Monatshefte Fur Chemie最新文献

{"title":"On the rearrangement of <i>N</i>-aryl-<i>N</i>-Boc-phosphoramidates to <i>N</i>-Boc-protected <i>o</i>-aminoarylphosphonates.","authors":"Edyta Kuliszewska,&nbsp;Friedrich Hammerschmidt","doi":"10.1007/s00706-017-2058-x","DOIUrl":"https://doi.org/10.1007/s00706-017-2058-x","url":null,"abstract":"<p><strong>Abstract: </strong>Various arylamines were converted in two steps to <i>N</i>-Boc-<i>N</i>-arylphosphoramidates. LiTMP and LDA induced directed <i>ortho</i>-metalation at temperatures from -78 to 0 °C. The ensuing [1,3]-migration of the phosphorus atom with its substituents from the nitrogen to the <i>ortho</i>-carbanionic carbon atom gave <i>N</i>-Boc-protected <i>o</i>-aminoarylphosphonates. The nature of the substituent of 3-substituted phenylphosphoramidates strongly influenced the regioselectivity of phosphonate formation. A crossover experiment with a deuterated phosphoramidate proved the intramolecular course of the rearrangement. Three representative <i>N</i>-Boc-<i>o</i>-aminoarylphosphonates were deprotected to access the corresponding <i>o</i>-aminoarylphosphonic acids.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 1","pages":"87-98"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-017-2058-x","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"35699349","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}

{"title":"A computational model to predict the Diels-Alder reactivity of aryl/alkyl-substituted tetrazines.","authors":"Dennis Svatunek,&nbsp;Christoph Denk,&nbsp;Hannes Mikula","doi":"10.1007/s00706-017-2110-x","DOIUrl":"https://doi.org/10.1007/s00706-017-2110-x","url":null,"abstract":"<p><strong>Abstract: </strong>The tetrazine ligation is one of the fastest bioorthogonal ligations and plays a pivotal role in time-critical in vitro and in vivo applications. However, prediction of the reactivity of tetrazines in inverse electron demand Diels-Alder-initiated ligation reactions is not straight-forward. Commonly used tools such as frontier molecular orbital theory only give qualitative and often even wrong results. Applying density functional theory, we have been able to develop a simple computational method for the prediction of the reactivity of aryl/alkyl-substituted tetrazines in inverse electron demand Diels-Alder reactions.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 4","pages":"833-837"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-017-2110-x","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36031585","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}

{"title":"Synthesis of novel ligands targeting phenazine biosynthesis proteins as a strategy for antibiotic intervention.","authors":"Nikolaus Guttenberger,&nbsp;Thomas Schlatzer,&nbsp;Mario Leypold,&nbsp;Sebastian Tassoti,&nbsp;Rolf Breinbauer","doi":"10.1007/s00706-017-2100-z","DOIUrl":"https://doi.org/10.1007/s00706-017-2100-z","url":null,"abstract":"<p><strong>Abstract: </strong>In this contribution, we report synthetic strategies towards potential ligands for the study of binding differences between PhzE, the first enzyme in the biosynthesis of phenazines, and the related enzyme anthranilate synthase. The ligands were designed with the overriding goal to develop new antibiotics via downregulation of phenazine biosynthesis.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 4","pages":"847-856"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-017-2100-z","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36031986","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}

{"title":"A practical guide for using lithium halocarbenoids in homologation reactions.","authors":"Serena Monticelli,&nbsp;Marta Rui,&nbsp;Laura Castoldi,&nbsp;Giada Missere,&nbsp;Vittorio Pace","doi":"10.1007/s00706-018-2232-9","DOIUrl":"10.1007/s00706-018-2232-9","url":null,"abstract":"<p><strong>Abstract: </strong>Lithium halocarbenoids are versatile reagents for accomplishing homologation processes. The fast α-elimination they suffer has been considered an important limitation for their extensive use. Herein, we present a series of practical considerations for an effective employment in the homologation of selected carbon electrophiles.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 7","pages":"1285-1291"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-018-2232-9","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36293487","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}

{"title":"Synthesis of unsymmetrical disulfanes bearing 1,2,4-triazine scaffold and their in vitro screening towards anti-breast cancer activity.","authors":"Danuta Branowska, Justyna Ławecka, Mariusz Sobiczewski, Zbigniew Karczmarzyk, Waldemar Wysocki, Ewa Wolińska, Ewa Olender, Barbara Mirosław, Alicja Perzyna, Anna Bielawska, Krzysztof Bielawski","doi":"10.1007/s00706-018-2206-y","DOIUrl":"10.1007/s00706-018-2206-y","url":null,"abstract":"<p><strong>Abstract: </strong>A new series of 1,2,4-triazine unsymmetrical disulfanes were prepared and evaluated as anticancer activity compounds against MCF-7 human breast cancer cells with some of them acting as low micromolar inhibitors. Evaluation of the cytotoxicity using an MTT assay, the inhibition of [³H]-thymidine incorporation into DNA demonstrated that these products exhibit cytotoxic effects on breast cancer cells in vitro. The most effective compounds with 59 and 60 µM compared to chlorambucil with 47 µM were disulfanes bearing methyl and methoxy substituent in an aromatic ring. Furthermore, all new 14 compounds were obtained with 22-74% yield via mild and efficient synthesis of the sulfur-sulfur bond formation from thiols and symmetrical disulfanes using 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). The molecular structure of the newly obtained compounds was confirmed by X-ray analysis. The conformational preferences of disulfide system were characterized using theoretical calculations at DFT level and statistical distributions of C-S-S-C torsion angle values based on the Cambridge Structural Database (CSD). The DFT calculations and CSD searching show two preferential conformations for C-S-S-C torsion angle close to ± 90° and relatively large freedom of rotation on S-S bond in physiological conditions. The molecular docking studies were performed using the human estrogen receptor alpha (ER<i>α</i>) as molecular target to find possible binding orientation and intermolecular interactions of investigated disulfanes within the active site of ER<i>α</i>. The S…H-S and S…H-C hydrogen bonds between sulfur atoms of bisulfide bridge and S-H and C-H groups of Cys530 and Ala350 as protein residues play crucial role in interaction with estrogen receptor for the most anticancer active disulfane.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 8","pages":"1409-1420"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6060961/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36389686","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}

{"title":"Direct determination of cadaverine in the volatile fraction of aerobically stored chicken breast samples.","authors":"Wojciech Wojnowski,&nbsp;Justyna Płotka-Wasylka,&nbsp;Kaja Kalinowska,&nbsp;Tomasz Majchrzak,&nbsp;Tomasz Dymerski,&nbsp;Piotr Szweda,&nbsp;Jacek Namieśnik","doi":"10.1007/s00706-018-2218-7","DOIUrl":"10.1007/s00706-018-2218-7","url":null,"abstract":"<p><strong>Abstract: </strong>To supplement the currently used methods for poultry meat shelf life assessment, it might be necessary to develop a technique for rapid headspace analysis of volatiles with no prior sample preparation step. Biogenic amines, in particular cadaverine, are considered meat spoilage indicators. Described in this article are the results of a preliminary investigation of the applicability of proton transfer reaction mass spectrometry in the determination of cadaverine concentration in the volatile fraction of poultry meat samples stored in aerobic conditions. Dispersive liquid-liquid microextraction-gas chromatography-mass spectrometry and determination of total viable bacteria were used as reference methods. It was determined that there is a good correlation (Pearson correlation of 0.96) between the concentration of cadaverine in the headspace of chicken meat samples stored over a period of 5 days and the total viable bacteria count. Based on the results, it can be concluded that the changes of cadaverine concentration in the meat samples' volatile fraction can be successfully monitored with a short time of a single analysis and with no sample preparation.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 9","pages":"1521-1525"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-018-2218-7","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36455421","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}

{"title":"Reliable calibration by nonlinear standard addition method in the presence of additive interference effects.","authors":"Marcin Wieczorek,&nbsp;Marek Dębosz,&nbsp;Paweł Świt,&nbsp;Aleksandra Piech,&nbsp;Joanna Kasperek,&nbsp;Paweł Kościelniak","doi":"10.1007/s00706-018-2203-1","DOIUrl":"https://doi.org/10.1007/s00706-018-2203-1","url":null,"abstract":"<p><strong>Abstract: </strong>The possibility of adapting the Standard Addition Method (SAM) to calibration in very difficult analytical conditions, namely when there is a need to determine an analyte with the use of nonlinear calibration graph and in the presence of matrix components causing additive interference effect, is investigated. To this aim the SAM in the common version and the Chemical H-point Standard Addition Method (C-HPSAM) realized by the flow injection technique were applied. Specifically, a flow manifold was used for construction of a set of nonlinear calibration graphs in different chemical conditions. As the graphs were intersected indicating both the additive interference effect and the analytical result free of this effect, the analyte concentration in the sample was able to be obtained with improved accuracy. The applicability of this approach was verified on the example of spectrophotometric determination of paracetamol in pharmaceuticals and of total acidity in wines. The C-HPSAM method enabled complete compensation of the additive effect and obtaining analytical results at a relative error not exceeding 6.0%.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 9","pages":"1567-1572"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-018-2203-1","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36455423","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}

{"title":"Insights in the determination of saxitoxin with fluorogenic crown ethers in water.","authors":"Bernhard J Müller, Günter Mistlberger, Ingo Klimant","doi":"10.1007/s00706-017-2074-x","DOIUrl":"10.1007/s00706-017-2074-x","url":null,"abstract":"<p><strong>Abstract: </strong>In this contribution, we present new insights and a critical discussion in the optical detection of saxitoxin using fluorophores with crown ethers. Fluorescence enhancement is caused by the reduction of photoinduced electron transfer upon complexation with the analyte. Our attempts to improve this detection method neither did yield a functioning sensor nor were the attempts to reproduce published data in this area successful. Due to the fact that only low concentrations of saxitoxin are available, multiple surrogates were investigated at high concentrations. However, no turn on response was observed. Moreover, a fluorescent decomposition product of saxitoxin that forms under UV light was discovered which was in our opinion misinterpreted as a sensor response by previous publications.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 3","pages":"493-497"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5859042/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"35944694","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}

{"title":"Application of X-ray powder diffraction and differential scanning calorimetry for identification of counterfeit drugs.","authors":"Izabela Jendrzejewska,&nbsp;Paweł Zajdel,&nbsp;Ewa Pietrasik,&nbsp;Zoja Barsova,&nbsp;Tomasz Goryczka","doi":"10.1007/s00706-018-2193-z","DOIUrl":"https://doi.org/10.1007/s00706-018-2193-z","url":null,"abstract":"<p><strong>Abstract: </strong>X-ray analysis confirmed that in all investigated samples, the active API (acetylsalicylic acid and ascorbic acid) was present. The values of the interplanar distance <i>d</i>_<i>hkl</i> for the studied samples are in good accordance with those presented in the ICDD database. The intensities of the diffraction lines depend on the content of the component in the tested preparation. Therefore, different intensities of lines for the APIs were observed in the obtained diffraction patterns. Thermal analysis of the studied substances showed that during the thermal analysis, the following phenomena might occur: dehydration and (or) melting, crystalline transformation. Moreover, it was found that the chemical structure of the studied compounds affects the process of their thermal decomposition. The data obtained during these investigations can be useful in quick tests of physicochemical discrepancies and abnormalities between potential components of pharmaceutical preparations. The evidence for the interaction can be obtained by comparing DSC and TG curves of the drug and the excipient, as well as those of their physical mixtures. For this reason, the study of characteristics of thermal decomposition of drugs and excipients is necessary. Based on the above investigations, it may be stated that a combination of two methods: XRPD and DSC can be used to distinguish the original drugs from counterfeit products, e.g., by checking for the presence of the correct API or by a comparison of the drugs fingerprint.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 5","pages":"977-985"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1007/s00706-018-2193-z","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36064559","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}

{"title":"Identification of a biliverdin geometric isomer by means of HPLC/ESI-MS and NMR spectroscopy. Differentiation of the isomers by using fragmentation \"in-source\".","authors":"Rafał Frański, Błażej Gierczyk, Łukasz Popenda, Małgorzata Kasperkowiak, Tomasz Pędzinski","doi":"10.1007/s00706-018-2161-7","DOIUrl":"10.1007/s00706-018-2161-7","url":null,"abstract":"<p><strong>Abstract: </strong>A commercially available biliverdin sample was analyzed by means of HPLC/ESI-MS and NMR spectroscopy. It was been found that beside the main IXα 5<i>Z</i>,10<i>Z</i>,15<i>Z</i> isomer, the sample contains also the geometric isomer IXα 5<i>Z</i>,10<i>Z</i>,15<i>E.</i> It was also found the isomers behave differentially upon \"in-source\" fragmentation in negative ion mode (in contrast to the their behavior upon \"in-source\" fragmentation in positive ion mode and to their behavior upon MS/MS fragmentation in both modes): the relative abundances of deprotonated molecules and fragment ions are significantly different for both isomers, which can be used as an analytical tool to differentiate between the isomers.</p><p><strong>Graphical abstract: </strong></p>","PeriodicalId":18766,"journal":{"name":"Monatshefte Fur Chemie","volume":"149 6","pages":"995-1002"},"PeriodicalIF":1.8,"publicationDate":"2018-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5972171/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"36209712","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}