Prof. Dr. Hamit Alyar danışmanlığındaki tezler
13 tez · Çankırı Karatekin Üniversitesi
Theoretical investigation of spectroscopic and some electronic properties of (E)-4-((P-tolylimino) methyl) phenyl acrylate Schiff base by DFT method
Schiff bases; They are compounds that have importance in various branches such as pharmacy, medicine, biological systems, cosmetics, agriculture, production of dyes, plastics industry, aircraft industry, liquid crystal technology, electronics industry and analytical chemistry. The present study aims to theoretically investigate the spectroscopic and electronic properties of (E)-4-((P-tolylimino) methyl) phenyl acrylate Schiff base using the Density Functional Theory (DFT) method. The structure of Schiff base molecule was theoretically elucidated by FT-IR and NMR spectroscopy. The molecular geometry of the Schiff base was drawn with the Gauss View 5.0 program and its structure was optimized using the B3LYP/6-311++G(d,p) theory level DFT method. After the optimization calculation, the harmonic frequency calculation was made and it was understood that the molecule was in a stable structure since no negative frequency was observed as a result of the calculation. Since the studied Schiff base does not have crystal data in the literature, it was compared with the structural parameters of similar molecules and it was seen that the results were compatible with the experimental data. The vibration frequencies were marked and it was seen that the calculated theoretical frequency values were in good agreement with the experimental spectra. The calculated NMR chemical shifts were also found to be in good agreement with the experimental values. Also, nonlinear optical (NLO) properties of Schiff base with HOMO-LUMO molecular orbital energies were calculated and found to have significant NLO activity.
Investigation of spectroscopic and some electronic properties of (E)-4-((4-chlorophenylimino)methyl)phenyl acrylate Schiff base by DFT method
Schiff bases (imines) are among the first compounds of interest because they are stable and easily synthesized. This interest in Schiff bases can be explained by the fact that they can be used in many biological systems, chemical catalysis, medicine and pharmacy, chemical analysis and new technologies. This study aims to theoretically investigate the spectroscopic and electronic properties of (E)-4-((4-chlorophenylimino)methyl)phenyl acrylate Schiff base using density functional theory (DFT) and the 6-311++G(d,p) basis set. . The structure of the Schiff base compound was theoretically elucidated by FT-IR, 1H-NMR and 13C-NMR spectroscopy. The structure of the compound was optimized at the B3LYP/6-311++G(d,p) theory level. After the optimization calculation, the harmonic frequency calculation was made and it was understood that the molecule was in a stable structure since no negative frequency was observed as a result of the calculation. Since the (E)-4-((4-chlorophenylimino)methyl)phenyl acrylate Schiff base does not have crystal data in the literature, it was compared with the structural parameters of similar molecules and it was seen that the results were compatible with the experimental data. The vibration frequencies were marked and it was seen that the calculated theoretical frequency values were in good agreement with the experimental spectra. The calculated NMR chemical shifts were also found to be in good agreement with the experimental values. Also, nonlinear optical (NLO) properties of Schiff base with HOMO-LUMO molecular orbital energies were calculated and found to have significant NLO activity. Finally, the molecular electrostatic potential (MEP) analysis was performed to study the reactivity and potential sites of electrophilic and nucleophilic attacks. The results of this study provide valuable insights into the spectroscopic and electronic properties of the (E)- 4-((4-chlorophenylimino)methyl)phenyl acrylate Schiff base and could be useful in designing novel organic materials with promising optical and electronic properties.
(E)-4-((P-tolilimino)metil)fenol Schiff bazının spektroskopik ve bazı elektronik özelliklerinin DFT metoduyla incelenmesi
Schiff' bazı primer aminlerdeki nitrojen atomunun çeşitli aldehit veya ketonlardaki karbonil grubu ile birleşerek azometin grubunu oluşturmasından oluşan organik bir bileşiktir. Schiff bazlarının ve metal komplekslerinin kullanım sahası oldukça geniştir. Schiff bazları; eczacılıkta, tıpta, biyolojik sistemlerde, kozmetikte, tarım alanında, boyar maddelerin üretiminde, plastik sanayisinde, uçak sanayisinde, sıvı kristal teknolojisinde, elektronik endüstrisinde ve analitik kimya gibi çeşitli dallarda öneme sahip bileşiklerdir. Bu bileşiklerin sentetik oksijen taşıyıcı, enzimatik reaksiyonlarda ara ürün oluşturucu, antitümör etkisi gibi özeliklerinin yanında bazı metal iyonlarına karşı seçici ve spesifik reaksiyon vererek spektrofotometrik reaktif olarak analitik kimyada kullanımları da önem taşımaktadır. Schiff Bazları genelde renkli katılardır. Bu özelliklerinden yararlanılarak boya endüstrisinde de oldukça fazla kullanılabilmektedir. Bunların dışında elektronik gösteri sistemleri içinde sıvı kristal olarak ve polimer oluşumunu hızlandırıcı olarak da kullanılabilmektedir. Bu çalışma, (E)- 4 - ((p-tolilimino)metil )fenol Schiff bazının spektroskopik ve elektronik özelliklerini yoğunluk fonksiyonel teorisi (DFT) ve 6-311++G(d,p) temel seti kullanarak teorik olarak incelemeyi amaçlamaktadır. Schiff bazı bileşiğinin yapısı FT-IR,1H-NMR ve 13C- NMR spektroskopisi ile teorik olarak aydınlatıldı. Bileşiğin yapısı B3LYP/6-311++G(d,p) teori düzeyinde optimize edildi. Optimizasyon hesabından sonra harmonik frekans hesabı yapıldı ve hesaplama sonucunda negatif frekans görülmediği için molekülün kararlı yapıda olduğu anlaşıldı. (E)- 4 - ((p-tolilimino)metil )fenol Schiff bazının literatürde kristal verileri olmadığı için benzer moleküllerin yapısal parametreleri ile karşılaştırılması yapıldı ve deneysel verilerle uyumlu sonuçlar elde edildiği görüldü. Titreşim frekanslarının işaretlemeleri yapıldı ve hesaplanan teorik frekans değerlerinin deneysel spektrumla iyi bir uyum içinde olduğu görüldü. Hesaplanan NMR kimyasal kaymalarının da deneysel değerlerle iyi bir uyum içinde olduğu bulundu. Ayrıca, Schiff bazının HOMO-LUMO moleküler orbital enerjileri ile doğrusal olmayan optik (NLO) özellikleri hesaplandı ve önemli ölçüde NLO aktivitesine sahip olduğu bulundu. Son olarak, elektrofilik ve nükleofilik saldırıların reaktivitesini ve potansiyel bölgelerini incelemek için moleküler elektrostatik potansiyel (MEP) analizi yapıldı. Bu çalışmanın sonuçları, (E)- 4 - ((p-tolilimino)metil )fenol Schiff bazının spektroskopik ve elektronik özelliklerine ilişkin değerli bilgiler sağlar ve gelecek vaat eden optik ve elektronik özelliklere sahip yeni organik materyallerin tasarlanmasında faydalı olabilir.
(3-aminometilpiridin)-salisiliden Schiff bazının spektroskopik ve bazı elektronik özelliklerinin DFT metoduyla incelenmesi
Bu tez çalışmasıda, (3-aminometilpiridin)-salisiliden Schiff bazı molekülünün yapısal, spektroskopik ve elektronik özellikleri B3LYP/6-311G++(d,p) düzeyinde Yoğunluk Fonksiyonel Teorisi (DFT) kullanarak incelendi. Moleküler geometri, bağ uzunlukları, titreşim modları ve elektronik özelliklere ilişkin teorik öngörüler, özellikle heteroatomik bağları içeren karmaşık yapıların modellenmesinde, deneysel verilerle güçlü bir uyum göstermektedir. Titreşimsel analiz, FT-IR spektrumunda temel fonksiyonel gruplara karşılık gelen pikler belirlemiş ve teorik frekansların deneysel değerlerle yakından örtüştüğü ortaya konulmuştur. NMR analizi, sübstitüentlerin ve elektronik etkilerin vurgulandığı detaylı kimyasal kayma verileri sağlayarak deneysel bulgularla uyum göstermektedir. HOMO-LUMO analizi, büyük bir enerji aralığını (4,9353 eV) ortaya koyarak yüksek kararlılık ve orta düzeyde reaktiviteye işaret etmektedir. İyonizasyon potansiyeli ve kimyasal sertlik gibi elektronik tanımlayıcılar, molekülün elektron kaybına karşı direncini ve orta dereceli elektrofilik doğasını doğrulamaktadır. Doğrusal olmayan optik (NLO) özellikler, polarizabilite ve hiperpolarizabilite ile değerlendirilmiş ve çalışılan molekül üre gibi referans malzemelere kıyasla yüksek çizgisel olmayan optik özellik gösterdiği saptanmıştır. Moleküler elektrostatik potansiyel (MEP) haritası, oksijen ve azot atomlarının elektrofilik merkezler, hidrojen atomlarının ise nükleofilik bölgeler olarak öne çıktığı reaktif bölgeleri vurgulamaktadır. Bu bulgular, Schiff bazı moleküllerinin karakterizasyonunda DFT yöntemlerinin doğruluğunu teyit etmektedir. Ayrıca, teorik ve deneysel yaklaşımları birleştirerek bu moleküllerin optoelektronik, doğrusal olmayan optik ve biyokimya alanlarındaki potansiyelini vurgulamakta ve ileri uygulamalar için yeni fırsatlar sunmaktadır.
Güneş pili uygulamaları için pencere katmanı olarak cu katkılı nano yapılı znxcd1-X S filmlerin üretimi
Bu çalışmada, ZnxCd1-xS ve ZnxCd1-xS: 0,3 Cu filmleri x=0, 0,3, 0,5, 0,7,1 325ºC sıcaklıkta cam altlıklar üzerinde kimyasal sprey piroliz tekniği (CSPT) kullanılarak hazırlanmıştır. X-ışını kırınımı (XRD) sonuçları, hazırlanan tüm filmlerin polikristal bir yapıya sahip olduğunu göstermiştir. "x" değeri 0,1'den 0,9'a yükseldikçe, Zn iyonlarının CdS kafesine bağlanması nedeniyle yoğunluk daha yüksek açılara doğru hafif bir kayma ile azalmaktadır. Bakır katkı işlemi, yoğunlukta bir azalmaya ve (FWHM)'de bir artışa yol açmış, bu da kristal boyutunda bir azalmaya neden olmuştur. (ZnxCd1-xS: 0,3 Cu) filmlerinin atomik kuvvet mikroskobu (AFM) görüntülerinin sonuçları, hazırlanan filmlerin iyi bir homojenliğe sahip olduğunu, filmin alt tabaka üzerinde iyi dağıldığını ve tüm filmlerde çatlak bulunmadığını göstermiştir. Tane boyutu artan (x) değeri ile azalmıştır. Taramalı mikroskop görüntüleri, partiküllerin nanopartikül boyutunda küresel bir şekle sahip olduğunu ve alt tabaka yüzeyinde neredeyse benzer ve iyi dağılmış olduğunu göstermektedir. Partikül boyutu artan (x) değeri ile azalmaktadır. EDX sonuçları kadmiyum (Cd), çinko (Zn), sülfür (S) ve bakırın (Cu) varlığını doğrulamıştır. Optik özelliklerin sonuçlarından, hazırlanan çözeltideki çinko (Zn) içeriğinin yüzdesindeki artış nedeniyle (x) değerindeki artışla geçirgenliğin arttığını, bunun da filmlerin kalınlığında bir azalmaya ve dolayısıyla filmlerin şeffaflığında bir artışa yol açtığını not ediyoruz. Optik enerji aralığı, hazırlanan çözeltideki çinko konsantrasyonunun artmasıyla artmaktadır. Elektriksel özellik sonuçları, tüm filmlerin negatif (n-tipi) iletkenlik sergilediğini ve hazırlanan filmlerin iki aktivasyon enerjisine sahip olduğunu ve çinko çözeltisinin konsantrasyonu arttıkça, hazırlanan filmlerdeki direncin arttığını ve iletkenliğin azaldığını göstermiştir. Yukarıda bahsedilen sonuçlara dayanarak, hazırlanan filmlerin güneş pillerinde pencere olarak kullanılabileceği düşünülmektedir.
Investigation of spectroscopic and electronic properties of some schiff basesderived from 2-hydroxy-3-methoxy-5-nitrobenzaldehyde by DFT method
In this study, the theoretical spectroscopic properties of MMP and FMP compounds were investigated and the obtained theoretical results were compared with some experimental values. For this purpose, firstly, MMP and FMP compouns were optimized by DFT method using the B3LYP functional and the 6-311G++(d,p) basis set. With the help of the optimized structure obtained, the chemical shift values of H- NMR and 13C-NMR were calculated in the gas phase by the Gaussian G09 (Linux) and Gauss View 5.0 programs according to the GIAO method. According to the results obtained, it was seen that the theoretical values were compatible with the experimental values. In the theoretical part of the study, the IR frequency values of the studied compounds were calculated using the same method and basis set, and vibration frequencies were marked. Finally, the nonlinear optical properties of the compounds of interest; Polarizability and hyperpolarizability values were calculated by making polar calculations in the single point energy calculation. As a result of the calculations, the energy band gaps between the HOMO and LUMO orbitals of MMP and FMP are 1.34 eV and 3.64 eV. First static hyperpolarizability of MMP and FMP were found as 29273.7 x10-33 and 26500.5 x10-33 esu, repectively.
Illumination of the structures of some sulfonamide compounds with biological activity by spectroscopic methods and investigation of their physical properties by DFT method
Sulfonamides are synthetic antibacterial compounds and broad-spectrum drugs that are active against various types of bacteria, generally gram-positive and gram-negative. With the widespread use of sulfonamides immediately after their discovery, a significant reduction in diseases caused by bacteria has been observed. In this study, the chemical structure of 2,4-dihydroxybenzaldehyde Sulfisoxazole Schiff base (S2M-S3) was tried to be elucidated by 1H-NMR, 13C-NMR and FT-IR spectroscopic methods. As a result of the vibration frequencies, 1H-NMR and 13C-NMR calculations, it was seen that the theoretical values were compatible with the experimental values. In addition, HOMO-LUMO molecular orbital energies, nonlinear optical properties such as polarizability, hyper polarizability (NLO) and molecular electrostatic potential (MESP) of S2M-S3, Cu (S2M-S3)2 and Pd (S2M-S3)2 compounds were investigated. As a result of the geometry optimization calculation, S=O and S-N bond lengths were obtained slightly longer than the results found in previous studies. The N-H bond length is in agreement with previous studies. In the calculations, the energy band gap between the HOMO and LUMO orbitals of the S2M-S3 compound was 4.09 eV and the initial static hyperpolarizability was 27677.7×10-33 esu. Keywords: FT-IR, NMR, NLO, DFT, HOMO, LUMO
Theoretical investigation of the spectroscopic, electronic and drug-free properties of 4-((6,7- dihidroksi-2-okso-2H-kromen-4-IL) metilamino)-N (3.4-dimetiloksiazol-5- IL) benzenesulfonamide compound
Sulfonamides or "sulfa drugs" are a group of drugs used to treat bacterial infections. They may be prescribed to treat urinary tract infections, bronchitis, eye infections, bacterial meningitis, pneumonia, ear infections, severe burns, traveler's diarrhea, and other conditions. In this thesis, it was first determined that 4- ((6,7-dihydroxy-2-oxo-2H-chromen-4-yl) methylamino) -N-(3,4-dimethyloxoazol-5-yl) benzenesulfonamide compound synthesized by Şeref Karadeniz. Stable structure was obtained by performing geometry optimization calculation and bond lengths, bond angles and torsion angles were determined. These structural parameters were compared with similar molecules found in the literature. Then, its spectroscopic properties such as FT-IR, 1H-NMR and 13C-NMR were calculated theoretically. The vibrational frequencies of the compound were assigned. The calculated theoretical results were compared with the experimental data. Finally, the electronic energies, dipole moments, highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energies, polarizability and hyperpolarizability values, molecular potential energy surface (MEP) of the studied compound were calculated and it was determined whether it exhibits drug properties in ADME work was carried out. Keywords: FT-IR, NMR, NLO, DFT, HOMO-LOMO, ADME
Theoretical investigation of the spectroscopic, electronic and drug-free properties of 4-((6,7-dihydroxy-2-oxo-2H-chromene-4-YL)methylamino) benzenesulfonamide compound
Sulfonamides are a prominent pharmacological family that has seen considerable usage in human and animal medicine due to their overall stability, bioavailability, and ease of production. In this study, first of all, the structural parameters of the 4-((6,7-dihydroxy-2-oxo-2H-chromen-4-yl) methylamino) benzenesulfonamide compound synthesized by Şeref Karadeniz were determined by optimization calculation. Then, HOMO-LUMO molecular orbital energies were calculated with their spectroscopic properties such as 1H-NMR, 13C-NMR, FT-IR. Finally, the nonlinear optical property (NLO) and molecular potential energy surface (MEP) of the compound were calculated and the ADME study was carried out to determine whether it showed drug properties. As a result, it was found that the experimental spectroscopic values and the calculation results were compatible with each other. With NLO and ADME studies, it was determined that the studied molecule showed nonlinear optical activity and drug properties. Calculations were performed with the DFT/B3LYP method and using the 6-311++ g (d, p) basis set. Keywords: FT-IR, NMR, NLO, DFT, HOMO- LUMO, ADME
Investigation of spectroscopic and nonlinear optical (NLO) properties of N2 ,N6 -BIS-[4-(aminosulfonyl) phenyl]-pyridine-2,6-dicarboxamide by DFT method
Sulfonamides are organic sulfur compounds containing -SO2NH2 group, and they are compounds with antimicrobial activity and antibacterial activity that prevent the growth of bacteria. The discovery of sulfonamides is an important milestone in human chemotherapeutic history. In 1935, it was found that the dye prontosil was metabolized in vivo to an active compound, sulfanilamide, and this active compound prevented streptococcal infections in mice. In this thesis, the stable structure of N2 ,N6 -bis-[4-(aminosulfonyl)phenyl]-pyridine-2,6-dicarboxamide compound synthesized by Adem Rıza BAYKAN was obtained by DFT method by performing geometry optimization calculation at B3LYP/6-311++G(d,p) level. Since the molecule studied in the literature has no experimental structural parameters, the theoretically calculated bond lengths and bond angles of the compound were compared with the experimental values of similar molecules in the literature. Especially S-O, S-N and N-C bond lengths were calculated as 1.461, 1.695 and 1.382 Ȧ, and it was seen that the calculated results were compatible with the experimental values in the literature. In addition, the spectroscopic properties of the molecule such as FT-IR, 1H-NMR and 13C-NMR were calculated with the same method and basis set. In the obtained FT-IR analysis results, it is seen that the values of 1263 and 1261 cm-1 calculated for the C-N stretching vibration coincide with the values of similar molecular groups in the literature. Finally, the HOMO and LUMO energies of the molecule at the B3LYP/6-311++G(d,p) level were calculated by the DFT method. The obtained HOMO and LUMO energy difference was found to be 4.685 eV. The nonlinear optical properties and molecular potential energy surface map of the studied iicompound were calculated using the same method and basis set. As a result of calculation, the compound was found to have a hyperpolarizability of 2665.2x10-33 esu. This value indicates that the hyperpolarizability of the compound is approximately 7.15 times greater than that of urea. In this thesis study, all calculations were performed with Gaussian 09 (Linux) and Gauss View 5.0 package programs.
Investigation of spectroscopic and electronic properties of N,N'-pentamethylenebis(p-toluenesulfonamide) (PTSPEN) by DFT method
Sulfonamides are synthetic antibacterial chemicals and broad-spectrum antibiotics that are effective against a variety of bacteria, primarily gram-positive and gram negative bacteria. This resulted in a substantial decline in bacterial-based disorders. Diseases that spread throughout the body are often treated with sulfonamides. In this work, the chemical structure of N,N'-pentamethylenebis(p-toluenesulfonamide) (ptspen) schiff base was determined using FT-IR, 1H-NMR and 13C-NMR spectroscopic methods by theoretically. Based on the calculations for vibration frequencies, 1H-NMR, and 13C-NMR, it was evident that the theoretical values and actual values were comparable. HOMO-LUMO molecular orbital energies, nonlinear optical characteristics such as polarizability, hyper polarizability (NLO), and molecular electrostatic potential (MESP) of N,N'-pentamethylenebis(p toluenesulfonamide) (ptspen) compound were also investigated. The total first static hyperpolarizability value of the studied compound is approximately 4.14 times greater than that of urea (1543.8x10-33 esu). This result showed us that the compound has small nonlinear optical activity. In this study, all calculations were performed with the DFT/B3LYP/6-311++G (d, p) level of theory in conjunction with the Gaussian 09 and Gauss View 5.0 package programs.
Investigation of spectroscopic and electronic properties of 2-hydroxyacetophenone methanesulfonylhydrazone by DFT method
In this thesis, quantum chemical calculations of the 2-hydroxyacetophenone methanesulfonylhydrazone sulfonamide compound, which was previously synthesized by Saliha Alyar, were made. First of all, the minimum energy structure of this compound, which has seven different conformations, was selected and its structure was optimized by the DFT B3LP/6-311++g (d, p) method. Then, the spectroscopic (such as 1H-NMR, 13C-NMR and FT-IR) and electronic properties of 2-hydroxyacetophenone methanesulfonylhydrazone were theoretically investigated. As a result of the calculations of the vibration frequencies of the studied compound, it has been seen that the theoretical values are compatible with the experimental values. In addition, HOMO LUMO molecular orbital energies, nonlinear optical (NLO) properties (such as polarizability, first hyperpolarizability) and molecular electrostatic potential (MESP) of 2-hydroxyacetophenone methanesulfonylhydrazone were investigated. As a result of the calculations, the energy band gap between the HOMO and LUMO orbitals of the investigated compound was 4.65 eV and the first static hyperpolarizability was 4674.7*10-33esu (approximately 12.34 times larger than urea). All calculations were made using DFT/B3LYP/6-311++G (d, p) theory level and Gaussian 09, Gauss View 5.0 package programs.
Investigation of spectroscopic and electronic properties of N,N'- diethylenebis (o-toluenesulfonamide) (otsen) by DFT method
Sulfonamides are synthetic antibacterial chemicals and broad-spectrum medications that are typically effective against both gram-positive and gram-negative bacteria. Sulfonamides are often used to treat infectious illnesses. The chemical structure of N,N'- diethylenebis (o-toluenesulfonamide) (otsen) was investigated using 1H-NMR, 13C-NMR, and FT-IR spectroscopic techniques in this work. As a consequence of the vibration frequency, 1H-NMR, and 13C-NMR calculations, it was determined that the theoretical and experimental values were consistent. In addition, HOMO-LUMO molecular orbital energies, nonlinear optical characteristics including polarizability, hyperpolarizability (NLO), and molecular electrostatic potential (MESP) of N,N'- diethylenebis (o-toluenesulfonamide) (otsen)) were studied. As a consequence of the geometry optimization computation, the S=O and S-N bond lengths were determined to be somewhat longer than those observed in prior research. Calculations determined that the energy band gap between the HOMO and LUMO orbitals of the studied compound was 5.56 eV and the initial static hyperpolarizability was 2228.1x10-33esu. All calculations were carried out with the DFT/B3LYP/6-311++G (d, p) level of theory and the Gaussian 09(Linux) and Gauss View 5.0 package programs.