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Synthesis, characterization, and photophysical and fluorescence sensor behaviors of a new water-soluble double-bridged naphthalene diimide appended cyclotriphosphazene 含环三磷腈的新型水溶性双桥萘二亚胺的合成、表征及其光物理和荧光传感器行为
4区 化学 Q3 Chemistry Pub Date : 2023-10-31 DOI: 10.55730/1300-0527.3613
SÜREYYA OĞUZ TÜMAY, SERKAN YEŞİLOT
A new water-soluble template of double-bridged naphthalene diimide appended cyclotriphosphazene was prepared, and its photophysical and sensor behaviors were evaluated. The characterization of novel double-bridged naphthalene diimide appended cyclotriphosphazene (6) was carried out by NMR (1 H, 13C, 31P) and mass spectroscopies. The photophysical behaviors of compound 6 were evaluated by UV-Vis absorption and fluorescence spectroscopies in various solvent systems and different concentrations. As an application for usability of the obtained water-soluble template in different applications, the fluorescence sensor property of compound 6 was investigated in the presence of many different competing species (organic acids, saccharides, nitroaromatic compounds, anions, and metal cations). The results obtained showed that compound 6 had selectivity against only the nitroaromatic species among the competing species tested.
制备了一种新型的双桥萘二亚胺附加环三磷腈水溶性模板,并对其光物理性能和传感器性能进行了评价。采用核磁共振(1h, 13C, 31P)和质谱对新型双桥萘二亚胺附加环三磷腈(6)进行了表征。利用紫外可见吸收光谱和荧光光谱研究了化合物6在不同溶剂体系和不同浓度下的光物理行为。为了验证所获得的水溶性模板在不同应用中的可用性,我们研究了化合物6在许多不同竞争物质(有机酸、糖类、硝基芳香族化合物、阴离子和金属阳离子)存在下的荧光传感器性能。结果表明,化合物6在竞争种中仅对硝基芳香族有选择性。
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引用次数: 0
Comparatively sonophotochemical and photochemical studies of phthalocyanines with cationic substituents on nonperipheral positions 非外周位置带阳离子取代基酞菁的声光化学和光化学比较研究
4区 化学 Q3 Chemistry Pub Date : 2023-10-31 DOI: 10.55730/1300-0527.3602
MUKADDES ÖZÇEŞMECİ, CEREN CAN KARANLIK, ALİ ERDOĞMUŞ, ESİN HAMURYUDAN
The term sonophotodynamic therapy (SPDT) refers to a combination of sonodynamic therapy (SDT) and photodynamic therapy (PDT), in which the efficacy of the treatment is boosted by utilizing the proper amount of a sensitizer that is responsive to both light and ultrasound. Although it has been proven in photophysicochemical studies that SPDT enhances singlet oxygen production, related studies in the literature are very limited. Considering this situation, this study aims to investigate the efficacy of synthesized phthalocyanines in terms of PDT and SPDT. The singlet oxygen quantum values calculated as 0.13 for 5, 0.44 for 6, and 0.61 for 7 in photochemical (PDT) application increased to 0.18, 0.86, and 0.92, respectively, with sonophotochemical (SPDT) application. According to the results, singlet oxygen production was more efficient with SPDT. This work will add to the body of knowledge on employing the SPDT approach to increase singlet oxygen generation
术语声光动力疗法(SPDT)是指声动力疗法(SDT)和光动力疗法(PDT)的结合,其中通过利用适量对光和超声均有反应的敏化剂来提高治疗效果。虽然在光物理化学研究中已经证明SPDT可以促进单线态氧的产生,但相关的文献研究非常有限。鉴于此,本研究旨在考察合成的酞菁在PDT和SPDT方面的功效。单线态氧量子值在光化学(PDT)应用中分别为0.13(5)、0.44(6)和0.61(7),在声光化学(SPDT)应用中分别增加到0.18、0.86和0.92。结果表明,SPDT的单线态产氧效率更高。这项工作将增加使用SPDT方法增加单线态氧生成的知识体系
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引用次数: 0
Synthesis of alnustone-like diarylpentanoids via a 4 + 1 strategy and assessment of their potential anticancer activity 4 + 1策略合成阿努斯通样二芳基戊烷类化合物及其潜在抗癌活性评价
4区 化学 Q3 Chemistry Pub Date : 2023-10-31 DOI: 10.55730/1300-0527.3609
NESLİHAN ÇELEBİOĞLU, ÖZLEM ÖZDEMİR TOZLU, HASAN TÜRKEZ, HASAN SEÇEN
Twelve compounds with a 1,5-diaryl-1-penten-3-one structure were synthesized and their cytotoxic activities were evaluated. The 1,5-diaryl-1-penten-3-one compounds were obtained via in situ enaminations of 4-phenyl-2-butanone and 4-(4-hydroxyphenyl)-2- butanone in the presence of pyrrolidine-AcOH, followed by condensation with six different benzaldehydes. The synthesized compounds were tested for their cytotoxic activity against human glioblastoma (U87-MG), breast (MCF-7), and prostate (PC-3) cancer cell lines. Some of the novel compounds exhibited remarkable cytotoxic action, especially against MCF-7 cancer cells.
合成了12个具有1,5-二芳基-1-戊烯-3- 1结构的化合物,并对其细胞毒活性进行了评价。在吡咯烷- acoh的存在下,通过4-苯基-2-丁酮和4-(4-羟基苯基)-2-丁酮的原位珐琅反应得到1,5-二烷基-1-戊烯-3- 1化合物,然后与6种不同的苯甲醛缩合。合成的化合物对人胶质母细胞瘤(U87-MG)、乳腺(MCF-7)和前列腺(PC-3)癌细胞的细胞毒活性进行了测试。一些新化合物表现出显著的细胞毒性作用,特别是对MCF-7癌细胞。
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引用次数: 0
A multifunctional thienothiophene member: 4-thieno[3,2-b]thiophen-3-ylbenzonitrile (4-CNPhTT) 一种多功能噻吩成员:4-噻吩[3,2-b]噻吩-3-基苯腈(4-CNPhTT)
4区 化学 Q3 Chemistry Pub Date : 2023-10-31 DOI: 10.55730/1300-0527.3608
RECEP İŞÇİ, TURAN ÖZTÜRK
,
Thieno[3,2-b]噻吩(TT)在有机电子学和光电子学领域受到了广泛的关注。在这项研究中,我们小组开发了一种有用的TT衍生物4-噻吩[3,2-b]噻吩-3-基苯并腈(4-CNPhTT),它具有强吸电子的4-CNPh片段,因为它一直是各种有机电子材料发展的来源。利用循环伏安法对4-CNPhTT进行了电化学聚合,讨论了聚合物膜的一些光学和电子性质,并进行了光谱电化学测量,研究了掺杂后聚合物膜的光学变化。此外,在单x射线晶体结构的支持下,4-CNPhTT在100 ~ 500µm不同量级的扫描电镜下被澄清。采用热重法和差热分析法研究了4-CNPhTT的热性能。所有观察到的性质表明,4-CNPhTT具有在TT家族中开发电子和光电子应用新材料的潜力
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引用次数: 1
Architecture design of TiO2 with Co-doped CdS quantum dots photoelectrode for water splitting TiO2与共掺杂CdS量子点光电极的结构设计
4区 化学 Q3 Chemistry Pub Date : 2023-10-31 DOI: 10.55730/1300-0527.3604
FATİH TEZCAN, ABRAR AHMAD, GÜLFEZA KARDAŞ
Photoelectrochemical hydrogen production is a critical key to solving the carbon-zero goal of countries due to renewable sources of solar light and combustion products of hydrogen-only water. Here, an architecture design for an n-type nano rosettes-rod TiO2 (RT) surface using CdS and Co-doped CdS quantum dots (QDs) is carried out utilizing the SILAR (simple ionic layer adsorption and reaction) method. Furthermore, the photocatalytic behaviour of Co-doped CdS QDs SILAR cycles deposition is investigated in various cycles, including 5, 8, 10, and 12. The FESEM, Raman XRD, Uv-Vis spectrometer, and vibration modes are used to evaluate the photoelectrode surface structure, crystal structure, and solar light absorption, respectively. FESEM images and XRD pattern revealed successive CdS QDS and Co-doped CdS QDs deposition on the RT boundary and rising SILAR cycles of Co-doped CdS QDs lead to further coverage of RT surface. UV-vis spectrometer indicated shifting solar light absorption to the visible region by applying more SILAR cycles of Co-doped CdS QDs deposition. The electrochemical parameters obtained from EIS showed total polarization resistance (Rp ) of the RT electrode dramatically decreased with 10 SILAR cycle Co-doped CdS QDs deposition (5093 Ω cm2 and 617 Ω cm2 ). Linear sweep voltammetry (LSV) and chronoamperometric photocatalytic performance measurements indicated Co-doped CdS QDs on RT extremely enhanced photoresponse under solar irradiation and 10 SILAR cycle Co-doped CdS QDs improved photocurrent density about fourfold according to blank RT electrode.
光电化学制氢是解决各国零碳目标的关键,因为太阳能可再生能源和氢水的燃烧产物。本文利用简单离子层吸附反应(SILAR)方法,利用CdS和共掺杂CdS量子点(QDs)进行了n型纳米玫瑰棒TiO2 (RT)表面的结构设计。此外,研究了共掺杂CdS QDs SILAR循环沉积的光催化行为,包括5、8、10和12个循环。利用FESEM、Raman XRD、Uv-Vis光谱仪和振动模式分别评价了光电极的表面结构、晶体结构和太阳光吸收。FESEM图像和XRD图谱显示CdS QDS和共掺杂CdS QDS连续沉积在RT边界上,共掺杂CdS QDS的SILAR循环周期增加导致RT表面进一步覆盖。紫外-可见谱仪表明,通过施加更多的SILAR循环,共掺杂CdS量子点沉积可以将太阳光吸收转移到可见光区。电化学参数显示,10个SILAR循环共掺杂CdS量子点沉积(5093 Ω cm2和617 Ω cm2)显著降低了RT电极的总极化电阻(Rp)。线性扫描伏安法(LSV)和光催化性能测试表明,共掺杂CdS量子点在RT上极大地增强了太阳辐照下的光响应,10个SILAR周期共掺杂CdS量子点使空白RT电极的光电流密度提高了约4倍。
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引用次数: 0
Benzimidazol-2-ylidene ruthenium complexes for C-N bond formation through alcohol dehydrogenation 苯并咪唑-2-酰基钌配合物通过醇脱氢形成C-N键
4区 化学 Q3 Chemistry Pub Date : 2023-10-31 DOI: 10.55730/1300-0527.3606
ZAHID NAWAZ, NEVİN GÜRBÜZ, MUHAMMED NAVEED ZAFAR, NAMIK ÖZDEMİR, BEKİR ÇETİNKAYA, İSMAİL ÖZDEMİR
A low temperature hydrogen borrowing approach to generate secondary amines using benzimidazole-based N-heterocyclic carbene (BNHC) ruthenium complexes is reported. A series of the piano-stool complexes of the type [(η6 -p-cymene)(BNHC)RuCl2 ] (1a-g) were synthesized via one-pot reaction of the NHC salt precursor, Ag2 O, and [RuCl2 (p-cymene)]2 and characterized using conventional spectroscopic techniques. The geometry of two precursors, [(η6 -p-cymene)(Me4BnMe2 BNHCCH2OxMe)RuCl2 ] (1f) and [(η6 -p-cymene)(Me5BnMe2 BNHCCH2OxMe)RuCl2 ] (1g), was studied by single crystal X-ray diffraction. These catalysts were found to dehydrogenate alcohols efficiently at temperatures as low as 50 °C to allow Schiff-base condensation and subsequent imine hydrogenation to afford secondary amines. Notably, this ruthenium-based procedure enables the N-alkylation of aromatic and heteroaromatic primary amines with a wide range of primary alcohols in excellent yields of up to 98%. The present methodology is green and water is liberated as the sole byproduct.
报道了用苯并咪唑基n -杂环碳(BNHC)钌配合物制备仲胺的低温借氢方法。以NHC盐前体ag2o和[RuCl2(对伞花烯)]2为原料,通过一锅反应合成了一系列[(η - 6 -对伞花烯)(BNHC)RuCl2] (1a-g)型钢琴-粪便配合物,并用常规光谱技术对其进行了表征。用单晶x射线衍射研究了[(η - 6 -p-cymene)(Me4BnMe2 BNHCCH2OxMe)RuCl2] (1f)和[(η - 6 -p-cymene)(Me5BnMe2 BNHCCH2OxMe)RuCl2] (1g)的几何结构。这些催化剂被发现在低至50℃的温度下有效地脱氢醇,使希夫碱缩合和随后的亚胺加氢产生仲胺。值得注意的是,这种基于钌的方法可以使芳香和杂芳香伯胺与各种伯醇进行n -烷基化,收率高达98%。目前的方法是绿色的,水作为唯一的副产品被释放出来。
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引用次数: 0
Homoprotocatechuate dioxygenase active site: Imitating the secondary sphere base via computational design 同源儿茶酸双加氧酶活性位点:通过计算设计模拟次生球基
4区 化学 Q3 Chemistry Pub Date : 2023-10-31 DOI: 10.55730/1300-0527.3598
MUHAMMED BUYUKTEMIZ, YAVUZ DEDE
Oxidative ring cleavage reactions have attracted great interest and various studies on the catechol ring-cleaving enzyme homoprotocatechuate dioxygenase (HPCD) have been reported in the literature. The available data on how the proton transfer takes place led us to design a potential HPCD model structure. A secondary sphere effect of utmost importance, the assistance of His200, which is critical for the catechol proton to migrate to dioxygen, was cautiously included on the first coordination shell. This was done mainly by modifying the axial ligands in the first coordination shell of HPCD such that the dual basic/acidic role in the proton transfer pathway of His200 was reproduced. Model systems with mono-, bi-, and tridentate ligands are reported. Energetically feasible reaction channels on synthetically promising ligand structures are identified. Key structural and electronic principles for obtaining viable proton transfer paths are outlined.
氧化环切割反应引起了人们的极大兴趣,对儿茶酚环切割酶同质原儿茶酚双加氧酶(HPCD)的各种研究已经在文献中报道。关于质子转移如何发生的现有数据使我们设计了一个潜在的HPCD模型结构。在第一个配位层上,我们小心翼翼地加入了一个次要的球效应,即对儿茶酚质子迁移到二氧至关重要的His200的辅助作用。这主要是通过修饰HPCD第一配位壳的轴向配体来实现的,从而再现了His200质子转移途径中的碱性/酸性双重作用。模型系统与单,双,和三叉戟配体报道。确定了具有合成前景的配体结构上能量可行的反应通道。概述了获得可行质子转移路径的关键结构和电子原理。
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引用次数: 0
Water-soluble phthalocyanine photosensitizers for photodynamic therapy 光动力治疗用水溶性酞菁光敏剂
4区 化学 Q3 Chemistry Pub Date : 2023-10-31 DOI: 10.55730/1300-0527.3583
İPEK ÖMEROĞLU, MAHMUT DURMUŞ
Photodynamic therapy (PDT) is based on a photochemical reaction that is started when a photosensitizing process is activated by the light and results in the death of tumor cells. Solubility is crucial in PDT applications to investigate the physical and chemical characteristics of phthalocyanines, but, unfortunately, most phthalocyanines show limited solubility especially in water. To increase the solubility of phthalocyanines in polar solvents and water, ionic groups such as -SO3 - , -NR3 +, -COO- , and nonionic groups such as poly-oxy chains are frequently added to the peripheral or nonperipheral positions of the phthalocyanine framework. Since water-solubility and NIR-absorbing properties are essential for efficient PDT activation, studies have been focused on the synthesis of these types of phthalocyanine derivatives. This review focuses on the photophysical, photochemical, and some in vitro or in vivo studies of the recently published ionic and nonionic phthalocyanine-mediated photosensitizers carried out in the last five years. This review will have positive contributions to future studies on phthalocyanine chemistry and their PDT applications as well as photochemistry
光动力疗法(PDT)基于光化学反应,当光激活光敏过程并导致肿瘤细胞死亡时,该反应就开始了。在PDT应用中,为了研究酞菁的物理和化学特性,溶解度是至关重要的,但不幸的是,大多数酞菁的溶解度有限,尤其是在水中。为了提高酞菁在极性溶剂和水中的溶解度,经常将- so3 -、- nr3 +、- coo -等离子基团和聚氧链等非离子基团添加到酞菁框架的外周或非外周位置。由于水溶性和nir吸收性能是有效的PDT活化的必要条件,研究一直集中在这些类型的酞菁衍生物的合成上。本文综述了近五年来新发表的离子和非离子酞菁介导的光敏剂的光物理、光化学和一些体外或体内研究。本文的综述将对今后酞菁化学及其PDT应用、光化学的研究有积极的贡献
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引用次数: 0
Arsenic speciation by using emerging sample preparation techniques: a review 新型样品制备技术对砷形态形成的影响
4区 化学 Q3 Chemistry Pub Date : 2023-10-31 DOI: 10.55730/1300-0527.3590
MUHAMMAD SAQAF JAGIRANI, MUSTAFA SOYLAK
Arsenic is a hazardous element that causes environmental pollution. Due to its toxicological effects, it is crucial to quantify and minimize the hazardous impact on the ecology. Despite the significant advances in analytical techniques, sample preparation is still crucial for determining target analytes in complex matrices. Several factors affect the direct analysis, such as trace-level analysis, advanced regulatory requirements, complexity of sample matrices, and incompatible with analytical instrumentation. Along with the development in the sample preparation process, microextraction methods play an essential role in the sample preparation process. Microextraction techniques (METs) are the newest green approach that replaces traditional sample preparation and preconcentration methods. METs have minimized the limitation of conventional sample preparation methods while keeping all their benefits. METs improve extraction efficacy, are fast, automated, use less amount of solvents, and are suitable for the environment. Microextraction techniques with less solvent consumption, such as solid phase microextraction (SPME) solvent-free methods, and liquid phase microextraction (LPME), are widely used in modern analytical procedures. SPME development focuses on synthesizing new sorbents and applying online sample preparation, whereas LPME research investigates the utilization of new solvents.
砷是一种造成环境污染的有害元素。由于其毒理学效应,量化和最小化其对生态的有害影响至关重要。尽管分析技术取得了重大进展,但样品制备对于确定复杂基质中的目标分析物仍然至关重要。有几个因素影响直接分析,如痕量水平分析,先进的法规要求,样品矩阵的复杂性,以及与分析仪器的不兼容。随着样品制备工艺的发展,微萃取方法在样品制备过程中发挥着重要的作用。微萃取技术(METs)是取代传统样品制备和预浓缩方法的最新绿色方法。METs最大限度地减少了传统样品制备方法的局限性,同时保留了它们的所有优点。METs提高了萃取效率,快速,自动化,使用较少的溶剂,并且适合环境。固相微萃取(SPME)无溶剂法和液相微萃取(LPME)等溶剂消耗较少的微萃取技术在现代分析过程中得到广泛应用。SPME的发展重点是合成新的吸附剂和应用在线样品制备,而LPME的研究则是研究新溶剂的利用。
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引用次数: 0
A facile tert-butyl nitrite-assisted preparation of deamino graphitic carbon nitride (DA-gCN) as a photocatalyst for the C-H arylation of heteroarenes using anilines as radical source 以苯胺为自由基源,亚硝酸盐叔丁基辅助制备脱氨基石墨氮化碳(DA-gCN)作为杂芳烃C-H基化的光催化剂
4区 化学 Q3 Chemistry Pub Date : 2023-10-31 DOI: 10.55730/1300-0527.3605
PALANI NATARAJAN, BEGÜMHAN KARAPINAR KOÇ, ÖNDER METİN
In pristine graphitic carbon nitride (g-CN), amino groups often function as structural defects that trap photogenerated charges, resulting in low photocatalytic activity as well as reaction with nitrite, aldehyde, etc., ensuing in poor product yield. Without significantly altering the optical characteristics, the removal of amino groups is necessary to increase the photocatalytic activity and structural stability of pristine g-CN. The deamino graphitic carbon nitride (DA-gCN-5) was prepared by tert-butyl nitrite (TBN)- treatment, characterized and used as a photocatalyst for the radical C-H arylation of heteroarenes using anilines as radical source. Indeed, the photophysical characteristics of DA-gCN-5 and those of pristine g-CN are very comparable, except that DA-gCN-5 has a fewer residual amino groups, higher crystallinity, and compressed structure with a different morphology. Moreover, DA-gCN-5- catalyzed C-H arylation reaction offers greater product yield in a shorter reaction time compared to that of pristine g-CN in the coupling between heteroarenes and the in situ generated aryl diazonium salts from anilines under visible light irradiation. The amino groups in pristine g-CN absorbed the TBN that was added to convert aniline into the appropriate diazonium ions during the reaction. As a result, deamino graphitic carbon nitride produced by chemical treatment has better photophysical properties and catalytic activity than pristine g-CN. Additionally, this is the first method that uses diazotization reaction for the preparation of deamino graphitic carbon nitride, as far as we are aware.
在原始石墨氮化碳(g-CN)中,氨基常作为结构缺陷捕获光生电荷,导致光催化活性低,与亚硝酸盐、醛等反应,产物收率低。在不显著改变光学特性的情况下,去除氨基是提高原始g-CN光催化活性和结构稳定性的必要条件。采用亚硝基叔丁基(TBN)法制备了脱氨基石墨氮化碳(DA-gCN-5),对其进行了表征,并以苯胺为自由基源,用作杂芳烃自由基C-H基化反应的光催化剂。事实上,DA-gCN-5的光物理特性与原始的g-CN非常相似,只是DA-gCN-5的残余氨基更少,结晶度更高,结构压缩,形态不同。此外,在可见光照射下,DA-gCN-5催化的C-H芳基化反应比原始g-CN在杂芳烃和苯胺原位生成芳基重氮盐的偶联反应在更短的反应时间内获得了更高的产物收率。原始g-CN中的氨基吸收了在反应过程中加入的将苯胺转化为适当重氮离子的TBN。结果表明,化学处理得到的脱氨基石墨氮化碳具有比原始g-CN更好的光物理性能和催化活性。此外,这是据我们所知的第一个利用重氮化反应制备脱氨基石墨氮化碳的方法。
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引用次数: 0
期刊
Turkish Journal of Chemistry
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