Transient [3,3] Cope rearrangement of 3,3-dicyano-1,5-dienes: computational analysis and 2-step synthesis of arylcycloheptanes.

A simple and modular route to arylcycloheptene scaffolds is reported. The two-step route from Knoevenagel adducts and allylic electrophiles is made possible through the design of a Cope rearrangement that utilizes a "traceless" activating group to promote an otherwise thermodynamically unfavorable transformation. Experimentally, the [3,3] rearrangement occurrs transiently at room temperature with a computed barrier of 19.5 kcal mol-1, which ultimately allows for three-component bis-allylation. Ring-closing metathesis delivers the arylcycloheptane and removes the activating group. This report describes the design and optimization of the methodology, scope and mechanistic studies, and computational analysis

Bis[1-(2-eth­oxy­phen­yl)-3-(4-nitro­phen­yl)triazenido]mercury(II)

In the title compound, [Hg(C14H13N4O3)2], the central Hg atom (site symmetry 2) is six-coordinated by two tridentate 1-(2-eth­oxy­phen­yl)-3-(4-nitro­phen­yl)triazenide ligands through two N and one O atoms. The mononuclear complex mol­ecules are connected into two parallel chains by inter­molecular C—H⋯O hydrogen-bonding inter­actions. These chains are connected to each other by face-to-edge C—H⋯π inter­actions between the CH of the ethoxy groups and the aromatic rings, resulting in a two-dimensional architecture in the ac plane

Treatment results of combined platelet-rich plasma and fat injection in patients with velopharyngeal insufficiency

Background: Velopharyngeal insufficiency causes hypernasal vocal quality and can also result in audible nasal air emission and difficulty in producing pressure consonants. The resulting speech is often socially unacceptable and can be difficult to understand. Platelet-rich plasma is an autologous derivative of whole blood. Today, the importance of clinical use of Platelet-rich plasma in the plastic surgery is considered. This study was designed to evaluate the effectiveness of combined Platelet-rich plasma and fat injection in the treatment of velopharyngeal insufficiency. Methods: In this prospective clinicaltrial study, of 15 patients including 9 males and 6 females and aged 15-20 years with mild/ moderate velopharyngeal insufficiency who were injected with 5 mL of combined Platelet-rich plasma (1 mL) and fat (4 mL) in the front volume in the posterior pharyngeal wall in the pre-vertebral fascia under sedation. Speech samples were recorded by nasoendoscopy before the injection, and at 6 weeks and 6 months after the injection. Assessment of pathologic speech was done by speech therapist. Results: Velar displacement showed significantly increased at 6 weeks after the injection (P=0.049). Velopharyngeal gap disappeared in 60% of patients at 6 weeks after the injection (P=0.019). Lateral pharyngeal wall movement showed significantly increased in 73.3% of the patients at 6 months after the injection (P=0.04). After the treatment, aerodynamic assessment showed significantly decreased in nasal air escape during phonation and repeat the words (P<0.05). Assessment speech therapist showed significantly improve quality of phonation in these patients (P<0.05). Conclusion: It seems that, combined Platelet-rich plasma and fat injection lead to improve voice resonance and reduce nasal air escape in all treated cases. It can be a promising alternative to major procedures, such as velopharyngoplasties, for the treatment of mild/ moderate velopharyngeal insufficiency

Vision Indicators for an Islamic University in Reference to the Qur'an and Hadith

Developing a vision and planning for bright futures in a way that will envisage growth and progress form the first and most fundamental step in designing the structure of any organization and institution. However, in spite of all efforts aimed at elevating the institution of university to the desired status of a university in our country, and in spite of all the concerns for Islamicizing universities as sacred institutions, the vision for a university whose values are based on Islamic teachings is not adequately developed yet. This paper therefore aims to have a look on general aspects of concepts of vision and Islamic university in order to determine the main characteristics of an Islamic university and the indicators for developing a vision for such a university. It also refers to the Qur’an verses and Islamic narrations from ahl ul-bayt [the fourteen Infallibles in the belief of Shi‘a] and makes inferences from these teachings to present an adequate vision for and a befitting picture of an Islamic university. This study introduces the Islamic university as an institution with five key aspects: academic identity, religious orientation, research capacity, efficiency for the society, and satisfaction-centeredness. It then develops an ideal vision for an Islamic University based on four indicators which, together, propose a model for an Islamic type of university. They include: knowledge, capability, goodness, and beauty

Factors Governing and Application of the Cope Rearrangement of 3,3-Dicyano-1,5-dienes and Related Studies

Cope and co-workers reported the [3,3] rearrangement of 3,3-dicyano-1,5-dienes in the early 1940s (“The Cope rearrangement”). However, these original substrates have remained largely unstudied until recently. Herein we explore styrene-deconjugating Cope rearrangements, a diastereoselective Cope rearrangement/deconjugative α-allylation sequence, and factors governing α- vs γ-allylation regioselectivity of Knoevenagel adduct allyl anions. Ultimately, these studies result in the synthesis of diverse and functionally dense polycycloalkane frameworks from abundant reagents using simple chemistry

Comparing three clinical prediction rules for primarily predicting the 30-day mortality of patients with pulmonary embolism: The “Simplified Revised Geneva Score,” the “Original PESI,” and the “Simplified PESI”

Background: Patients with suspected pulmonary embolism (PE) should be evaluated for the clinical probability of PE using an applicable risk score. The Geneva prognostic score, the PE Severity Index (PESI), and its simplified version (sPESI) are well-known clinical prognostic scores for PE. The purpose of this study was to analyze these clinical scores as prognostic tools. Materials and Methods: A historical cohort study was conducted on patients with acute PE in Al-Zahra Teaching Hospital, Isfahan, Iran, from June 2013 to August 2014. To compare survival in the 1-month follow-up and factor-analyze mortality from the survival graph, Kaplan–Meier, and log-rank logistic regression were applied. Results: Two hundred and twenty four patients were assigned to two “low risk” and “high risk” groups using the three versions of “Simplified PESI, Original PESI, and Simplified Geneva.” They were followed for a period of 1 month after admission. The overall mortality rate within 1 month from diagnosis was about 24% (95% confidence interval, 21.4–27.2). The mortality rate of low risk PE patients was about 4% in the PESI, 17% in the Geneva, and <1% in the simplified PESI scales (P < 0.005). The mortality rate among high risk patients was 33%, 33.5%, and 27.5%, respectively. Conclusions: Among patients with acute PE, the simplified PESI model was able to accurately predict mortality rate for low risk patients. Among high risk patients, however, the difference between the three models in predicting prognosis was not significant

Synthesis, spectroscopic and DFT investigation of dimethyl-2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-3-(triphenylphosphinylidene)succinate

WOS: 000286850600017Dimethyl-2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-3-(triphenylphosphinylidene)succinate has been synthesized and characterized by elemental analysis, FT-IR and H-1, C-13 and P-31 NMR. The vibrational wavenumbers, gauge including atomic orbital (GIAO) H-1 and C-13 chemical shift values of title compound in the ground state have been computed with density functional theory method (DFT) and the B3LYP functional. The basis sets used are 6-311G(d,p) and 6-31G(d). The harmonic vibrational wavenumbers have been computed and the scaled values have been compared with the experimental FT-IR spectra. The complete assignments have been performed on basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Most of the computed wavenumbers are found to be in good agreement with the observed spectrum. (C) 2010 Elsevier B.V. All rights reserved.Ahi Evran UniversityAhi Evran UniversityThe author (Y. Erdogdu) would like to thank Ahi Evran University Research Fund for its financial support. Please acknowledge to Ms. Lydia Rhyman, who carefully reviewed my manuscript

Overcoming Kinetic and Thermodynamic Challenges of Classic Cope Rearrangements

Systematic evaluation of 1,5-dienes bearing 3,3-electron-withdrawing groups and 4-methylation results in the discovery of a Cope rearrangement for Meldrum's acid-containing substrates that have unexpectedly favorable kinetic and thermodynamic profiles. The protocol is quite general due to a concise and convergent synthesis from abundant starting materials. Furthermore, products with an embedded Meldrum's acid moiety are prepared, which, in turn, can yield complex amides under neutral conditions. We have now expanded the scope of the reductive Cope rearrangement, which, via chemoselective reduction, can promote thermodynamically unfavorable [3,3] sigmatropic rearrangements of 3,3-dicyano-1,5-dienes to form reduced Cope rearrangement products. The Cope rearrangement is found to be stereospecific and can yield enantioenriched building blocks when chiral, nonracemic 1,3-disubstituted allylic electrophiles are utilized. We expand further the use of Cope rearrangements for the synthesis of highly valuable building blocks for complex- and drug-like molecular synthesis