Asymmetric complexes, 3,10-di( p-Xbenzoyl)-2, 4,9,11-tetramethyl-1,5,8,12-monobenzotetraazacyclo[14]annulenenickel(II), with X¼CH 3 , H, Cl, NO 2 and OCH 3 , have been synthesized and characterized. IR spectra of benzoylated compounds show an intense band attributed to C¼O stretching in the region 1627-1655 cm À1 . Hammett plots of 1/ max of ! * and LMCT transitions have positive (þ 0.224) and negative slopes (À0.250), respectively. 1 H NMR spectra exhibit deshielding effects due to benzoyl groups, while methyl protons show shielding effects. Substituent effects in 1 H and 13 C NMR are similar. Voltammograms have two irreversible oxidation peaks due to the ligands in the ranges þ 290 to þ 350 mV and þ 540 to þ 600 mV, respectively. Reduction and oxidation peaks (metal-based) are found at þ 0.840 to þ 0.930 V and À2.580 to À2.840 V, respectively. Hammett plots of the first two oxidation potentials are linear with slopes of þ 0.028. Metal-based redox potentials (E op and E rp ) are dependent on substituents. The structure of the chloro-substituted complex 4 (orthorhombic, C222 1 , a ¼ 8.918(5), b ¼ 28.282(5), c ¼ 26.490(5) Å , Z ¼ 4, R1 ¼ 0.0392 and wR2 ¼ 0.0987) was solved using single-crystal X-ray diffraction methods.
Background Cardiac rehabilitation (CR) is recommended for patients with cardiovascular disease. However, the participation and completion rates for hospital-based CR are low, and home-based CR has been suggested as an alternative. This study aimed to develop a home-based CR program and assess its feasibility over a 6-week period in patients with left ventricular dysfunction or a history of myocardial infarction (MI).Methods The study consisted of two parts: Pilot Study 1 focused on developing an exercise protocol, while Study 2 aimed to assess the feasibility of a 6-week home-based CR program. Eight patients participated in Study 1 and 16 participated in Study 2. The home-based CR exercise program in Study 2 was developed based on the results of Study 1 and included two exercise education sessions and four telephone counseling sessions.Results Participants expressed overall satisfaction with the exercise program in Study 1. Heart rate increased in response to exercise, but this did not correspond with perceived exertion. In Study 2, 13 out of 16 participants (81.3%) completed the 6-week home-based CR program, with a participation rate of 100% in both exercise education and phone counseling sessions. Adherence to the exercise protocol was 83.1% and no serious adverse events were observed. At the beginning of the study, only three out of 13 participants (23.1%) met the requirements for both aerobic and resistance exercises, but at the end of the 6-week program, 10 out of 13 participants (76.9%) fulfilled the requirements.Conclusion The exercise program developed in this study was safe and feasible, and the 6-week home-based CR program was feasible and effective in increasing the physical activity levels of patients with left ventricular dysfunction without any reported adverse effects.
Several tetraazaannulenenickel(II) complexes have been synthesized by a one-step template method in a high yield. The replacement of the central metal atom, by other transition metals, is possible only by demetallating nickel complexes. These complexes have been known to possess different chemical and thermal stabilities and electrocatalytic activities by substituents at the methine sites such as psubstituted benzoyl chloride, nicotinyl chloride and acetyl chloride, etc.1-5 These tetraazaannulene complexes were mostly symmetric nickel(II) complexes with substituents at methine sites, while the examples of asymmetric complexes were rarely reported. 3,[5][6][7][8][9] In previous papers we have reported on the reaction, spectral and electrochemical properties and crystal structures of the asymmetric monobenzotetraaza- [14]annulenenickel(II) complexes with five types of psubstituted benzoyl or thiophenecarbonyl groups at the methine sites.10-12 Also, we have studied the crystal structures of asymmetric monobenzotetraaza [14]annulenepalladium(II) and -copper(II) complexes. 13,14 On the other hand, no one has investigated on the reaction, property and crystal structure of the asymmetric palladium(II) complex with para substituted benzoyl groups at the methine sites, as π-conjugated electron system.In the present work, we report that the synthesis and characterization of new asymmetric 3,10-dibenzoylmonobenzotetraaza[14]annulenepalladium(II) complexes, also the electronic effects of the substituents of the p-Xbenzoyl group (X = CH 3 , H, Cl and NO 2 ) on the infrared, electronic absorption and NMR spectra and cyclovoltammograms for the complexes. The structure of complex 2 is identified by X-ray diffraction analysis.
Experimental SectionMaterials and measurements. The solvents such as methanol, ethanol, acetonitrile and dichloromethane were refluxed over calcium hydride or sodium metal under nitrogen, and checked for purities by GC just before use. Tetraethylammonium perchlorate (TEAP) used as a supporting electrolyte, was prepared and purified by the method described by Kolthoff and Coetzee. 15
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