A. E. Pogonin, Darya A. Postnikova, Artyom Y. Shagurin, Danila V. Belov, S. Usoltsev, Y. Marfin
{"title":"Assignment of the Vibrations of Unsubstituted BODIPY and Aza-BODIPY","authors":"A. E. Pogonin, Darya A. Postnikova, Artyom Y. Shagurin, Danila V. Belov, S. Usoltsev, Y. Marfin","doi":"10.6060/mhc213973p","DOIUrl":"https://doi.org/10.6060/mhc213973p","url":null,"abstract":"","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167309","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}
I. P. Limarev, G. E. Zelinskii, A. Vologzhanina, Y. Zubavichus, Y. Voloshin
{"title":"Preparation and Synchrotron X-Ray Structure of an Apically- and Ribbed-Functionalized Iron(II) Clathrochelate Decorated with Six Methoxyl and Two Carboxyl Terminal Groups","authors":"I. P. Limarev, G. E. Zelinskii, A. Vologzhanina, Y. Zubavichus, Y. Voloshin","doi":"10.6060/mhc210843z","DOIUrl":"https://doi.org/10.6060/mhc210843z","url":null,"abstract":"","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167434","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}
N. Lebedeva, E. S. Yurina, M. A. Lebedev, A. N. Kiselev, S. Syrbu, Yury A. Gubarev
{"title":"Spectral Сharacterization of Сomplexes of Tetra- and Tricationic Porphyrins with DNA Duplex","authors":"N. Lebedeva, E. S. Yurina, M. A. Lebedev, A. N. Kiselev, S. Syrbu, Yury A. Gubarev","doi":"10.6060/mhc214031g","DOIUrl":"https://doi.org/10.6060/mhc214031g","url":null,"abstract":"","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167659","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}
Here, we report the results of investigation of the reactions between cobalamins (Cbls) and hypothiocyanite (OSCN – ), a product of thiocyanate oxidation by hydrogen peroxide in the presence of lactoperoxidase. In the case of aquacobalamin, the product, the UV-vis spectrum of which differs from the UV-vis spectra of Cbl(III)-complexes with SCN – , SO 3 2- , OCN – and CN – anions, is formed and attributed to hypothiocyanitocobalamin. This complex reacts with selenomethionine at substantially lower rate than the free OSCN – . Cyano- and methyl-Cbls are relatively stable in the presence of OSCN – . Glutathionylcobalamin is transformed to hypothiocyanitocobalamin in the presence of OSCN – excess via the oxidation of glutathionyl-ligand and subsequent binding of OSCN – by Cbl(III).
{"title":"Interaction of Cob(III)alamins with Hypothiocyanite. Evidence for the Formation of Hypothiocyanitocobalamin","authors":"Ilia A. Dereven’kov, V. S. Osokin","doi":"10.6060/mhc201128d","DOIUrl":"https://doi.org/10.6060/mhc201128d","url":null,"abstract":"Here, we report the results of investigation of the reactions between cobalamins (Cbls) and hypothiocyanite (OSCN – ), a product of thiocyanate oxidation by hydrogen peroxide in the presence of lactoperoxidase. In the case of aquacobalamin, the product, the UV-vis spectrum of which differs from the UV-vis spectra of Cbl(III)-complexes with SCN – , SO 3 2- , OCN – and CN – anions, is formed and attributed to hypothiocyanitocobalamin. This complex reacts with selenomethionine at substantially lower rate than the free OSCN – . Cyano- and methyl-Cbls are relatively stable in the presence of OSCN – . Glutathionylcobalamin is transformed to hypothiocyanitocobalamin in the presence of OSCN – excess via the oxidation of glutathionyl-ligand and subsequent binding of OSCN – by Cbl(III).","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71166398","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}
B. Egorova, L. Zamurueva, A. Zubenko, A. V. Pashanova, Z. S. Pillai, O. Fedorova, S. Kalmykov
Triacetate of 15-benzoazacrown-5 compound (H 3 BA3A) is a new ligand that has shown advantages towards chelation of some cations. In this paper H 3 BA3A was consequently studied for binding of lead cation. With respect to nuclear properties of 212 Pb radioisotope it can be used for therapy of various oncological diseases mainly due to alpha-emitting daughter radionuclide 212 Bi. Complexes of such radionuclides are considered as parts of targeted radiopharmaceuticals that can be conjugated with biomolecules to provide address delivery to cancerous tissues. Medical radionuclides are commonly short-lived and biomolecules are often heat-sensitive. That is why fast and stable complexation of trace amounts of lead cations in biologically relevant media without additional heating higher than 37 °C is important and challenging task. At the beginning we determined complexation constants in wide pH range including different protonated and hydrolyzed complex species via potentiometric titration technique. The obtained values are high enough for lead chelates logβ(BA3APb – ) = 17.2 (1). Structural features of complex in aqueous solution were established due to 1 H and 13 C NMR spectroscopy. High resolution of obtained spectra and comparison with spectrum of deprotonated ligand shows presence of one rigid conformer of complexed form in the aqueous solution with C s symmetry. In order to study labelled compounds we used longer lived isotope of lead 210 Pb isolated from solution of 226 Ra. Using thin layer chromatography and gamma-spectrometry it was found that 100 μM of ligand is enough to completely chelate 210 Pb in the tracer concentration related to radiopharmaceutical concentration of 212 Pb. According to pH speciation obtained in complexation constant determination, pH 5.5–6 was selected for labelling experiments. Noteworthy, the labeled compound was obtained within 1–5 minutes at room temperature as well as upon heating at 90 o C. Macrocyclic H 3 BA3A demonstrates fast complexation apparently due to larger crown cavity compared to cyclen cavity in H 4 DOTA. This was indirectly shown in potentiometric titration where waiting time for curve’s points was no longer than 5 minutes indicating that equilibrium was achieved within 5 minutes. In order to evaluate possible trans-chelation and trans-metallation of complex in living organism we performed challenging experiments in static conditions: in presence of nine-fold excess of serum proteins, biologically relevant cations 5 mM Ca 2+ , 5 mM Mg 2+ , 0.1 mM Zn 2+ , 0.1 mM Cu 2+ , 0.1 mM Fe 3+ and isotonic solution of 0.15 M NaCl. It was shown that the 100 % intactness of complex can be kept for up to two days of incubation in competing media. Summarizing, the H 3 BA3A forms highly stable complex with lead cation not only in model solution, but also in presence of challenging agents. This stability is provided by high stability constants and rigid structure in solution. 2 O solution using combined glass/AgCl ele
15-苯并氮杂冠-5化合物三乙酸酯(h3ba3a)是一种新型配体，具有螯合某些阳离子的优势。因此，本文研究了h3ba3a与铅阳离子的结合。就212 Pb放射性同位素的核性质而言，它可用于治疗主要由α -放射子放射性核素212 Bi引起的各种肿瘤疾病。这些放射性核素的复合物被认为是靶向放射性药物的一部分，可以与生物分子偶联以向癌组织提供地址递送。医用放射性核素通常是短寿命的，生物分子通常是热敏的。这就是为什么在不额外加热高于37°C的情况下，在生物相关介质中快速稳定地络合微量铅阳离子是一项重要而具有挑战性的任务。首先用电位滴定法测定了不同质子化和水解络合物在较宽pH范围内的络合常数。得到的值足够高，使得铅螯合物logβ(BA3APb -) = 17.2(1)。通过1h和13c NMR谱确定了水溶液中配合物的结构特征。所得光谱的高分辨率和与去质子化配体光谱的比较表明，水溶液中存在一种具有C s对称的络合型刚性构象。为了研究标记化合物，我们使用了从226 Ra溶液中分离出来的寿命较长的同位素铅210 Pb。通过薄层色谱和γ -能谱分析发现，在与放射性药物浓度212 Pb相关的示踪剂浓度下，100 μM的配体足以完全螯合210 Pb。根据络合常数测定得到的pH形态，选择pH 5.5-6进行标记实验。值得注意的是，标记的化合物在室温和90℃加热下均在1-5分钟内获得。大环H 3 BA3A的络合速度快，这显然是由于与H 4 DOTA中的环腔相比，其冠腔更大。这在电位滴定法中间接显示，曲线点的等待时间不超过5分钟，表明在5分钟内达到平衡。为了评估复合体在生物体中可能的反式螯合和反式金属化，我们在静态条件下进行了具有挑战性的实验:存在9倍过量的血清蛋白，生物相关阳离子5 mM ca2 +， 5 mM Mg 2+， 0.1 mM Zn 2+， 0.1 mM Cu 2+， 0.1 mM Fe 3+和0.15 M NaCl等渗溶液。结果表明，在竞争培养基中，复合体的100%完整性可保持2天。综上所述，h3ba3a不仅在模型溶液中，而且在挑战剂存在的情况下，都与铅阳离子形成了高度稳定的配合物。这种稳定性是由溶液中的高稳定常数和刚性结构提供的。在使用标准缓冲液进行适当的校准程序后，使用组合玻璃/AgCl电极的2o溶液。
{"title":"Triacetate of Benzoazacrown Compound as a Chelator for Lead Cations Promising for Targeted Radiopharmaceuticals","authors":"B. Egorova, L. Zamurueva, A. Zubenko, A. V. Pashanova, Z. S. Pillai, O. Fedorova, S. Kalmykov","doi":"10.6060/mhc210440e","DOIUrl":"https://doi.org/10.6060/mhc210440e","url":null,"abstract":"Triacetate of 15-benzoazacrown-5 compound (H 3 BA3A) is a new ligand that has shown advantages towards chelation of some cations. In this paper H 3 BA3A was consequently studied for binding of lead cation. With respect to nuclear properties of 212 Pb radioisotope it can be used for therapy of various oncological diseases mainly due to alpha-emitting daughter radionuclide 212 Bi. Complexes of such radionuclides are considered as parts of targeted radiopharmaceuticals that can be conjugated with biomolecules to provide address delivery to cancerous tissues. Medical radionuclides are commonly short-lived and biomolecules are often heat-sensitive. That is why fast and stable complexation of trace amounts of lead cations in biologically relevant media without additional heating higher than 37 °C is important and challenging task. At the beginning we determined complexation constants in wide pH range including different protonated and hydrolyzed complex species via potentiometric titration technique. The obtained values are high enough for lead chelates logβ(BA3APb – ) = 17.2 (1). Structural features of complex in aqueous solution were established due to 1 H and 13 C NMR spectroscopy. High resolution of obtained spectra and comparison with spectrum of deprotonated ligand shows presence of one rigid conformer of complexed form in the aqueous solution with C s symmetry. In order to study labelled compounds we used longer lived isotope of lead 210 Pb isolated from solution of 226 Ra. Using thin layer chromatography and gamma-spectrometry it was found that 100 μM of ligand is enough to completely chelate 210 Pb in the tracer concentration related to radiopharmaceutical concentration of 212 Pb. According to pH speciation obtained in complexation constant determination, pH 5.5–6 was selected for labelling experiments. Noteworthy, the labeled compound was obtained within 1–5 minutes at room temperature as well as upon heating at 90 o C. Macrocyclic H 3 BA3A demonstrates fast complexation apparently due to larger crown cavity compared to cyclen cavity in H 4 DOTA. This was indirectly shown in potentiometric titration where waiting time for curve’s points was no longer than 5 minutes indicating that equilibrium was achieved within 5 minutes. In order to evaluate possible trans-chelation and trans-metallation of complex in living organism we performed challenging experiments in static conditions: in presence of nine-fold excess of serum proteins, biologically relevant cations 5 mM Ca 2+ , 5 mM Mg 2+ , 0.1 mM Zn 2+ , 0.1 mM Cu 2+ , 0.1 mM Fe 3+ and isotonic solution of 0.15 M NaCl. It was shown that the 100 % intactness of complex can be kept for up to two days of incubation in competing media. Summarizing, the H 3 BA3A forms highly stable complex with lead cation not only in model solution, but also in presence of challenging agents. This stability is provided by high stability constants and rigid structure in solution. 2 O solution using combined glass/AgCl ele","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167094","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}
A. Yagodin, A. Martynov, Yulia G. Gorbunova, A. Tsivadze
New benzoannelated phthalocyanine H 2 A 3 B has been synthesized by cross-condensation of 4,5-dibutoxyphthalonitrile A and naphthalonitrile B bearing two diethyleneglycol substituents. UV-Vis and 1 H NMR measurements performed for H 2 A 3 B showed that the presence of free OH-groups in H 2 A 3 B enhances its aggregation in solution in comparison with its O-tetrahydropyranyl derivative H 2 A 3 Bt , which can be considered as a way to control the physicochemical properties of asymmetric phthalocyanines.
{"title":"Benzoannelated A3B-Phthalocyanines with Diethyleneglycol Substituents: Synthesis and Control of Aggregation","authors":"A. Yagodin, A. Martynov, Yulia G. Gorbunova, A. Tsivadze","doi":"10.6060/mhc210541m","DOIUrl":"https://doi.org/10.6060/mhc210541m","url":null,"abstract":"New benzoannelated phthalocyanine H 2 A 3 B has been synthesized by cross-condensation of 4,5-dibutoxyphthalonitrile A and naphthalonitrile B bearing two diethyleneglycol substituents. UV-Vis and 1 H NMR measurements performed for H 2 A 3 B showed that the presence of free OH-groups in H 2 A 3 B enhances its aggregation in solution in comparison with its O-tetrahydropyranyl derivative H 2 A 3 Bt , which can be considered as a way to control the physicochemical properties of asymmetric phthalocyanines.","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167161","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}
Ivan Yu Kurochkin, V. A. Olshevskaya, A. Zaitsev, Nina I. Girichevac, G. V. Girichev
{"title":"Vibrational Spectra of 5,10,15,20-Tetraphenylporphyrin (H2TPP) and Platinum(II) 5,10,15,20-Tetra(phenyl/pentafluorophenyl)porphyrins (PtTPP and PtTF5PP)","authors":"Ivan Yu Kurochkin, V. A. Olshevskaya, A. Zaitsev, Nina I. Girichevac, G. V. Girichev","doi":"10.6060/mhc224109g","DOIUrl":"https://doi.org/10.6060/mhc224109g","url":null,"abstract":"","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167692","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}
{"title":"From Porphyrin Chemical Dimers to Complex Multicomponent Nanoassemblies: Some Rare Phenomena and Relaxation Processes","authors":"E. Zenkevich, D. Zahn, C. von Borczyskowski","doi":"10.6060/mhc214085z","DOIUrl":"https://doi.org/10.6060/mhc214085z","url":null,"abstract":"","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71167923","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}
V. O. Nikulin, K. P. Birin, Yulia G. Gorbunova, A. Tsivadze
{"title":"Ammonium Imidazoporphyrin – a Newborn in a Family of Porphyrins for Hybrid Materials","authors":"V. O. Nikulin, K. P. Birin, Yulia G. Gorbunova, A. Tsivadze","doi":"10.6060/mhc224231b","DOIUrl":"https://doi.org/10.6060/mhc224231b","url":null,"abstract":"","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71168018","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}
I. S. Mikhel, K. Gavrilov, S. Zheglov, Ivan M. Novikov, K. P. Birin, A. Chernyadyev, V. Tyurin
The synthesis of the tetradentate diamidophosphite ( L ) containing four 1,3,2-diazaphospholidine rings and a porphyrin moiety, its characterization and application in asymmetric Pd-catalyzed reactions are reported. The best results (up to 63 % ee) were obtained for the Pd-catalyzed allylic alkylation of (E)-1,3-diphenylallyl acetate with dimethylmalonate. The complex L [Ru(p-cymene)Cl 2 ] 4 was synthesized in situ and characterized by spectroscopic data. The structure of the compounds obtained is discussed based on 1 H, 13 C, 13 C DEPT, 31 P, 1 H- 13 C HSQC, 1 H- 13 C HMBC, 1 H- 1 H COSY, 1 H- 1 H ROESY NMR spectroscopy, as well as UV-Vis and fluorescence spectroscopy.
报道了含4个1,3,2-重氮膦环和1个卟啉基团的四齿二磷酯(L)的合成、表征及其在不对称pd催化反应中的应用。pd催化(E)-1,3-二苯丙烯酯乙酸酯与二甲基丙二酸酯的烯丙基烷基化反应获得了最佳结果(ee达63%)。原位合成了配合物L [Ru(对伞花烃)Cl 2] 4，并用光谱数据对其进行了表征。用1 H、13 C、13 C DEPT、31 P、1 H- 13 C HSQC、1 H- 13 C HMBC、1 H- 1 H COSY、1 H- 1 H ROESY核磁共振波谱以及紫外可见光谱和荧光光谱对所得化合物的结构进行了讨论。
{"title":"First Tetradentate Diamidophosphite Based on [5,10,15,20-Tetrakis(4-hydroxyphenyl)porphyrinato]zinc: Synthesis, Spectral Features, Coordination, and Application in Asymmetric Pd-Catalyzed Reactions","authors":"I. S. Mikhel, K. Gavrilov, S. Zheglov, Ivan M. Novikov, K. P. Birin, A. Chernyadyev, V. Tyurin","doi":"10.6060/mhc200918g","DOIUrl":"https://doi.org/10.6060/mhc200918g","url":null,"abstract":"The synthesis of the tetradentate diamidophosphite ( L ) containing four 1,3,2-diazaphospholidine rings and a porphyrin moiety, its characterization and application in asymmetric Pd-catalyzed reactions are reported. The best results (up to 63 % ee) were obtained for the Pd-catalyzed allylic alkylation of (E)-1,3-diphenylallyl acetate with dimethylmalonate. The complex L [Ru(p-cymene)Cl 2 ] 4 was synthesized in situ and characterized by spectroscopic data. The structure of the compounds obtained is discussed based on 1 H, 13 C, 13 C DEPT, 31 P, 1 H- 13 C HSQC, 1 H- 13 C HMBC, 1 H- 1 H COSY, 1 H- 1 H ROESY NMR spectroscopy, as well as UV-Vis and fluorescence spectroscopy.","PeriodicalId":18090,"journal":{"name":"Macroheterocycles","volume":null,"pages":null},"PeriodicalIF":1.4,"publicationDate":"2021-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"71166496","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}
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