Porfirazin esaslı süpramoleküler yapılar

Porphyrins, phthalocyanines, tetrabenzo porphyrins and porphyrazines which are tetrapyrrole derivatives. Because of both theoretical studies and applications in advanced materials science, tetrapyrrole derivatives receive extensive attention. Porphyrins are important not only from biological aspect but also for coordination chemistry as catalysis and material science. Phthalocyanines which are used in electro-photography, optic data collection, gas sensor, liquid crystal, laser technology and the photodynamic therapy of tumors as well as their classical fields as pigments and dyes, are completely synthetic materials. Porphyrazines that have functionalized groups at pheripheral positions have the potential to exhibit novel optical, magnetic and electronic properties. They also maintain some additional features superior to the values met in related materials. Additions of the transition metal ion in the inner core of a porphyrazine offer new ways to induce, modify and control molecular properties. The starting point for a novel porphyrazine structure with eight (1-naphthyl) groups bound to the periphery is 1,2-bi ( naphthyl )dinitrile which was obtained by oxidative coupling of 1-naphthylacetonitrile in the presence of I2. The solid product was obtained in a yield of 21%. It was a mixture of maleo-and fumaro-nitriles and the latter was present in higher ratio as expected from the presence of bulky naphthyl substituents. The mixture of maleo-and fumaro-nitrile reluctance to turn into porphyrazine under the usual conditions (i.e. Mg(OR)2 in refluxing propanol or butanol) points out the lower ratio of the maleonitrile component. This problem was solved by activation of the fumaronitrile derivative to the corresponding pyrroline derivative 3,4-(1-naphthyl)pyrroline-2,5-diimine which cyclizes quite easily to porphyrazine at reflux temperature of propanol or butanol. Conversion of 3,4-(1-naphthyl)pyrroline-2,5-diimine into porphyrazine was achieved by the template effect of magnesium butanolate. Cyclotetramerization gave green-colored octakis(1-naphthyl) porphyrazinato magnesium in yield (70%). It is soluble in chloroform, dichloromethane and acetone, but insoluble in apolar hydrocarbon solvents such as n-hexane. Intensive research interest on peripherally functionalized porphyra-zines during the last decade has shown that these tetrapyrrol derivatives should be considered in many respects as an alternative to phthalocyanines. The porphyrazine macrocycles afford a skilful platform to build up detailed molecular superstructures and this property coupled with a full and well-improved synthetic chemistry has surpassed to the synthesis of different catalytically essential metallo porphyrazines and original model compounds of various functions. In this study magnesium porphyrazinate substituted with eight (1-naphthyl) groups on the peripheral positions has been synthesized by cyclotetramerization of 3, 4-(1-naphthyl)pyrroline-2,5-diimine in the presence of magnesium butanolate. Its demetallation by treatment with trifluoroacetic acid result with a partially oxidized product, namely, octakis(1-naphthyl)-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper(II) acetate, zinc (II) acetate and cobalt (II) acetate led to the metallo derivatives, [octakis (1-naphthyl)-2-seco-2, 3-dioxoporphyrazinato]M (II) (M= Cu, Zn, Co). These new compounds have been characterized by elemental analysis, together with FT-IR, 1H NMR, UV-Vis and mass spectral data. Since naphthyl groups are comparable with dimethylamino groups as electron donors to 18-  electron system of the inner core , in the demetallation reaction, relatively strong acids (e.g. trifluoroacetic acid) inhibits the electron donating strength of the dimethylamino groups much more than naphthyls. Sterical tension due to the presence of eight bulky naphthalene units around the core might be another reason for the cleavage of one of pyrrol rings. These should be taken together with the oxidation resulting from singlet oxygen cycloaddition reactions as described in early works. The presence of an electron donating group on the periphery causes a bathochromic shift on Q bands. UV-Vis spectra of porphyrazines (1, 3-5 in CHCl3) prepared in the present work exhibited intense single Q band absorption of the   transitions around 632-644 nm and B bands in the UV region around 340-348 nm.For metal-free derivative (2), Q band is split into two peaks at 620 and 676 nm as a consequence of the lowering of the symmetry of porphyrazine core. In conclusion, new seco-porphyrazines with eight naphthyl groups have been described; Together with their high electron donating property, steric requirements of the eight bulky naphthyl substituents can be the reasons leading to oxidized seco-porphyrazines. Keywords: Seco-porphyrazine, porphyrazine, pyrroline, copper, zinc, cobalt. Porfirinler, ftalosiyaninler, tetrabenzo-porfirinler ve porfirazinler tetrapirol türevleridir. Bu yapılar, son yıllarda hem temel bilim hem de uygulamalı çalışmalar için üzerinde önemle durulan konulardan birini oluşturmaktadır. Porfirinler sadece biyoloji açısından önem taşımakla kalmayıp zengin koordinasyon kimyası, kataliz ve malzeme bilimindeki uygulamaları ile de ilgi çekmektedir. Ftalosiyaninler, tamamen sentetik ürünlerdir. Bunların boyar madde ve pigment olarak değerlendirilmesi yanında enerji dönüşümü, elektrofotografi, optik veri toplanması, gaz sensör, sıvı kristal, lazer teknolojisi için kızılötesi boyar madde ve tek boyutlu metaller gibi pek çok uygulaması bulunmaktadır. Fonksiyonel substitüent taşıyan porfirazinler üzerinde yoğun çalışmalar yapılmaktadır. Bu tetrapirol türevlerinin birçok açıdan fitalosiyaninlere alternatif olabileceği düşünülmektedir. Porfirazinlerin makrohalkaları oldukça işlevsel makro moleküllerin oluşturulmasını sağlar. Bu tür makrohalkalı bileşikler, biyolojik etkileri nedeniyle, oldukça önemli bileşiklerdir. Halka üyesi olarak azot, kükürt ve oksijen gibi atomları içeren heterohalkalı bileşikler hem endüstrinin çeşitli alanlarında hem de tıpta yaygın bir şekilde kullanılmaktadırlar. Bu çalışmada peripheral konumlarında sekiz adet naftil grubu bulunan magnezyum forfirazin 3,4-(1-naftil)pirolin-2,5-diimin’nin magnezyum butanolat mevcudiyetinde halkalaşması sonucu elde edilmiştir. Bu madde trifloroasetik asit ile işleme tabi tuturak metalsizleştirilmiştir. İşlem sonucunda kısmi oksitlenmiş bir bileşik olan oktakis(1-naftil)-2-seko-porfirazin-2,3-dion’un oluştuğu belirlenmiştir. Metalsiz seko-porfirazinin bakır(II) asetat, çinko(II) asetat ve kobalt(II) asetat ile reaksiyonundan metalli türevleri olan [oktakis(1-naftil)-2-seko-2,3-dioksopor-firazinat]M(II) bileşikleri elde edilmiştir (M=Cu, Zn, Co). Oluşturulan yeni bileşikler FT-IR, 1H NMR, UV-Vis ve kütle spektrumları alınarak elementel analizleri yapılarak karakterize edilmiştir. Anahtar Kelimeler: Seko-porfirazin, porfirazin, pirolin, bakır, çinko, kobalt

Parental attitudes in children with persistent developmental stuttering: a case-control study

Background: Clinical experiences emphasize the possible role of parental attitudes and behaviours in shaping stuttering behaviors however, the number of studies in this area is still insufficient. Objective: Our aims were to compare parental attitudes in children with and without stuttering and to determine the effect of parental attitudes on stuttering severity. Methods: We used an age and gender matched case control design with 24 children with stuttering and 22 healthy school children. Demographic information form and Parental Attitude Research Instrument (PARI) were enrolled by the mothers. Results: According to our results; there was a statistically significant difference in parental attitudes of children with and without stuttering. Our results showed that excessive maternal control of the child and the expectations of obedience from the child more frequently observed in parents of the children with stuttering. Also there was a significant positive correlation with the severity of stuttering and excessive maternal control of the child, the expectations of obedience from the child and marital conflict. Discussion: In conclusion, there was an important difference in parental styles of study group and this difference was related to the severity of stuttering. Clinicans should address parental attitudes in this samples

Mirtazapine-Related manic / hypomanic shift: Mini review and case report

Mirtazapine-related manic / hypomanic shift: mini review and case report Mirtazapine is a pharmacological agent frequently used both as an antidepressant and as a hypnotic sedative agent. However, manic shift, an important side effect of other antidepressants, has not been adequately addressed in the treatment of mirtazapine, and the evidence has been only available from case reports. This mini-review and case report aimed to compile case reports on mirtazapine related manic shifts and to report a case where a manic shift was determined relatively early compared to that in these cases

Cleft lip and cleft palate: a disease with multiple risk factors in a pregnant woman

Clefts of the lip and/or palate (CLP) are currently the most common craniofacial birth defects that arise as a result of failure of facial embryonic processes to fuse. CLP etiology, which involves both genetic and environmental factors, is highly complex; its molecular basis remains largely unknown. In the current study we present a case report of a woman with prenatal diagnosis of cleft lip and palate, who had multiple risk factors including genetics, advanced age, family history, antiepileptic drug usage, consanguineous marriage and smoking. Her previous child was born with CLP, and this also contributes. Data of our study supports the hypothesis of a multifactorial etiology for CLP

A study on improving of lamb yield by three lambing in two years in Awassi sheep

İvesi koyunlarında iki yılda üç kuzulatma uygulamasının döl verim ölçütleri üzerine etkilerinin araştırıldığı bu çalışma, Mustafa Kemal Üniversitesi Ziraat Fakültesi Araştırma ve Uygulama Çiftliği Selam Hayvancılık İşletmesinde yürütülmüştür. Çalışmada 3 yaşlı İvesi koyunları iki yılda üç kuzulatma (İYÜK) ve yılda tek kuzulatma (YTK) olarak iki gruba ayrılmıştır. İYÜK grubunda çiftleştirmeler Ocak, Eylül ve Mayıs aylarında yapılmıştır. Ocak ve Mayıs çiftleştirmelerinde kızgınlık oluşturmak için progesteron içeren süngerler 14 gün süreli ve intra-vaginal olarak uygulanmış, süngerlerin alınmasını takiben hayvan başına 500 IU PMSG enjeksiyonu yapılmıştır. Eylül ayı İvesi koyunlarının doğal çiftleştirme mevsimi içerisinde yer aldığı için, İYÜK grubu koyunlarına bu ayda, sadece kızgınlık toplulaştırmak amacı ile progesteron içeren süngerler uygulanmıştır. YTK grubunda ise herhangi bir hormon uygulanmaksızın Ağustos- Eylül döneminde serbest koç katımı yapılmıştır. Deneme sonucunda yılda koç altı koyun başına kuzu verimi İYÜK grubunda YTK grubundan %39.4 daha fazla olmuştur. İYÜK grubu içerisinde en yüksek kuzulama oranı ve kuzu verimi Eylül ayındaki çiftleştirmeden elde edilirken, bu dönemin kuzuları tüm deneme grupları içerisinde en düşük doğum ağırlığına sahip olmuşlardır.This study was carried out at Animal Production Unit of Mustafa Kemal University Agriculture Faculty Research and Training Farm aiming to investigate the effects of three lambing in two years on reproductive characteristics. Awassi sheep of three years old were assigned into two groups as three lambing in two years (TLTY) and once lambing in one year (OLOY). Ewes of TLTY were mated on January, September and May. Progesterone-sponges were applied for 14 days intra-vaginally on the mating periods in TLTY group. After withdrawing of the sponges 500 iu/head of PMSG was injected to ewes except the September mating. For September mating ewes were applied the sponges only for oestrus synchronisation. It is known that September is the natural mating season for Awassi sheep. On the other hand, the OLOY group were mated from the beginning of August to the end September without any hormone treatment. It was found that litter size of TLTY was 39.4% of higher than that of OLOY group. The highest fertility and litter size were obtained for TLTY group in September mating while the birth weight was lowest in this period among the groups

SPATIAL DEVELOPMENT, LOCATION AND CLUSTERING POTENTIAL OF FOREIGN INVESTMENTS – CASE OF IZMIR

Yabancı sermaye yatırımları ülkelerin ekonomik gelişiminde önemi bir rol oynarken özellikle finans gücü, teknoloji gelişimi, dış pazarlara açılma vb. konularda büyük avantaj sağlamaktadır. Bu nedenle yabancı sermayeli yatırımların varlığı ülke ekonomisinin gelişiminde önemli bir yere sahiptir. Son yıllarda ekonomik kalkınmaya ilişkin tartışmalarda kümelenme de artan bir önem kazanmıştır. Dünya çapında birçok hükümet, kümelenmeleri bölgesel kalkınmada kurumsal gelişme ve yeniliğin potansiyel itici güçleri olarak görmektedir. Kümelenme girişimleri, kaynakların ve finansmanın hedef bölgelerin ötesine yayılabilen yüksek büyüme ve gelişme potansiyeline sahip hedef alanlarda yoğunlaşmasına (yayılma ve çoğaltıcı etkiler) izin vermeleri açısından da etkili politika araçları olarak kabul edilmektedir (UNIDO, 2020). Bu nedenle kümelenme sürecinde yabancı sermayenin varlığı küme gücünü arttırırken, özellikle kümenin gelişiminde ve devamlılığının sağlanmasında önemli bir yer olan uluslararası network bağlantılarının oluşmasında da itici bir güç oluşturmaktadır. Bu bağlamda bu çalışmanın amacı da; İzmir’deki yabancı sermayeli firmaların yer seçim tercihlerini, sektörel dağılımını ve kümelenme potansiyelini ortaya koyarak, yabancı sermayeli firmaların ve potansiyel kümelerin gelişimi için öneri stratejiler geliştirmektir. Yöntem olarak da, İzmir çalışma alanında yer alan yabancı sermayeli firmaların kümelenme potansiyelini tespit etmek amacı ile Üç Yıldız Modeli, rekabetçilik avantajını ortaya koymak için ise Porter Elmas Modeli kullanılmıştır. Böylelikle bu çalışmanın; ihracat potansiyelinin gelişiminde önemli bir araç olan yabancı sermayeli yatırımların sektörel tercihleri ve kümelenme potansiyeli ortaya konarak, İzmir’in sanayi gelişim politikalarının oluşturulmasında ve desteklenmesinde bir araç olarak kullanılan küme geliştirme çalışmalarında yol gösterici olması beklenmektedir.While foreign capital investments play an important role in the economic development of countries, especially financial power, technology development, opening to foreign markets, etc. provides great advantages. For this reason, the presence of foreign capital investments has an important place in the development of the country\u27s economy. In recent years, clustering has gained increasing importance in discussions on economic development. Many governments around the world see clusters as potential drivers of institutional development and innovation in regional development. Clustering initiatives are also recognized as effective policy tools in that they allow for the concentration of resources and finance in target areas with high growth and development potential (diffuse and multiplier effects) that can spread beyond the target regions (UNIDO; 2020). For this reason, while the presence of foreign capital in the clustering process increases the power of the cluster, it also creates a driving force in the formation of international network connections, which is an important place in the development and continuity of the cluster.In this context, the aim of this study is; It is to develop suggested strategies for the development of foreign capital companies and potential clusters by revealing the location selection preferences, sectoral distribution and clustering potential of foreign capital companies in İzmir. As a method, the Three Star Model was used to determine the clustering potential of the foreign capital companies in the Izmir study area, and the Porter Diamond Model was used to reveal the competitive advantage. Thus, this study; It is expected to guide the cluster development studies, which are used as a tool in the creation and support of industrial development policies of İzmir, by revealing the sectoral preferences and clustering potential of foreign capital investments, which are an important tool in the development of export potential

Subklinik mastitisli Anadolu mandalarında epidermal büyüme faktörü değerlerinin (EGF) araştırılması

Subclinical mastitis (SCM) is a serious disease of farm animals. There are many studies on SCM that aim to make the diagnosis practical, economical and reliable. It was the aim of the present study comparison of epidermal growth factors (EGF) ratios in animals with and without subclinical mastitis as an indictor of SCM in Anatolian water buffaloes. A study was carried out in a total of on 35 milk samples from 20 healthy and 15 mastitic mammary quarters of clinical healthy and nonpregnant buffaloes. Samples were examined using California mastitis test (CMT) as cow side test to detect of SCM before being transferred to the laboratory. Microbiological culture was also performed to determine bacterial contamination. Level of EGF and somatic cell count (SCC) was determined in all samples. As a result of the comparison of the EGF concentration between the SCM (+) and SCM (-) groups, the SCM (+) group was found to be higher than the SCM (-) group. EGF tests may be a useful tool in determining subclinical mastitis.Subklinik mastitis (SKM), çiftlik hayvanlarının ciddi bir hastalığıdır. Subklinik mastitis tanısının pratik, ekonomik ve güvenilir olmasını amaçlayan birçok çalışma vardır. Bu çalışmada Anadolu mandalarında SKM'in bir göstergesi olarak subklinik mastitis olan ve olmayan hayvanlarda epidermal büyüme faktörleri (EGF) oranlarının karşılaştırılması amaçlanmıştır. Çalışma klinik olarak sağlıklı ve gebe olmayan 20 sağlıklı ve 15 mastitisli meme lobundan alınan toplam 35 süt örneğinde yürütülmüştür. Süt örnekleri alınır alınmaz, laboratuvara transferi gerçekleştirilmeden önce Kaliforniya mastitis test (CMT) ile saha koşullarında SKM tespiti yapıldı. Bakteriyel kontaminasyonu belirlemek amacıyla mikrobiyolojik kültür yapıldı. Tüm örneklerde EGF düzeyi ve somatik hücre sayısı (SCC) belirlendi. EGF konsantrasyonunun SKM (+) ve SKM (-) grupları arasındaki karşılaştırma sonucunda, SKM (+) grubunun SKM (-) grubundan daha yüksek olduğu bulundu. EGF testlerinin subklinik mastitisin belirlenmesinde yararlı bir araç olabileceği kanısına varılmıştır

Attractive versus Repulsive Excitonic Interactions of Colloidal Quantum Dots Control Blue- to Red-Shifting (and Non-shifting) Amplified Spontaneous Emission

Tunable, high-performance, two-photon absorption (TPA)-based amplified spontaneous emission (ASE) from near-unity quantum efficiency colloidal quantum dots (CQDs) is reported. Besides the absolute spectral tuning of ASE, the relative spectral tuning of ASE peak with respect to spontaneous emission was shown through engineering excitonic interactions in quasi-type-II CdSe/CdS core/shell CQDs. With core shell size adjustments, it was revealed that Coulombic exciton-exciton interactions can be tuned to be attractive (type-I-like) or repulsive (type-II-like) leading to red- or blue-shifted ASE peak, respectively, and that nonshifting ASE can be achieved with the right core shell combinations. The possibility of obtaining ASE at a specific wavelength from both type-I-like and type-II-like CQDs was also demonstrated. The experimental observations were supported by parametric quantum-mechanical modeling, shedding light on the type-tunability. These excitonically engineered CQD-solids exhibited TPA-based ASE threshold as low as 6.5 mJ/cm(2) under 800 nm excitation, displaying one of the highest values of TPA cross-section of 44 660 GM

Uterin Serviksin Minimal Deviasyon Adenokarsinomu MDA

Minimal deviasyon adenokarsinom MDA servikal adenokarsinomların %1-3 oranında görülen bir varyantıdır.Nadir görülmesi nedeniyle standart tanısal metot ve tedavi protokolü yoktur. Uterin servikste 10-12 cm boyutunda kitlesi olan vakamızda tanı servikal biyopsi ile konamadı.Manyetik rezonans görüntülemede MRI MDA tanısı düşünüldü ve operasyon sonrası tanı kondu. Postoperatif olarak adjuvant kemoradyoterapi KRT uygulandı ve hasta 16 aylık bir süre rekürrens olmadan izlend

The influence of alcohol related accidents on health care cost

Introduction: Road traffic accidents are globally leading causes of mortality and morbidity. Alcohol is among the most frequently used pleasure-inducing substances in the world. Use of motor vehicle under the influence of alcohol is completely illegal in some countries. However, it is allowed up to a certain level of eth- anol in blood in other countries. Traffic accidents caused by alcohol consumption are known to cause more harmonhealthofindividuals.Thealcoholaffectsnervoussystem. Alcoholslowsreflexesandimpairsbalance. In other words, alcohol intake reduces capability of individuals while using any motor vehicle. This study aims to search the health care cost of individuals who had traffic accidents under the influence of alcohol.  Methods: This present study included 657 patients who were admitted to the E.R. resulting from traffic accidents between the dates 01.01.2017–01.06.2017. Demographic information of the patients, their time of hospital admission, medical analyses and examinations, the cost of those analyses and examinations, and their ethanol levels were recorded.  Results: 657 patients were included in the study. 460 (68.1) of those patients were males. Their age average was 35.57 ± 15.18. 61 (9.0%) of the patients were seen to have ethanol positive blood. The health care expenditures of ethanol positive patients were found to be 374,75 ± 251,3 TL whereas the expenditures of ethanol free patients were identified to be 283,17 ± 222,72 TL. The health care expenditures of ethanol positive patients were seen to have substantially increased. (p = 0,003).  Conclusions: Alcohol intake is known to be a leading cause of traffic accidents that generally results in deaths and heavy injuries. This present study displays that traffic accidents caused by alcohol consumption increases the cost of health care as well.