A Practical, One-Pot Synthesis of Highly Substituted Thiophenes and Benzo[b]thiophenes from Bromoenynes and o-Alkynylbromobenzenes

An efficient synthesis of thiophenes and benzo[b]thiophenes has been developed from easily available bromoenynes and o-alkynylbromobenzene derivatives. This novel one-pot procedure involves a Pd-catalyzed C–S bond formation using a hydrogen sulfide surrogate followed by a heterocyclization reaction. Moreover, in situ functionalization with selected electrophiles further expands the potential of this methodology to the preparation of the corresponding highly substituted sulfur heterocycles.Junta de Castilla y Leon (BU021A09 and GR-172) and Ministerio de Ciencia e Innovacion (MICINN) and FEDER (CTQ2010-15358 and CTQ2009-09949/BQU) for financial support. P.G.-G. and M.A.F.-R. thank MICINN for "Juan de la Cierva" and "Ramon y Cajal" contractsJunta de Castilla y Leon (BU021A09 and GR-172) and Ministerio de Ciencia e Innovacion (MICINN) and FEDER (CTQ2010-15358 and CTQ2009-09949/BQU) for financial support. P.G.-G. and M.A.F.-R. thank MICINN for "Juan de la Cierva" and "Ramon y Cajal" contractsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Organic Letters, copyright © American Chemical Society after peer review and technical editing by the publisher

Tuning the electrical conductance of metalloporphyrin supramolecular wires

In contrast with conventional single-molecule junctions, in which the current flows parallel to the long axis or plane of a molecule, we investigate the transport properties of M(II)-5,15-diphenylporphyrin (M-DPP) single-molecule junctions (M=Co, Ni, Cu, or Zn divalent metal ions), in which the current flows perpendicular to the plane of the porphyrin. Novel STM-based conductance measurements combined with quantum transport calculations demonstrate that current-perpendicular-to-the-plane (CPP) junctions have three-orders-of-magnitude higher electrical conductanc than their current in-plane (CIP) counterparts, ranging from 2.10−2 G0 for Ni-DPP up to 8.10−2 G0 for Zn-DPP. The metal ion in the center of the DPP skeletons is strongly coordinated with the nitrogens of the pyridyl coated electrodes, with a binding energy that is sensitive to the choice of metal ion. We find that the binding energies of Zn-DPP and Co-DPP are significantly higher than those of Ni-DPP and Cu-DPP. Therefore when combined with its higher conductance, we identify Zn-DPP as the favoured candidate for high conductance CPP single-molecule devices

Functionalized Poly(3-hexylthiophene)s via Lithium–Bromine Exchange

Poly(3-hexylthiophene) (P3HT) is one of the most extensively investigated conjugated polymers and has been employed as the active material in many devices including field-effect transistors, organic photovoltaics and sensors. As a result, methods to further tune the properties of P3HT are desirable for specific applications. Herein, we report a facile postpolymerization modification strategy to functionalize the 4-position of commercially available P3HT in two simple steps–bromination of the 4-position of P3HT (Br–P3HT) followed by lithium−bromine exchange and quenching with an electrophile. We achieved near quantitative lithium–bromine exchange with Br–P3HT, which requires over 100 thienyl lithiates to be present on a single polymer chain. The lithiated-P3HT is readily combined with functional electrophiles, resulting in P3HT derivatives with ketones, secondary alcohols, trimethylsilyl (TMS) group, fluorine, or an azide at the 4-position. We demonstrated that the azide-modified P3HT could undergo Cu-catalyzed or Cu-free click chemistry, significantly expanding the complexity of the structures that can be appended to P3HT using this method.National Science Foundation (U.S.) (ECCS-0939514

НАРУШЕНИЕ МАКРОМОЛЕКУЛЯРНОЙ СТРУКТУРЫ КАРДИОМИОЦИТОВ АЛЛОТРАНСПЛАНТАТА СЕРДЦА КАК ПРИЗНАК ХРОНИЧЕСКОГО ОТТОРЖЕНИЯ

Chronic rejection, especially cardiac allograft vasculopathy, is a major limiting factor for long-term transplant survival. This process affects not only the blood vessels, but also cardiomyocytes. However, there are extremely few reports on the evaluation of their macromolecular structure state. The aim of the study was to evaluate the structural proteins of cardiomyocytes (actin, myosin, troponin I, titin, desmin, vinculin) of heart allografts in different periods after the operation (from 6 days to 15 years). Major changes of macromolecular structure were revealed in late period after transplantation (6 months – 15 years). The contribution of humoral immune response in the process of chronic cardiac allograft rejection was observed: in eight of twelve recipients episodes of acute humoral rejection had been repeatedly registered; disorders of the expression of 5 proteins out of 6 characterized were found in recipients with recurrent and persistent antibody-mediated rejection. Хроническое отторжение, и прежде всего болезнь коронарных артерий, является основным лимитирую- щим фактором длительной функции аллотрансплантата сердца. Данный процесс затрагивает не только со- суды, изменениям также подвержены и кардиомиоциты. Однако сообщений, касающихся оценки состоя- ния их макромолекулярной структуры, крайне мало. Целью нашей работы явилось исследование состояния структурных белков кардиомиоцитов (актин, миозин, тропонин I, титин, десмин, винкулин) аллотрансплан- тата сердца в разные периоды после операции (от 6 дней до 15 лет). Основные изменения макромолекуляр- ной структуры выявлены в подгруппе позднего периода (6 мес.–15 лет). Продемонстрирован вклад гумо- рального звена иммунного ответа в процесс хронического отторжения аллотрансплантата сердца: у восьми из двенадцати реципиентов данной подгруппы неоднократно регистрировали эпизоды острого антитело- опосредованного отторжения; нарушения экспрессии пяти белков из шести охарактеризованных были об- наружены у реципиентов с возвратным и персистирующим антителоопосредованным отторжением.

ТРАНСПЛАНТИРОВАННОЕ СЕРДЦЕ. ПРАВОЖЕЛУДОЧКОВАЯ НЕДОСТАТОЧНОСТЬ, ОТТОРЖЕНИЕ ИЛИ МИОКАРДИТ?

The differentiation of the cases of the right ventricular failure in transplanted heart should be complex and challenging. The 28-year old man with dilated cardiomyopathy underwent orthotopic heart transplantation. After transplantation developed right ventricular failure. The biopsy (n = 5) didn’t reveal any signs of myocardial rejection. There were noted some signs of inflammation in lateral right ventricular wall only by gated SPECT. The right ventricular failure increased and 6 months later there was successfully performed the heart retransplantation on the patient. The virusological study revealed the Epstein–Barr virus in myocardium. The explanted heart research excluded limphoproliferative disease by immunogystochemical tests. The final diagnosis is myocarditis. Дифференцирование причин правожелудочковой недостаточности пересаженного сердца должно быть комплексным. Мужчина 28 лет с дилатационной кардиомиопатией был подвергнут ортотопической трансплантации сердца. После трансплантации развилась прогрессирующая правожелудочковая недо- статочность. Биопсия (в количестве 5) не выявила признаков отторжения миокарда. Только при gated SPECT были отмечены признаки воспаления в боковой стенке ПЖ. Правожелудочковая недостаточность нарастала, и спустя 6 месяцев больному успешно была выполнена ретрансплантация сердца. Вирусоло- гическое исследование выявило наличие вируса Эпштейна–Барр в миокарде. Иммуногистохимические исследования эксплантированного сердца исключили лимфопролиферативное заболевание. Заключи- тельный диагноз – миокардит.