Rapid Ring-Opening Metathesis Polymerization of Monomers Obtained from Biomass-Derived Furfuryl Amines and Maleic Anhydride

Well-controlled and extremely rapid ring-opening metathesis polymerization of unusual oxanorbornene lactam esters by Grubbs third-generation catalyst is used to prepare a range of bio-based homo- and copolymers. Bio-derived oxanorbornene lactam monomers were prepared at room temperature from maleic anhydride and secondary furfuryl amines by using a 100 % atom economical, tandem Diels–Alder lactamization reaction, followed by esterification. Several of the resulting homo- and copolymers show good control over polymer molecular weight and have narrow molecular weight distributions

Tools and techniques for solvent selection: green solvent selection guides

Driven by legislation and evolving attitudes towards environmental issues, establishing green solvents for extractions, separations, formulations and reaction chemistry has become an increasingly important area of research. Several general purpose solvent selection guides have now been published with the aim to reduce use of the most hazardous solvents. This review serves the purpose of explaining the role of these guides, highlighting their similarities and differences. How they can be used most effectively to enhance the greenness of chemical processes, particularly in laboratory organic synthesis and the pharmaceutical industry, is addressed in detail

Jakość życia pacjentów z napadowym migotaniem przedsionków po ablacji okrążającej żył płucnych

Background: Atrial fibrillation (AF) is the most common arrhythmia and is associated with a deterioration of quality of life (QoL). Catheter ablation is a therapeutic strategy for some patients with AF. The effectiveness of pulmonary vein isolation is still under assessment. Aim: To assess the long-term influence of circumferential pulmonary vein ablation (CPVA) on QoL in patients with AF. Methods: The study population consisted of 33 patients (26 males, age 54.2 ± 9 years) with highly symptomatic (EHRA II–III) drug refractory paroxysmal AF, who underwent CPVA. A clinical examination, electrocardiogram (ECG), and Holter ECG were performed before and during a one-year follow-up. The SF-36 Medical Outcomes Survey Short-Form QoL questionnaire, scored on a 0–100 scale for each of eight domains: bodily pain (BP), general health (GH), mental health (MH), physical functioning (PF), role-emotional (RE), role-physical (RP), social functioning (SF), and vitality (V), was collected before and one year after CPVA. Results: In the one-year follow-up 27 (82%) patients were free of AF. EHRA symptoms were improved one-year after CPVA regardless of CPVA efficacy. After the follow-up the SF-36 questionnaire results improved significantly in all of the subscales in patients without a recurrence of AF after CPVA. In subjects with a recurrence of AF, all of the subscales did not indi­cate any statistically significant differences. There was an association between the CPVA and the following QoL domains: GH (p = 0.018), PF (p = 0.042), and V (p = 0.041). The highest values of the GH and V domains were found in the non-re­currence patients one year after CPVA. Conclusions: CPVA results in the clinical improvement of patients with symptomatic AF regardless of the final arrhythmia termination. Patients after successful CPVA experienced a significant improvement in all of the subscales of the QoL.Wstęp: Migotanie przedsionków (AF) jest jedną z najczęstszych arytmii i wiąże się z pogorszeniem jakości życia (QoL). Izolacja żył płucnych (CPVA) jest jedną z metod terapeutycznych wykorzystywaną u objawowych pacjentów z AF, a jej kompleksowe efekty są wciąż w fazie oceny. Cel: Celem pracy była obserwacja odległych wyników CPVA i ich wpływ na QoL chorych z AF przed i po CPVA. Metody: Badaniem objęto 33 pacjentów (26 mężczyzn), w wieku: 54,2 ± 9 lat z symptomatycznym opornym na farmakote­rapię AF (EHRA II–III), którzy byli poddani CPVA. Badania kliniczne, elektrokardiograficzne (EKG) oraz EKG metodą Holtera i SF-36 przeprowadzono przed, a także rok po CPVA. Jakość życia oceniano za pomocą Kwestionariusza SF-36 Survey Short­-Form. W formularzu SF-36 zastosowano skalę 0–100 dla każdego z 8 parametrów QoL, takich jak: odczucie bólu (BP), ogólny stan zdrowia (GH), stan zdrowia psychicznego (MH), funkcjonowanie fizyczne (PF), stan emocjonalny (RE), stan cielesny (RP), funkcjonowanie społeczne (SF) i witalność (V). Wyniki: Po roku od zabiegu CPVA 27 (82%) pacjentów nie miało napadów AF. Objawy AF (w skali EHRA) uległy zmniejszeniu niezależnie od skuteczności CPVA. Analiza QoL wykazała znaczną poprawę w zakresie wszystkich ocenianych parametrów u pacjentów bez nawrotu arytmii. U chorych z nawrotem AF żaden oceniany parametr QoL nie wykazywał istotnych zmian po roku obserwacji. Stwierdzono związek między CPVA i następującymi parametrami QoL: GH (p = 0,018), PF (p = 0,042), V (p = 0,041). Najwyższe wartości GH i V wykazano u chorych bez nawrotu AF w czasie roku po CPVA. Wnioski: Zabieg CPVA prowadzi do redukcji objawów AF niezależnie od efektu, jakim jest ostateczne ustąpienie arytmii. Pacjenci po skutecznym CPVA odczuwają znaczną poprawę QoL w zakresie każdego ocenianego parametru

Kinetically E-selective macrocyclic ring-closing metathesis

Macrocyclic compounds are central to the development of new drugs, but preparing them can be challenging because of the energy barrier that must be surmounted in order to bring together and fuse the two ends of an acyclic precursor such as an alkene (also known as an olefin). To this end, the catalytic process known as ring-closing metathesis (RCM) has allowed access to countless biologically active macrocyclic organic molecules, even for large-scale production. Stereoselectivity is often critical in such cases: The potency of a macrocyclic compound can depend on the stereochemistry of its alkene; alternatively, one isomer of the compound can be subjected to stereoselective modification (such as dihydroxylation). Kinetically controlled Z-selective RCM reactions have been reported, but the only available metathesis approach for accessing macrocyclic E-olefins entails selective removal of the Z-component of a stereoisomeric mixture by ethenolysis, sacrificing substantial quantities of material if E/Z ratios are near unity. Use of ethylene can also cause adventitious olefin isomerization- A particularly serious problem when the E-alkene is energetically less favoured. Here, we show that dienes containing an E-alkenyl-B(pinacolato) group, widely used in catalytic cross-coupling, possess the requisite electronic and steric attributes to allow them to be converted stereoselectively to E-macrocyclic alkenes. The reaction is promoted by a molybdenum monoaryloxide pyrrolide complex and affords products at a yield of up to 73 per cent and an E/Z ratio greater than 98/2. We highlight the utility of the approach by preparing recifeiolide (a 12-membered-ring antibiotic) and pacritinib (an 18-membered-ring enzyme inhibitor), the Z-isomer of which is less potent than the E-isomer. Notably, the 18-membered-ring moiety of pacritinib- A potent anti-cancer agent that is in advanced clinical trials for treating lymphoma and myelofibrosis-was prepared by RCM carried out at a substrate concentration 20 times greater than when a ruthenium carbene was used.National Institutes of Health (U.S.) (Grant GM-59426)National Science Foundation (U.S.) (Grant CHE-1362763