Studies on Reactions of Cyclopropanated Pyrrole: Synthesis of Bis-β-homoproline, Tropane- and Pyrrolidinone-derivatives

Cyclopropanated pyrroles have been accompanied in lots of reactions due to its versatility and capability to approach to more complex molecules. The unique reactivity of cyclopropanated pyrroles results from the three-membered ring which has a tendency to release the ring strain and the substituents around it to provide the electronic characteristics. As described in first chapter in the main part, the dimerization of cyclopropanated pyrrole 60c was catalyzed by the hidden Brønsted acid generated from the gold catalyst and phenylacetylene. Under such mild condition, dimer 121 was obtained as a single diastereomer in a good yield which could be then straightforwardly transformed into bis-β-homoproline 146 after hydrogenation, ring opening and deprotection. The synthesis of enantiopure 146 and the evaluation of its activity as an organocatalyst are still to be explored. Next in second chapter, cycloaddition of substrate 60b and 60d has been investigated. The cycloaddition reaction utilized 1,3-dipole generated in-situ from substrate 60d under heating condition which was then reacted with various dipolarophiles. The reaction could occur without a catalyst and by simple procedure, the desired tropane products could be obtained stereoselectively in high yields. Further functionalizations to get access to cocaine or ferruginine derivatives are currently ongoing in the working group. In the last chapter, the literature known procedure for enantioselectie pyrrolidinone synthesis has been employed to the substrate 249. In order to generate chiral 249, an asymmetric rhodium-catalyzed cyclopropanation was performed which was followed by bromohydrin formation and subsequent oxidation to afford the intermediate 257. In the end, chiral pyrrolidinone 258 and 259 were obtained by radical ring opening reaction with AIBN and n-Bu3SnH. All of performed reactions has shown to retain high enantiopurity of intermediates and products. In summary, three different applications of cyclopropanated pyrrole 60 have been explored and demonstrated. From bis-β-homoproline 146 to tropane- (197) and pyrrolidinone-derivative (258 and 259), such complex compounds could be successfully synthesized from substrate 60 and high stereoselectivity could be achieved in all transformations

The Impact of Pacific Lutheran on Collective Bargaining at Catholic Colleges and Universities

In 1979, the Supreme Court found that teachers at a Catholic parochial school were exempt from the National Labor Relations Act (NLRA) because of First Amendment religious infringement risks. Subsequently, the National Labor Relations Board (NLRB) has faced controversy over its efforts to delineate an appropriate test for the religious exemption in the higher education context. This uncertainty over the NLRB’s test has resulted in time-consuming litigation and hampered faculty’s ability to organize at schools where Board jurisdiction would not present a significant risk of First Amendment infringement. This paper argues that the Board’s recent decision in Pacific Lutheran University will bring much-needed stability in this area of the law because the new religious exemption test is carefully crafted to protect both constitutional and statutory interests. More faculty will be able to exercise their right to organize, and this wider experience with collective bargaining within Catholic colleges universities will reveal how speculative the constitutional entanglement risks actually are under the NLRA

Stereoselective Synthesis of Tropanes via a Retro-6 p Electrocyclic Ring-Opening / Huisgen [3+2]-Cycloaddition Cascade of Monocyclopropanated Heterocycles. Stereoselektive Synthese von Tropanen über eine 6π-elektrocyclische Ringöffnung/ Huisgen-[3+2]-Cycloadditionskaskade von monocyclopropanierten Heterocyclen

The synthesis of tropanes via a microwave-assisted, stereoselective 6 pi-electrocyclic ring-opening/ Huisgen [3+2]-cycloaddition cascade of cyclopropanated pyrrole and furan derivatives with electron-deficient dipolarophiles is demonstrated. Starting from furans or pyrroles, 8-aza- and 8-oxabicyclo[3.2.1]octanes are accessible in two steps in dia- and enantioselective pure form, being versatile building blocks for the synthesis of pharmaceutically relevant targets, especially for new cocaine analogues bearing various substituents at the C-6/C-7 positions of the tropane ring system. Moreover, the 2-azabicyclo[2.2.2]octane core (isoquinuclidines), being prominently represented in many natural and pharmaceutical products, is accessible via this approach

Effects of interval and sprint training under hypobaric hypoxia on aerobic, anaerobic, and time trial performance in elite Korean national male mountain bike cyclists—a pilot study

The purpose of our study to determine the effects of interval hypoxic training (IHT) and repeated sprint training in hypoxia (RSH) on metabolic and cardiac function during submaximal exercise, aerobic and anaerobic performance, and time trial performance in elite Korean national male mountain bike (MTB) cyclists. The participants included elite Korean national male MTB cyclists (n = 4) preparing for the 19th Asian Games in Hangzhou 2022. The hypoxic training frequency was 90 min (3 days per week for 4 weeks). Before and after hypoxic training, metabolic and cardiac functions during submaximal exercise, aerobic performance, anaerobic performance and time trial performance were measured. Oxygen uptake, carbon dioxide excretion, and heart rate tended to decrease, and stroke volume, end-diastolic volume and cardiac output tended to increase. In aerobic, anaerobic and time trial performances, the peak torque in aerobic performance significantly increased (p = 0.046). Maximal oxygen uptake and exercise time in aerobic performance, relative peak power, relative mean power, post-exercise blood lactate level, fatigue index in anaerobic performance, and time trial performance showed an improved tendency (all p = 0.068). Our pilot study confirmed that although the sample size was small, IHT and RSH can potentially improve athletic performance in elite Korean national male MTB cyclists

Lab-Scale Exploration of Abiotic Transformation Approaches for Groundwater Remediation of Per- and Polyfluoroalkyl Acids

Per- and polyfluoroalkyl acids (PFAAs), a group of per- and polyfluoroalkyl substances (PFASs), have been extensively used in relatively large amount since the 1950s for industrial and consumer applications such as surfactants, coatings, paper packing products, and fire-fighting foams (e.g., aqueous film-forming foams (AFFFs)) due to their unique surfactant property and extremely chemically and thermally stable nature. Of the known PFAAs, long chain perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) have received increasing attention in recent years due to their global distribution, environmental persistence, biological recalcitrance, bioaccumulative properties, and potential toxicities. Recently, other PFAAs such as 6:2 fluorotelomer sulfonate (6:2 FTSA) and perfluorohexane sulfonate (PFHxS) were also added to the list of USEPA Unregulated Contaminant Monitoring Regulation (UCMR3). Research presented here focused on exploring at the lab-scale 4 technologies with potential for use in-situ remediation of groundwater contaminated with PFAAs: (1) the abiotic oxidation of PFOA, 6:2 FTSA, and PFOS using heat-activated persulfate (PS, 4.2~84 mM) at 20~60 °C; (2) nanosized zero valent iron coated with palladium (Pd0/nFe0 NPs) to transform PFOS, which was not transformed with PS; (3) vitamin B12 (VB12) with nanosized zero valent zinc (nZn0) to defluorinate both branched (br-) and linear (L-) PFOS and PFHxS isomers; and (4) permanganate (PM)-based technologies to transform PFOS in buffered and unbuffered solutions at 65 °C. In all studies, PFAA removal (or transformation) was quantified by comparing the combined PFAA mass in aqueous phase and extracts if solid particles were present to the initial PFAA mass measured in the applied PFAA solutions. PFOA was successfully oxidized using heat-activated PS sequentially removing CF2 groups to shorter chain perfluoroalkyl carboxylic acids (PFCAs). 6:2 FTSA was also oxidized first breaking the ethyl linkage and CF2–CH 2 bond generating PFCAs with subsequent CF2 removal like PFOA. No PFOS removal was observed even at 90 °C and using higher PS concentrations (84 mM). In the Pd0/nFe0 NPs systems, ~26% of PFOS removal was observed in 6 d at 45 °C and initial pH of 3.4 whereas at 21 d, PFOS removal was reduced to \u3c ~5%. Furthermore, generation of F– and SO42– as products of PFOS transformation was not observed indicating that PFOS was not transformed. X-ray diffraction analysis (XRD) indicated that apparent PFOS removal with Pd0/nFe0 NPs was due to strong adsorption of PFOS (not extractable) onto Fe(OH)3 formed via nFe0 corrosion. Subsequently, PFOS was released through the conversion of Fe(OH) 3 to less sorptive FeO(OH) via Fe(II) catalyzed transformation. In the process of exploring the reasons for apparent PFOS removal with Pd 0/nFe0 NPs, PFOS as well as other PFAAs were found to form complexes with Fe(II/III) ions. Complexed PFOS was not detected for quantification by mass spectrometry (MS). In the VB12 with nZn0 systems, br- isomers of PFOS and PFHxS were successfully defluorinated. However, L-isomers were not altered; thus, limiting its usefulness for groundwater remediation given the dominance of L-isomer. As organic intermediates/products of br-PFOS and br-PFHxS defluorination, C8- and C7- based polyfluorinated sulfonates and C6- and C5- based polyfluorinated sulfonates were identified, respectively. Lastly, no PFOS removal was observed using PM-based technologies even with the use of Ru(III), NaHSO3, Fe(II), 2,2’-azino-bis(3-ethyl benzothiazoline)-6-sulfonate (ABTS), microsized zero valent metals: mMg0 and mFe0 to catalyze the reaction. None of the technologies explored were successful in transforming both L- and br- per/polyfluoroalkyl caboxylates and sulfonates that co-occur at most sites. However, this study has contributed to insight into the intermediates/products and defluorination pathways of br-PFOS and PFHxS which can be used to design other remediation strategies and to study fate and transport of them in environment mediums

Role of Borate Buffer in Organic Degradation by Peroxymonosulfate in the Presence of Metal Oxides

The effects of borate ions on the reactivity of peroxymonosulfate (PMS) during organic degradation in the presence of metal oxides were examined. The metal oxides exhibited catalytic abilities for the degradation of carbamazepine (CBZ) but not for phenol (PN). Scavenging experiments revealed the absence of radical generation during PN degradation in the presence of the various metal oxides and borate buffer. This indicated that the borate buffer hindered the catalytic abilities of the metal oxides for producing radicals via the PMS oxidant, especially during the faster degradation of compounds such as PN. Various concentrations of borate ions were assessed for enabling pH control and permitting catalytic activity. Fe2O3 was found to accelerate and inhibit PN degradation at borate-ion concentrations of 2 mM and 5–20 mM, respectively. Only the 20 mM borate-ion solutions were successful at maintaining the initial pH for 2 d. Phosphate buffer, which was examined as an alternative, also disrupted radical formation but not as considerably as that of the borate ions with metal oxides. This study demonstrates the significance of enabling pH control and permitting the catalytic activity for ensuring the effective use of oxyanions as buffers

Stability Analysis of Denoising Autoencoders Based on Dynamical Projection System

In this study, we give a stability analysis of denoising autoencoder(DAE) from the novel perspective of dynamical systems when the input density is defined as a distribution on a manifold. We demonstrate the connection between the corrupted distribution and the learned reconstruction function of a nonlinear DAE, which motivates the use of a dynamic projection system (DPS) associated with the learned reconstruction function. Utilizing the constructed DPS, we prove that the high-density region of the corrupted data distribution asymptotically converges to the data manifold. Then, we show that the region is the attracting stable equilibrium manifold of the DPS which is completely stable. These results serve a theoretical basis of the DAE in recognizing the high-density region of the highly corrupted data with large deviations through the DPS. The effectiveness of this analysis is verified by conducting experiments on several toy examples and real image datasets with various types of noise

기술자인가, 리더인가? CIO의 역할 변화에 대한 고찰

Information Technology (IT) has been changed over time. So has the role of Chief Information Officer (CIO) . Failures of IT after the dot-com bubble coupled with its seemingly disappointing outcomes resulted in CIO roles being hidden under a cloud. With little research done investigating their roles. however. CIOs are challenged to conform to the business environments under continuous transformation. Thus. to achieve better CIO performance, researchers as well as practitioners need to recognize their renewed leadership. First. we review leadership from general perspectives to ameliorate the understanding of leadership needed in the IT department. Second. we suggest a leadership role framework, viewing the CIO role as a leader in dynamic business environments. Last. using this framework. we analyze the stream of CIO leadership in connection with the historical perspectives . The framework will contribute to providing a guideline for continuous examination of CIO leadership role.2000년대 닷컴 버블의 붕괴와 함께 정보기술에 대한 투자비용에 비해 결과물이 명확 하지 않다는 지적들이 잇따라 나오면서 기업은 정보기술의 기능을 의심하기 시작하였다. 정보시스템의 투자위험성을 줄이고 이룰 보다 효율적으로 관리하기 위하여 고용한 최고 정보책임자(Chief Information Officer. CIO)의 역할과 리더십의 중요성 또한 점차 간과되어 최근에 들어서는 관련 연구가 미비한 실정이다. 본 논문에서는 기업 내 IT 환 경의 변화가 CIO의 역할에 영향을 미친다는 관점에 따라 리더십 역할과 환경과의 관계 를 나타낸 프레임워크를 제시하고, 이를 바탕으로 현재까지의 CIO 리더십 역할의 변화 를 탐색하였다. 첫째로. 문헌연구를 통해 리더에게 기대되는 다양한 역할을 리더십 역할 (Leadership Role)이라 정의하였다. 둘째로, 정보기술이 발전함에 따라 CIO가 이행해 야 하는 리더십 역할은 어떻게 바뀌는지를 체계적으로 알아보기 위해 리더십 역할 모델 (Leadership Role Model)을 구축하였다. 마지막으로. 위에서 제시한 모델을 바탕으로 정보시스템의 변천과정을 시계열적으로 분석하여. 각 시대마다 CIO에게 요구되는 리더 십역할은 어떤 것이 있는지 살펴보았다

Privacy-Preserving Fair Learning of Support Vector Machine with Homomorphic Encryption

Fair learning has received a lot of attention in recent years since machine learning models can be unfair in automated decision-making systems with respect to sensitive attributes such as gender, race, etc. However, to mitigate the discrimination on the sensitive attributes and train a fair model, most fair learning methods have required to get access to the sensitive attributes in training or validation phases. In this study, we propose a privacy-preserving training algorithm for a fair support vector machine classifier based on Homomorphic Encryption (HE), where the privacy of both sensitive information and model secrecy can be preserved. The expensive computational costs of HE can be significantly improved by protecting only the sensitive information, introducing refined formulation and low-rank approximation using shared eigenvectors. Through experiments on the synthetic and real-world data, we demonstrate the effectiveness of our algorithm in terms of accuracy and fairness and show that our method significantly outperforms other privacy-preserving solutions in terms of better trade-offs between accuracy and fairness. To the best of our knowledge, our algorithm is the first privacy-preserving fair learning algorithm using HE

Semi-supervised distributed representations of documents for sentiment analysis

Learning document representation is important in applying machine learning algorithms for sentiment analysis. Distributed representation learning models of words and documents, one of neural language models, have overcome some limits of vector space models such as bag-of-words model and have been utilized successively in many natural language processing tasks including sentiment analysis. However, because such models learn the embeddings only with a context-based objective, it is hard for embeddings to reflect the sentiment of texts. In this research, we address this problem by introducing a semi-supervised sentiment-discriminative objective using partial sentiment information of documents. Our method not only reflects the partial sentiment information, but also preserves local structures induced from original distributed representation learning objectives by considering only sentiment relationships between neighboring documents. Using real-world datasets, the proposed method has been validated by sentiment visualization and classification tasks. The visualization results of Amazon review datasets demonstrate the enhancement of the sentiment class separation when document representations of our proposed method are compared to other methods. Sentiment prediction from our representations also appears to be consistently superior to other representations in both Amazon and Yelp datasets. This work can be extended to develop effective document embeddings applied to other discriminative tasks. (C) 2019 Elsevier Ltd. All rights reserved