1,2-DIAMINATION OF ALKENES VIA REDUCTION OF 1,2,3-TRIAZOLINIUM IONS

1,2-Diamine substructures are prevalent functional motifs in natural products, pharmaceutical compounds, and ligands. The interesting functionalities of 1,2-diamines have inspired many synthetic chemists to design various methodologies for preparing these structures from simple precursors such as alkenes. In this work, we described two different but related methods using simple and easily accessible reagents for 1,2-diamination of alkenes. In the first method, an alkene undergoes 1,3-dipolar cycloaddition with an organic azide to form a 1,2,3-triazoline. Subsequent N-alkylation of the generated 1,2,3-triazoline gives the 1,2,3-triazolinium ion, which is then hydrogenated over Raney Ni with a balloon of H2 to produce 1,2-diamine. Traditionally, it has been believed that a 1,2,3-triazoline is an unstable species in the presence of heat or light and will readily extrude N2 to form an imine or an aziridine. However, most of the 1,2,3-triazolines prepared in this work were stable to the extrusion of N2 at the temperature required for their formation. In the second method, an alkene undergoes 1,3-dipolar cycloaddition with a 1,3-diaza-2-azoniaallene (azidium ion, our neologism) to afford a 1,2,3-triazolinium ion directly. The 1,2,3-triazolinium ions are reduced to the corresponding 1,2-diamines using the same conditions described above. As was expected, cyclic alkenes provide cis 1,2-diamines, and acyclic trans alkenes provide threo 1,2-diamines due to syn cycloaddition of the alkene to the azidium ion and preservation of the stereochemistry of the 1,2,3-triazolinium ion during the hydrogenation. Surprisingly, the reduction of acyclic cis alkenes proceeded with complete or partial inversion of relative stereochemistry instead of the complete formation of the expected erythro isomer. We hypothesized that this isomerization occurs during the hydrogenation step by Raney Ni. More surprisingly, the reduction of the 1,2,3-triazolinium derived from 5-hexen-2-one produced the diamine product with an additional C–C bond. The X-ray crystallographic analysis and 1D/2D NMR spectra confirmed the structure and the relative stereochemistry of the synthesized 1,2,3-triazolinium ions and 1,2-diamines. Additionally, we had planned to apply the developed 1,2-diamination methodology toward the total synthesis of loline alkaloids. Lolines are a group of nitrogen-containing natural products produced in cool-season grasses and have shown insecticidal and antifeedant properties. In our designed retrosynthesis, disconnection between C(3) and N(4) in loline tricyclic ring, will lead us to the bicyclic intermediate consist of tetrahydrofuran and pyrrolidine ring. We hypothesized that this intermediate can be produced by hydrogenolysis of the corresponding 1,2,3-triazolinium ion synthesized from 2-deoxy-D-ribose (the ether linkage provider). In my attempt toward this total synthesis, the corresponding 1,2,3-triazoline was synthesized as a first key intermediate in seven steps from 2-deoxy-D-ribose. The N-alkylation of the 1,2,3-triazoline, reduction of the produced 1,2,3-triazolinium ion, and completion of the final stages of this total synthesis are still under investigation

Evaluation of Fractional CO2 Laser Efficacy in Acne Scar

INTRODUCTION: Acne scar is formed after severe episodes of acne in teen and earlyadult years. Several treatment options have been used for depressed acne scars suchas punch grafting, punch excision carbon dioxide (CO2) laser etc. Moreover, Studiesshow that laser skin resurfacing such as CO2 fractional can effectively treat depressedacne scars. We investigated the efficacy of fractional CO2 laser in acne scar.METHODS: In this clinical trial; we used CO2 fractional laser (Unit: eCO2 LutronicKorea; FDA approved) in 15 female cases with an age range of 20-40 years old.They underwent 3 sessions of laser resurfacing at one month intervals. In the first session we used laser with a density of 150 and fluency of 70 with a 4mm diameter circular spot in static mode on depressed acne scars, and we exerted laser with density of 100 and fluency 70 with 12 mm diameter square spot in static mode on all involved skin in the other sessions. Photographs were taken before every process. The patients and another dermatologist filled the questionnaire concerning the percent of improvement. Finally, we compared photographs and evaluated the efficacy of CO2 fractional laser in acne scars.RESULTS: Objective and subjective improvement was estimated about 20-70% and 30-70%, respectively, without any erythema, permanent hyperpigmentation and other adverse effects. The important point is that, participants returned back to work after 4-7 days.CONCLUSION: The Fractional CO2 laser resurfacing can be used as a safe and efficacious method to treat depressed acne scar

The Impact of Attending EFL Classes on the Iranian Female Learners’ Attributional Complexity

The multi-layered reality of EFL classes is of great significance in its impact upon the learners’ emotions and attitudes. In this study, it is suggested that teachers by taking a humanistic approach, along with making use of the unique features of their classes, could affect the learners’ thought patterns and cause attitude and behavior change. In particular, the teacher is believed to possess the power to have an impact upon the learners’ attributional complexity or the way they interpret the causes of others’ social behaviors. Attributional complexity, a term coined by Fletcher (1986), is “a psychological construct that describes the degree to which an individual is interested in understanding the causes of others’ behavior” (as cited in Fast, Reimer & Funder, 2008, p. 209). The current study aimed at unfolding the effect of attending foreign language learning classes on the Iranian female EFL learners’ attributional complexity. To this end, 33 Iranian female EFL learners (beginners), and 33 Iranian female non-EFL learners completed Attributional Complexity Scale before and after the EFL courses. The results of the t-tests showed that attributional complexity of the EFL learners did not change significantly after the time interval. The obtained results were believed to be due to the EFL learners’ relative lack of a required level of language proficiency in their first course of English, which enables them to involve in social interactions and benefit the language classes in a way that their thought patterns are affected. In addition, the period of language courses were believed to be too short for this change in EFL learners. Furthermore, it is believed that there is a great need to train teachers and try to actualize the potentialities of EFL classes, due to the endowments of the language teachers and the nature of their classes

The feasibility of using specialized sand for making mosaic of ready mixed mortar

Studies show that mortar and concrete are used as the main materials in more than 80% of technologies. Therefore, pay attention how to increase workability and improve performance required of mortar and concrete. Mortar can be made in numerous ways, but studies have shown that the ready mixed mortar has many advantages compared to others, but without quality control and production monitoring, the customer confidence would be missed. The aim of this study is to investigate the possibility of using specialized sand in the factory for making mosaic mortar mix and controlling mortar properties. In this study, mortar specimens were created by specialized sand for making mosaic, and ordinary sand in different ratio of cement to sand. Also, specimens were produced by the ready mix mortar. The results of the compressive strength and water retention of mortar, the comparisons of fracture specimens and scanning electron microscope (SEM) images showed the possibility of using specialized sand mosaic in the production of dry mortar

Comparison the efficacy of pre-emptive oral celecoxib with acetaminophen in controlling post-operative pain and nausea after lower limb surgery under general anesthesia

IntroductionUp to now, there is no single opinion on how to control pain after surgeryand molecular and clinical research in this area has been continuing. This study aimed to compare the effect of premedication with oral administration of celecoxib and acetaminophen on postoperative pain relief in the lower extremity surgery under general anesthesia.                                                         Materials and methods:In a prospective, randomized, double-blinded, clinical trial study, 70 patients undergoing lower limb surgery under general anesthesia were distributed into two equal groups. In the first and second group, oral acetaminophen 1000 mg orcelecoxib 400 mg capsules were prescribed one hour before the operation, respectively. Postoperative painand nausea severity in both groups were evaluatedby VAS score and compared with each other. ResultsAssessment of pain intensity at 1, 2, 6, 12 and 24 hours after surgery revealed that acetaminophen group at the first hour had more intensity of  postoperative pain (5.46±1.17) compared with celecoxib group(4.31±1.32)(P <0.001). In the rest of the time, there was no significant difference between the two groups. Analysis of variance with repeated observations showed, the trend of postoperative pain intensity during the study in both groups had a significant difference (p = 0.013). The intensity of nausea in the first hour after surgery was significantly more in acetaminophen group compared with celecoxib group (2.8±1.1 vs. 2.2±1.3, p<0.034). Conclusions:Celecoxib may be a better choice in reducing pain and nausea after surgery compared with acetaminophen. Considering no significant adverse effects in many studies, celecoxib may be used as a pre-emptive medication to reduce pain after lower extremity surgery.Key words: Premedication, Post-operative, PONV, pain, Celecoxib, Acetaminophe

Comparing the effect of Metoclopramide and Ketamine as a preemptive analgesia on postoperative pain

زمینه و هدف: جهت کنترل و یا کمک به کاهش درد پس از عمل جراحی از داروها و روشهای مختلف استفاده می شود. آنالژزی پیشگیرانه (Preemptive Analgesia) یکی از روشهایی است که در آن قبل از شروع جراحی از تزریق داروهای ضد درد نظیر مخدرها، کتامین و... استفاده می شود. در برخی از تحقیقات از متوکلوپرامید وریدی جهت کاهش درد پس از عمل جراحی استفاده شده است. این مطالعه با هدف بررسی تاثیر مقایسه ای تزریق داخل وریدی دو داروی کتامین و متوکلوپرامید نیم ساعت قبل از القای بیهوشی بر روی درد و میزان مصرف مخدر پس از جراحی انجام شد. روش بررسی: در این مطالعه کارآزمایی بالینی دو سویه کور تعداد 86 بیمار کلاس 1 و 2 بیهوشی کاندیدای عمل جراحی شکم تحت بیهوشی عمومی، به صورت در دسترس انتخاب و بطور تصادفی ساده به دو گروه تقسیم شدند. در گروه اول متوکلوپرامید (mg 10) و در گروه دوم کتامین (mg/kg 3/0) نیم ساعت قبل از القای بیهوشی به صورت داخل وریدی تزریق شد. نمره درد، میزان مصرف مخدر در ریکاوری و 24 ساعت اول پس از عمل جراحی، طول مدت اقامت در ریکاوری، زمان خروج لوله تراشه و عوارض مختلف از قبیل تهوع، استفراغ، بیقراری، عوارض روانی و...ارزیابی و ثبت گردید. اطلاعات با استفاده از آزمون های آماری کای اسکوار، t و آنالیز واریانس مشاهدات تکرار شده تجزیه و تحلیل گردید. یافته ها: میانگین نمره درد (VAS) در 24 ساعت اول پس از عمل جراحی در گروه متوکلوپرامید 04/3±98/3 و در گروه کتامین 32/3±93/5 بود (05/0

Exploring the telemedicine implementation challenges through the process innovation approach: A case study research in the French healthcare sector

Telemedicine is not a simple technology but a context-dependent innovation implying significant process modifications. Despite the growing interest in telemedicine implementation, it still does not form part of the healthcare organizations' recurrent activities due to several obstacles. The neglect of process change is one of the renowned barriers. This work's originality lies in using the “process innovation” concept as an analytical tool to understand the telemedicine implementation issues from the process change perspective. The qualitative method is chosen based on five telemedicine acts through two case studies in France, a university hospital, and a network of expertise. Findings indicate that implementation requires context adaptation at the level of technology, culture, and strategy. The interaction of these determinants with change enablers and hinders creates the implementation paradigm. In conclusion, we should emphasize the implementation as a whole rather than distinct elements. Managers may prepare the context and integrate the enablers, but the main task is defining an implementation strategy benefiting the stakeholders. This work fills the literature gap in using the process innovation concept to analyze telemedicine implementation challenges and contributes to understanding the context adaptation. It also provides practical implications about the implementation conditions from the process change perspective. © 2021 Elsevier Lt