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The controlled, self-assembled synthesis of multinuclear coordination compounds can be performed via different approaches. Frequently, steric, geometric and/or electronic factors located at the ligand systems predefine the way in which metal ions can assemble them to large aggregates. For the compounds in the present paper, also the Pearson’s acidities and preferred coordination geometries of the metal ions have been used as organization principles. The ligand under study, 2,6-dipicolinoylbis(N,N-diethylthiourea), H2L1ethyl, possesses ‘soft’ sulfur and ‘hard’ nitrogen and oxygen donors. One-pot reactions of this compound with [AuCl(tht)] (tht = tetrahydrothiophene) and M3+ salts (M = Sc, Y, La, Ln, Ga, In) give products with gold-based {Au3(L1ethyl)3}3+ or {Au2(L1ethyl)2}2+ coronands, which host central M3+ ions. The formation of such units is templated by the M3+ ions and the individual size of the coronand rings is dependent on the ionic radii of the central ions in a way that small ions such as Ga3+ form a [Ga{Au2(L1ethyl)2}]+ assembly, while larger ions (starting from Sc3+/In3+) establish neutral [M{Au3(L1ethyl)3}] units with nine-coordinate central ions.

Potential tetradentate thiocarbamoylbenzamidine derivatives H4L have been synthesized from the corresponding benzimidoyl chlorides and triglycine. They are suitable chelating agents for the oxidotechnetium(V) and oxidorhenium(V) cores and form stable, neutral [MO(HL)] complexes with an equatorial SN3 coordination sphere and an additional, uncoordinated carboxylic group, which can be used for bioconjugation. Representatives of the rhenium and Tc-99 products have been isolated and analyzed with spectroscopic methods and X-ray diffraction. Bioconjugates of these complexes with angiotensin-II have been synthesized and structurally characterized. Analogous (99)mTc complexes have been produced and tested in vitro and in vivo. The experiments confirm a considerable stability for the [(99)mTc(HL)] product as well as for its bioconjugate and recommend this class of compounds for further bioconjugation studies towards clinical applications.

Potential tetradentate thiocarbamoylbenzamidine derivatives H4L have been synthesized from the corresponding benzimidoyl chlorides and triglycine. They are suitable chelating agents for the oxidotechnetium(V) and oxidorhenium(V) cores and form stable, neutral [MO(HL)] complexes with an equatorial SN3 coordination sphere and an additional, uncoordinated carboxylic group, which can be used for bioconjugation. Representatives of the rhenium and Tc-99 products have been isolated and analyzed with spectroscopic methods and X-ray diffraction. Bioconjugates of these complexes with angiotensin-II have been synthesized and structurally characterized. Analogous (99)mTc complexes have been produced and tested in vitro and in vivo. The experiments confirm a considerable stability for the [(99)mTc(HL)] product as well as for its bioconjugate and recommend this class of compounds for further bioconjugation studies towards clinical applications.

Cyclization reactions dominated attempts to synthesize N-alkyl- or N-dialkyl-N'-benzoylthiourea ligands having an alkyne group at the amine residue. While exclusively thiazolidine or thiazole derivatives could be isolated during reactions of benzoyl chloride, (NH4)SCN and N-methypropargylamine, an open-chain benzoylthiourea was obtained with unsubstituted propargylamin. But also the latter product isomerized under the influence of a strong base and heat to the corresponding cyclic derivatives. The resulting heterocycles, a 5-methylenthiazolidine (HL4) and a 5-methylthiazole (HL5), react with (NBu4)[ReOCl4]/PPh3 mixtures or [ReOCl3(PPh3)(2)] under formation of the neutral Re(III) complex [ReCl2(PPh3)(2)(L4)] and the cationic Re(V) compound [ReO2(PPh3)(2)(HL5)], respectively. The products have been isolated in crystalline form and studied spectroscopically and by X-ray diffraction. (C) 2016 Elsevier Ltd. All rights reserved.

A new propargyl-substituted thiocarbamoylbenzamidine has been synthesized. The compound acts as a tetradentate ligand and forms stable complexes with {(ReO)-O-V}(3+) and {(TcO)-O-V}(3+) cores. Click couplings of the resulting complexes with benzylazide lead to prototype triazole derivatives, which were analyzed by NMR and IR spectroscopy and mass spectrometry, as well as by X-ray diffraction. A similar coupling procedure has been applied to an azido-modified angiotensin-II peptide, which gives the desired rhenium(V) bioconjugate in good yield. The ease of this coupling and the stability of the conjugate recommend such tetradentate thiocarbamoylbenzamidines also for clinically relevant bioconjugates with Tc-99m.

Cyclization reactions dominated attempts to synthesize N-alkyl- or N-dialkyl-N'-benzoylthiourea ligands having an alkyne group at the amine residue. While exclusively thiazolidine or thiazole derivatives could be isolated during reactions of benzoyl chloride, (NH4)SCN and N-methypropargylamine, an open-chain benzoylthiourea was obtained with unsubstituted propargylamin. But also the latter product isomerized under the influence of a strong base and heat to the corresponding cyclic derivatives. The resulting heterocycles, a 5-methylenthiazolidine (HL4) and a 5-methylthiazole (HL5), react with (NBu4)[ReOCl4]/PPh3 mixtures or [ReOCl3(PPh3)(2)] under formation of the neutral Re(III) complex [ReCl2(PPh3)(2)(L4)] and the cationic Re(V) compound [ReO2(PPh3)(2)(HL5)], respectively. The products have been isolated in crystalline form and studied spectroscopically and by X-ray diffraction. (C) 2016 Elsevier Ltd. All rights reserved.

A new propargyl-substituted thiocarbamoylbenzamidine has been synthesized. The compound acts as a tetradentate ligand and forms stable complexes with {(ReO)-O-V}(3+) and {(TcO)-O-V}(3+) cores. Click couplings of the resulting complexes with benzylazide lead to prototype triazole derivatives, which were analyzed by NMR and IR spectroscopy and mass spectrometry, as well as by X-ray diffraction. A similar coupling procedure has been applied to an azido-modified angiotensin-II peptide, which gives the desired rhenium(V) bioconjugate in good yield. The ease of this coupling and the stability of the conjugate recommend such tetradentate thiocarbamoylbenzamidines also for clinically relevant bioconjugates with Tc-99m.

Materials based on the cationic copper(II) hexanuclear 18-membered metallacrown [18-MCCuII-N(2ph) -6] (2phH=2-piconyl hydrazide) and tetrafluoroborate, perchlorate, nitrate, sulfate, and perrhenate anions were prepared by an easy method in aqueous medium. Single-crystal X-ray characterization of six members of this new family of complexes showed that the anions are attached to the metallacrown by direct coordination to a copper cation or by hydrogen-bonding interaction with the center of the hexamer. The stable cationic nature of the complexes and their ability to bind different anions allows them to adsorb and immobilize environmentally relevant anions such as MO (M=Tc, Re). The MO trapping capacities suggest that these materials would be useful in the treatment of oxoanionic contaminants in water.

2 v. 24 cm., Making of America (MOA), (dlps) AGA1712.0001.001, (lccallno) BT 21 .H143 1861, http://quod.lib.umich.edu/t/text/accesspolicy.html

xix, 405 p. 23 cm., "The editors have abridged this work, omitting matter which was of ... little interest in Great Britain and the United States".--Introd., "Chapters I. to ... XXIV. are translated by Mr. Gage; chapters XIV to XXIII...by Mr. Stuckenberg.", Making of America (MOA), (dlps) AJE7678.0001.001, (lccallno) B 2621 .H143, http://quod.lib.umich.edu/t/text/accesspolicy.html

2 v. 24 cm., Making of America (MOA), (dlps) AGA1712.0001.001, (lccallno) BT 21 .H143 1861, http://quod.lib.umich.edu/t/text/accesspolicy.html

xix, 405 p. 23 cm., "The editors have abridged this work, omitting matter which was of ... little interest in Great Britain and the United States".--Introd., "Chapters I. to ... XXIV. are translated by Mr. Gage; chapters XIV to XXIII...by Mr. Stuckenberg.", Making of America (MOA), (dlps) AJE7678.0001.001, (lccallno) B 2621 .H143, http://quod.lib.umich.edu/t/text/accesspolicy.html

von Dr. K.R. Hagenbach, Prof. der Theol.

HC, C, BMC, Goff, Haebler, Vindel, Vindel, Incunables impresos en España en la BN, Aguiló, Ribelles, Serrano, IBE, CIBN Madrid, GW, ISTC, Martín Abad, Impresores tomados de IBE. Atribuido por otras fuentes al taller de Nicolás Spindeler por encargo de Jaume Vila, Sign.: a-m⁸, no⁶, Letra gótica de dos tamaños, 30 líneas, Capitales e iniciales xilografiadas

Escrivá, Joan, Fenollar, Bernat: Contemplacio a Jesus crucifficat. Roiç de Corella, Joan: Oració a la sacratissima Verge Maria tenint son fill deu Iesus en la falda deuallat de la creu, H, GW, Haebler, Kurz, Vindel, Vindel, Incunables impresos en España en la BN, Aguiló, Ribelles, Serrano, IBE, CIBN Madrid, ISTC, Martín Abad, Impresores tomados de IBE, Sign.: a-h⁸, i-l⁶, Letra gótica (99g), 30-33 líneas, Primera página de la dedicatoria y del texto a dos tintas, Dos grabados xilográficos a página completa. Iniciales xilografiadas al comienzo del texto

HR, GW, BMC, Goff, Haeb, Kurz, Vindel, Vindel, F. Incunables impresos en España en la BN, Pastor, IBE, ISTC, CIBN Madrid (1945), Martín Abad, Sign.: a⁶ b⁴ a-z⁶ A-C⁶ D⁴ [ ]⁶, Letra gótica en 2 tamaños, Texto a 2 columnas, 42 líneas, Iniciales xilografiadas, Algunos huecos para iniciales, letras de aviso, En portada escudo de los Reyes Católicos xilografiado, Tras el colofón, grabado xilográfico representando a la Virgen imponiendo la casulla a San Ildefonso

HCR, Goff, Haeb, Kurz, Vindel, Vindel, F. Incunables impresos en España en la BN, Pastor, IBPORT, IBE, ISTC, GW, CIBNMadrid (1945), Martín Abad, [ ]² a-n⁶ o-p⁴, Letra gótica en 2 tamaños, Texto a 2 columnas, 39-40 líneas, Iniciales xilografiadas, Huecos para iniciales, letras de aviso, Grabado xilográfico tras el colofón

Haebler, Kurz, Vindel, Vindel, Incunables impresos en España en la BN, Pastor, Weale-Bohatta, IBE, CIBN Madrid, GW, ISTC, Martín Abad, Sign.: []⁸, a-zA-K⁸, L⁴, M-R⁸, Letra gótica de varios tamaños, Texto a dos columnas (33 líneas), Texto a dos tintas. Iniciales lombardas

Haebler, Kurz, Vindel, Vindel, Incunables impresos en España en la BN, Ribelles, Serrano, BMC, Goff, IBE, GW, ISTC, Martín Abad, Impresores tomados de IBE, Sign: []a-z[et]⁸, Letra gótica (99g), 27 líneas, Huecos para iniciales, Texto a dos tintas

CR, GW, BMC, Goff, Haeb, Kurz, Vindel, Pastor, IBPORT, IBE, ISTC, Martín Abad, Impresor tomado de IBE, Sign.: []⁶, a-q⁸, r⁶, Letra gótica de varios tamaños, 30 líneas, Grabados xilográficos a página completa en []6v y r6v. Iniciales xilografiadas

H, IGI, Goff, Haebler, Vindel, Vindel, Incunables impresos en España en la BN, Serrano, IBPORT, IBE, CIBN Madrid, Anglés y Subirá, GW, ISTC, Martín Abad, Sign.: ab⁸, c⁶, d-g⁸, h⁶, i⁸, Letra gótica de varios tamaños, Texto a dos columnas (42 líneas), Iniciales xilografiadas

HC, IGI, IBE, CIBN Madrid, CIBN Paris, Haebler, Vindel Arte, Aguiló Fuster, Ribelles Comín, GW, ISTC, Martín Abad, Datos de impresión tomados de IBE, Sign.: a-y⁸ z⁶, Letra gótica en 2 tamaños, Texto a dos columnas (40 líneas), Huecos para iniciales, con y sin letras de aviso, Errores en la foliación original a partir del f. XXXX

Vindel, IBE, CIBN Madrid, GW, ISTC, Martín Abad, Datos de impresión tomados de IBE, Letra gótica de dos tamaños, 58 líneas

Pie de imprenta deducido del análisis tipográfico. El tipo de letra es el adscrito a "Hagembach Sucesor", Norton, p. 370-371, Sign.: a⁸, Port. con grab. xil. representado al maestro con los discípulos, Inic. grab., En h. a2v grab. xil. que representa el rito de alzar la Sagrada Forma

Norton, Martín Abad. Post-incunables, Existen al menos dos composiciones: variante A que comienza: Indulgētia del hospital de señor Santiago. [C]Hristi noīe [et] beati Iacobi inuocato. A todos sea manifiesto como el papa alexandro sexto ... enel hospital ... ; variante B (L.3) ... alexāndro ...e⁻nl hospital ..., Lugar de impresión e impresor tomados de Martín Abad, Fecha de impresión tomada de fin de texto, Impreso por una sola cara, Letra gótica, Firma xil.: "D. Decanus Cōpstelanus admjtor.", Inicial grabada con la imagen de Santiago, Sello circular xilográfico con el monograma MC, Viñeta xilográfica de Santiago en batalla

Martín Abad. Post-Incunables, Pérez Pastor. toledo, Norton, Mención de responsabilidad consta en la h. IIII, Datos del pie de imp. tomados del colofón, Nombre del taller tipográfico tomado de Norton, Sign.: a--m8, A6, En v. de portada, garab. xil. con un caballao rodeado de los signos del zodíaco, Grabados xil. con los signos del zodíaco en h. II y III

Encabezamiento tomado Martín Abad, "Postincunables Ibéricos", 61, Impresor tomado de Martín Abad, "Postincunables Ibéricos", 61, Sign.: a-q⁸, r¹², Portada con orla tipográfica y escudo xilográfico cardenalicio, Texto con apostillas marginales

Norton, Según Martín Abad, Julián. Post-incunables ibéricos. 295, existen dos variantes de impresión, diferenciadas en la línea 6 del texto. La variante A: (l. 6) ... sustētatione ; la variante B: (l. 6) ... sustentatione ... . Este impreso correspondería a la variante A., Fecha de impresión tomada del texto, Lugar de impresión e impresor tomado de Martín Abad, Julián. Post-incunables ibéricos. 295, Impreso por una sola cara, Letra gótica, Firma xilográfica: "D. Decanus Compostelanus ...", Sello circular xilográfico con el símbolo del Christus e iniciales MG, Viñeta xilográfica de Santiago Matamoros

El traductor consta en colofón, Letra gótica, Pie de imprenta tomado de colofón, Norton, 1037, lo atribuye al Sucesor de Pero Hagenbach, Sign.: a8, b10

Norton, Marín Abad. Post-Incunables, Pérez Pastor. Toledo, Nombre del traductor tomado del fol. I, Existe emisión en vitela y dos estados, uno que dice en el colofón "Toletana/iussu..." y otro que dice en cambio: "Toletana/i sui ...", El pie de imp. consta en colofón, en r. de h. CL, Según Norton, 1042, el impresor es el Sucesor de Pedro Hagembach, Sign.: A4, a-s8, t6, Letra gót., Inic. grab., Port. con esc. arzobispal del Cardenal Cisneros, como arzobispo de Toledo

HC, BMC, IGI, Goff, Haeb, Kurz, Vindel, Vindel, Incunables impresos en España en la BN, Pastor, Weale-Bohatta, IBPORT, IBE, ISTIC, CIBN Madrid (1945), Martín Abad, [ ]⁸ a-z⁸ A-Z⁸ Aa-Nn⁸, Letra gótica en 2 tamaños, Texto a 2 columnas (32 líneas), Errores de foliación: 55 en lugar de 60 ; 144 en lugar de 147 ; 173 en lugar de 180 ; 233 en lugar de 223 ; 227 en lugar de 230 ; 226 en lugar de 231 ; 252 en lugar de 257 ; 267 en lugar de 217 ; 283 en lugar de 282 ; 320 en lugar de 314 ; 311 en lugar de 318 y 375 en lugar de 376, Huecos para iniciales e iniciales lombardas grabadas, Texto a 2 tintas, Apostillas marginales, Notación musical con pentagrama en tinta roja, Portada con grabado xilográfico que representa un escudo formado con el capelo cardenalici y en el campo la escena de la imposición de la casulla a San Ildefonso y con la inscripción "Indui eum vestimento salutis sacerdotes eius induam salutari" ; todo enmarcado por una orla xilografiada formada por 8 tacos, con decoración principalmente vegetal, Grabado xilográfico representando a Cristo crucificado con la Virgen y San Juan a los pies de la cruz (h. 229v)

C, GW, BMC, Haeb, Vindel, Vindel, F. Incunables impresos en España en la BN, Aguiló, Serrano, IBE, ISTC, CIBN Madrid (1945), Martín Abad, a-k⁸ l⁶, Letra gótica en 2 tamaños, 32 líneas, Iniciales xilografiadas, Texto a 2 tintas en h. a2

Norton, Pie de imprenta tomado del colofón, El impresor es, según Norton, el Sucesor de Pedro Hagenbach, Sign.: a-h⁸, i¹⁰, Letra gótica, Grabado xilográfico en portada que representa la investidura de San Ildefonso y, en la parte superior, a San Francisco recibiendo los estigmas, todo enmarcado por orla de cuatro piezas, Escudo xilográfico real en recto de la última hoja

Pérez Pastor. Toledo, Norton, Vega, Jesusa. La imprenta en Toledo, Martín Abad. Post-incunables ibéricos, Traducción del original árabe Mukhtār al-hilam wa-mahāsin al-kalim (Diccionario Filológico de Literatura Medieval Española, p. 224), Sign.: a-f⁸, Error de paginación: h. XXVIII por XVII ; h. XXIX por XX, Error de signatura: diiii por diii, Texto a dos columnas, Letra gótica, Iniciales grabadas, Grabado xilográfico en portada representando a un escriba, enmarcado por una orla de ocho tacos

O pé de imprenta consta no colofón, Sign.: [ ]\p4\s, a-l\p8\s, m-n\p6\s, Letra gótica, Texto a dúas columnas, Portada con marca de Pedro Hagembach dentro dunha orla

Copia digital : Biblioteca Virtual de Andalucía, Copia digital : Biblioteca Navarra Digital, Copia digital : Biblioteca Virtual de Patrimonio Bibliográfico (Ministerio de Educación, Cultura y Deporte), Copia digital : Universitat de Valencia, RODERIC, La obra fue traducida por Alonso de Cartagena, según Martín Abad, Post-incunables Ibéricos, 1417, Lugar y año constan en colofón; según Martín Abad la obra fue impresa por los sucesores de Pedro Hagembach, Sign.: a-p\p6\s, L. gót, Port. con grab. xil