978","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Astragaloside IV Inhibits the Pyroptosis in the Acute Kidney Injury through Targeting the SIRT1/FOXO3a Axis.","authors":"Chengxi Zha, Yaya Qi, Fujun Xing, Jiansheng Li","doi":"10.1248/cpb.c24-00151","DOIUrl":"https://doi.org/10.1248/cpb.c24-00151","url":null,"abstract":"<p><p>Acute kidney injury (AKI) is a commonly encountered critical condition in clinical settings, often resulting from sepsis, infections or ischemia. Astragaloside IV (AS-IV) is the primary active component of Astragalus. The functions of Astragalus are mainly related to AS-IV, showing remarkable therapeutic effects in anti-inflammatory, antioxidant, immune-enhancing, and anti-tumor aspects. This study aimed to explore the role of AS-IV in AKI development. Lipopolysaccharide (LPS) was used to stimulate the HK-2 cells and rats to establish the AKI model in vivo and in vitro. After AS-IV treatment, the cell viability, pyroptosis rate, lactate dehydrogenase (LDH) activity, interleukin (IL)-18 and IL-1β contents, and cleaved-caspase-1, GSDMD-N, SIRT, FOXO3a protein levels were detected. Caspase-1 levels were analyzed by immunofluorescence staining. Additionallly, the acetylation levels of FOXO3a were detected by immunoprecipitation and Western blot assays. AS-IV treatment promoted the cell viability, and inhibited the pyroptosis, LDH activity, caspase-1 levels in the LPS stimulated HK-2 cells. AS-IV treatment decreased the IL-18 and IL-1β contents, cleaved-caspase-1 and GSDMD-N protein levels in both LPS stimulated HK-2 cells and rats. Furthermore, after EX527 treatment, a Sirtuin 1 (SIRT1) inhibitor, the role of AS-IV in the LPS stimulated HK-2 cells were reversed. AS-IV treatment increased the protein levels and decreased the acetylation levels of FOXO3a, which was reversed after EX527 treatment. Co-immunoprecipitation (CO-IP) assay and immunofluorescence staining confirmed that SIRT1 interacted with FOXO3a. In conclusion, this research demonstrated that AS-IV treatment inhibited the pyroptosis occurrence in LPS stimulated HK-2 cells and rats. This may be related to the SIRT1 mediated deacetylation of FOXO3a.</p>","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":"72 10","pages":"923-931"},"PeriodicalIF":1.5,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142543938","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Synthesis of 2-Substituted Indoles via Migration Reaction of 3-Substituted Indoles with Triflic Acid.","authors":"Kosuke Nakashima, Yuka Kudo, Yasuyuki Matsushima, Shin-Ichi Hirashima, Tsuyoshi Miura","doi":"10.1248/cpb.c23-00792","DOIUrl":"10.1248/cpb.c23-00792","url":null,"abstract":"<p><p>This study showcases the 1,2-migration reactions of alkyl and aryl groups on the indole molecule. Trifluoromethanesulfonic acid effectively facilitates the migration of the substituent from C3- to C2-position of the indole structure. The resulting C2-substituted indoles offer a valuable pathway for the synthesis of natural products and medicinal compounds.</p>","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":"72 3","pages":"336-339"},"PeriodicalIF":1.7,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140206351","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Magnetic Polystyrene Nanoparticles Prepared by Emulsion Solvent-Evaporation for the Chemiluminescent Immunoassay.","authors":"Hiroaki Ichimaru, Masashi Kurimoto, Shigetoshi Kikuchi","doi":"10.1248/cpb.c23-00864","DOIUrl":"10.1248/cpb.c23-00864","url":null,"abstract":"<p><p>In clinical diagnosis, magnetic polystyrene nanoparticles (MPS NPs) are commonly applied to, e.g., the chemiluminescent immunoassay (CLEIA). However, the conventional preparation method of MPS NPs requires a long duration of heating to form polymer particles, which is inefficient. In this study, we prepared MPS NPs by emulsion solvent-evaporation without heating. We evaluated the effect of the solvent in the water and organic phases on the magnetic particle content. MPS NPs prepared by 4% (v/v) MeOH aqueous solution and adding stearic acid (SA) (4MeSA-MPS NPs) exhibited the highest magnetic particle content. Furthermore, CLEIA analysis indicates that the C-reactive protein detection limit is 80 pg/mL. Thus, 4MeSA-MPS NPs are promising for clinical diagnoses.</p>","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":"72 3","pages":"340-344"},"PeriodicalIF":1.7,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140305050","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Guoqing Sui, Lili Shu, Ailing Zhang, Dan Li, Shuhua Cao
{"title":"Sulfonate Derivatives Containing a Kakuol Moiety as Potential Fungicidal Candidates: Design, Synthesis and Antifungal Activity Evaluation.","authors":"Guoqing Sui, Lili Shu, Ailing Zhang, Dan Li, Shuhua Cao","doi":"10.1248/cpb.c23-00857","DOIUrl":"10.1248/cpb.c23-00857","url":null,"abstract":"<p><p>As a part of our continuing exploration to discover new potential promising fungicide candidates, eighteen sulfonate derivatives (3a-3r) containing a kakuol moiety were designed and synthesized. Synthetic sulfonate derivatives were tested comprehensively for antifungal activities against four plant pathogenic fungi (Botrytis (B.) cinerea, Valsa (V.) mali, Fusarium (F.) graminearum, Sclerotinia (S.) sclerotiorum), and their structure activity relationships were summarized. Especially, derivatives 3i and 3j exhibited remarkable activity against V. mali, with the inhibition rates of 99.8 and 100%, which were slightly superior to that of carbendazim (98.9%), a reference fungicide. Moreover, derivatives 3a, 3k and 3q possess the broader antifungal spectrum against three tested plant pathogenic fungi with inhibition rates over 60%. Structure-activity relationship (SAR) analysis indicated that the introduction of 2-F or 3-F into the benzene ring would give rise to a remarkable increase of the antifungal activity against V. mali.</p>","PeriodicalId":9773,"journal":{"name":"Chemical & pharmaceutical bulletin","volume":"72 2","pages":"186-189"},"PeriodicalIF":1.7,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139721801","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}