Browsing by Subject "Chemical reactions"

Now showing 1 - 7 of 7

Open Access
Application of the Ugi reaction with multiple amino acid-derived components: Synthesis and conformational evaluation of piperazine-based minimalist peptidomimetics
(Royal Society of Chemistry, 2015) Stucchi, M.; Cairati, S.; Cetin-Atalay, R.; Christodoulou, M.S.; Grazioso G.; Pescitelli G.; Silvani, A.; Yildirim, D.C.; Lesma G.
The concurrent employment of α-amino acid-derived chiral components such as aldehydes and α-isocyanoacetates, in a sequential Ugi reaction/cyclization two-step strategy, opens the door to the synthesis of three structurally distinct piperazine-based scaffolds, characterized by the presence of l-Ala and/or l-Phe-derived side chains and bearing appropriate functionalities to be easily applied in peptide chemistry. By means of computational studies, these scaffolds have been demonstrated to act as minimalist peptidomimetics, able to mimic a well defined range of peptide secondary structures and therefore potentially useful for the synthesis of small-molecule PPI modulators. Preliminary biological evaluation of two different resistant hepatocellular carcinoma cellular lines, for which differentiation versus resistance ability seem to be strongly correlated with well defined types of PPIs, has revealed a promising antiproliferative activity for selected compounds. © The Royal Society of Chemistry 2015.
Open Access
Aza-Nazarov cyclization reactions via anion exchange catalysis
(American Chemical Society, 2019) Dönmez, Selin E.; Soydaş, E.; Aydın, Gökçen; Şahin, O.; Bozkaya, U.; Türkmen, Yunus Emre
A catalytic aza-Nazarov cyclization between 3,4-dihydroisoquinolines and α,β-unsaturated acyl chlorides has been developed to access α-methylene-γ-lactam products in good yields (up to 79%) as single diastereomers. The reactions proceed efficiently when AgOTf is used as an anion exchange catalyst with a 20 mol % loading at 80 °C. Computational studies were performed to investigate the reaction mechanism, and the findings support the role of the −TMS group in reducing the reaction barrier of the key cyclization step.
Open Access
Intimate relationship between structural deformation and properties of single-walled carbon nanotubes
(Cambridge, 2002) Yıldırım, Taner; Gülseren, Oğuz; Çıracı, Salim
Carbon nanotubes continue to surprise scientists with their novel properties. Recently we have discovered many intimate relationships between structural deformation and the properties of single-walled nanotubes (SWNT), that could be important in technological applications. From first-principles we show that by using pressure, carbon nanotubes can be covalently joined to form one and two-dimensional networks of interlinked nanotubes. We also find that the band gap of an insulating nanotube can be engineered by elliptical distortion, which is found to be in the elastic range. This could allow the fine-tuning of the properties of SWNTs via reversible deformation and ultimately lead to variable quantum devices. Finally, we have very recently shown that the chemical reactivity of nanotubes can be tuned by elliptical deformation, which may provide a way to attach various atoms such as H and metals to a specific location on a nanotube.
Open Access
Modeling and cross coupling controller development for a 6DOF laser micro-machining system
(IEEE, 2017) Kerimoğlu, Serhat; Çakmakçı, Melih
In recent years, studies on manufacturing systems have proved the importance of cooperation of positioning systems with laser cutting technology. The performance of the manufacturing system can be improved by utilizing both laser and positioning systems together. In this study, modeling and cross coupling controller development of a micromachining system which can perform on non-linear contoured surfaces is presented. Laser micromachining system is designed and assembled including a nanosecond Q-switched pulsed fiber laser, a 6-DOF hexapod manipulator, a granite table in order to absorb vibrations and an external cabin system to isolate the whole system for safety and health issues. The positioning system used here has fast response and precise positioning capabilities with a wide range of workspace. However, its performance of machining non-linear surfaces can be further improved by using a cross coupled control algorithm. On top of the loop based controllers an add-on controller is developed to improve the contouring performance by including the effects of the other feedback loops on the overall controller. Actual laser cutting results also show improvements due to the improvements in the positioning system performance.
Open Access
On the possibility of grafting conducting polymers into insulating ones
(Elsevier, 1996) Bahçeci, S.; Toppare, L.; Yurtsever, E.
The possibility of grafting between conducting polymers, like polypyrrole (PPy) and polyaniline (PAn), and insulating polymers, such as polybisphenol A carbonate (PC) and polyamide (PA), is studied via semi-empirical methods using the AM1 parametrization. Several experimental studies on the issue have previously revealed that a chemical interaction exists between the couples (PAn-PC, PPy-PC and PPy-PA) during the electrochemical synthesis of PAn and PPy in the insulating host matrices. Here we present additional theoretical evidence indicating that such grafting is possible, at least for small oligomers.
Open Access
Rapid access to hydroxyfluoranthenes via a domino Suzuki–Miyaura/intramolecular Diels–Alder/ring-opening reactions sequence
(American Chemical Society, 2022-04-07) Ahmadli, Dilgam; Şahin, Yeşim; Çalıkyılmaz, Eylül; Şahin, Onur; Türkmen, Yunus E.
In this work, we developed an efficient method for the rapid construction of fluoranthene skeleton to access a variety of substituted hydroxyfluoranthenes. The 1-iodo-8-alkynylnaphthalene derivatives, which serve as substrates for the key fluoranthene-forming step, were prepared via selective monoalkynylative Sonogashira reactions of 1,8-diiodonaphthalene. The domino reaction sequence which involves a sequential Suzuki–Miyaura coupling, an intramolecular Diels–Alder reaction, and an aromatization-driven ring-opening isomerization has been shown to give substituted hydroxyfluoranthenes in up to 92% yield. This work demonstrates the utility of designing new domino reactions for rapid access to substituted polycyclic aromatic hydrocarbons (PAHs).
Open Access
Studies directed toward the synthesis of aspidophytine: construction of its perhydroquinoline core
(American Chemical Society, 2016) Türkmen, Y. E.; Gravel, M.; Rawal, V. H.
We have developed an efficient route for the synthesis of the perhydroquinoline core of the indole alkaloid aspidophytine (2), starting from commercially available and inexpensive 3-acetylpyridine. This densely functionalized perhydroquinoline core displays four contiguous stereocenters including an all-carbon quaternary center. The synthetic sequence features a highly effective Diels-Alder reaction using a carbamate-substituted siloxy diene accompanied by a spontaneous intramolecular substitution of the newly formed 3°-alkyl bromide with a carbamate group. The installation of the electron-rich aniline moiety was accomplished via a TBSOTf-mediated intramolecular aza-Michael reaction, and the relative stereochemistry of the aza-Michael product (30) was confirmed by X-ray crystallographic analysis. Among the useful transformations that were developed through this study is a highly enantioselective Diels-Alder reaction of a versatile cyclic carbamate siloxy diene.