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Bifunctional Phenol Quinone Methide Precursors: Synthesis and Biological Activity 双官能酚醌甲基化物的合成及其生物活性
IF 0.3 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2019-01-28 DOI: 10.5562/CCA3455
Matija Sambol, K. Ester, A. Husak, Đ. Škalamera, I. Piantanida, N. Basarić
New bifunctional quinone methide (QM) precursors, bisphenols 2a–2e, and monofunctional QM precursor 7 were synthesized. Upon treatment with fluoride, desilylation triggers formation of reactive intermediates, QMs, which was demonstrated by trapping QM with azide or methanol. The ability of QMs to alkylate and cross-link DNA was assayed by investigation of the effects of QMs to DNA denaturing, but without conclusive evidence. Furthermore, treatment of a plasmid DNA with compounds 2a–2e and KF, followed by the analysis by alkaline denaturing gel electrophoresis, did not provide evidence for the DNA cross-linking. MTT test performed on two human cancer cell lines (MCF7 breast adenocarcinoma and SUM159 pleomorphic breast carcinoma), with and without fluoride, indicated that 2a–2e or the corresponding QMs did not exhibit cytotoxic activity, in line with the lack of ability to cross-link DNA. The lack of reactivity with DNA and biological activity were explained by sequential formation of QMs where bifunctional cytotoxic reagent is probably never produced. Instead, the sequential generation of monofunctional QM followed by a faster hydrolysis leads to the destruction of biologically active reagent. The findings described here are particularly important for the rational design of new generation of QM precursor molecules that will attain desirable DNA reactivity and cytotoxicity.
合成了新的双功能醌甲酰胺(QM)前体、双酚2a–2e和单功能QM前体7。在用氟化物处理时,脱硅引发反应性中间体QMs的形成,这通过用叠氮化物或甲醇捕获QM来证明。QMs烷基化和交联DNA的能力是通过研究QMs对DNA变性的影响来测定的,但没有确凿的证据。此外,用化合物2a-2e和KF处理质粒DNA,然后通过碱性变性凝胶电泳进行分析,并没有为DNA交联提供证据。在两种人类癌症细胞系(MCF7乳腺癌和SUM159多形性乳腺癌)上进行的MTT测试表明,在有氟和无氟的情况下,2a–2e或相应的QM没有表现出细胞毒性活性,这与缺乏交叉连接DNA的能力一致。与DNA缺乏反应性和生物活性的原因是QMs的连续形成,其中可能从未产生双功能细胞毒性试剂。相反,单功能QM的顺序生成,随后是更快的水解,导致生物活性试剂的破坏。这里描述的发现对于新一代QM前体分子的合理设计特别重要,该分子将获得所需的DNA反应性和细胞毒性。
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引用次数: 2
Self-Assembling Monolayers of Stearic Acid in Protection of Steel 硬脂酸自组装单分子膜对钢的保护作用
IF 0.3 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2018-12-30 DOI: 10.5562/CCA3436
Katarina Marušić, H. O. Ćurković
Carbon steel corrodes severely in presence of sodium chloride and it needs additional protection to be used in marine environments. This work investigates the possibility of using a layer of stearic acid as protection for carbon steel. Stearic acid was applied on the steel by two types of treatments: chemical preparation - by immersion of a steel sample in the SA solution and electrochemical preparation – by imposing a corresponding potential to the system. The results have shown that although both treatments result in obtaining an ordered aliphatic monolayer and both treatments increase the hydrophobicity of the surface, protection that the electrochemical preparation offers is stable in time, while the protection the chemical preparation offers is not.
碳钢在氯化钠的存在下会严重腐蚀,需要额外的保护才能在海洋环境中使用。这项工作探讨了使用硬脂酸层作为碳钢保护的可能性。硬脂酸通过两种处理方式作用于钢上:化学制备——将钢样品浸入SA溶液中;电化学制备——通过对系统施加相应的电位。结果表明,虽然两种处理都能得到有序的脂肪族单层,而且两种处理都增加了表面的疏水性,但电化学制备提供的保护在时间上是稳定的,而化学制备提供的保护则不是。
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引用次数: 3
Chromatographic and voltammetric characterization of chlorogenic acids in coffee samples 咖啡样品中绿原酸的色谱和伏安表征
IF 0.3 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2018-12-30 DOI: 10.5562/CCA3439
I. Tomac, L. Jakobek, M. Šeruga
The accurate and precise characterization of eight chlorogenic acids (CGAs) isomers, caffeoylquinic acids (5-CQA, 4-CQA, 3-CQA), dicaffeoylquinic acids (3, 5-diCQA, 4, 5-diCQA, 3, 4-diCQA), and feruloylquinic acids (5-FQA, 4- FQA), was carried out using different brands of coffee. High-performance liquid chromatography (HPLC), differential pulse (DPV) and square- wave voltammetry (SWV) were applied for the investigation. HPLC proved to be an accurate and precise method for separation, identification and quantification of CGAs isomers in coffee extracts. DPV and SWV have shown that electrochemical behaviour of coffee extracts was very similar to that of CGAs isomers and DPV and SWV can be used for the correct characterization of CGAs in coffee. All three techniques have shown a very high correlation of CGAs content in all investigated coffee samples. Therefore, HPLC, DPV and SWV methods can be used in combination as very selective, sensitive and precise methods for characterization of CGAs isomers in coffee extracts.
使用不同品牌的咖啡对八种绿原酸(CGA)异构体,即咖啡酰奎宁酸(5-CQA,4-CQA,3-CQA)、二咖啡酰奎宁酸(3,5-diCQA,4,5-DIQA,3,4-dCQA)和阿魏酰奎宁酸类(5-FQA,4-FQA)进行了准确和精确的表征。采用高效液相色谱法(HPLC)、微分脉冲法(DPV)和方波伏安法(SWV)进行了研究。高效液相色谱法被证明是一种准确、准确地分离、鉴定和定量咖啡提取物中CGAs异构体的方法。DPV和SWV表明,咖啡提取物的电化学行为与CGAs异构体的电化学行为非常相似,DPV和SW V可用于正确表征咖啡中的CGAs。所有三种技术都表明,在所有研究的咖啡样品中,CGAs含量具有非常高的相关性。因此,HPLC、DPV和SWV方法可以作为非常选择性、灵敏和精确的方法组合用于表征咖啡提取物中CGAs异构体。
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引用次数: 2
Voltammetric study of organic matter components in the upper reach of the Krka River, Croatia 克罗地亚Krka河上游有机物组分的伏安法研究
IF 0.3 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2018-12-30 DOI: 10.5562/CCA3443
Slađana Strmečki, I. Ciglenečki, M. G. Udovič, M. Marguš, E. bura-Nakić, J. Dautović, M. Plavšić
The increased amount of organic matter (OM) accompanied with the development of hypoxia/anoxia and appearance of the sulphur species are indicators of eutrophication in natural waters. To predict biogeochemical and ecological changes, specific OM components in the Lake Brljan (the karst Krka River, Croatia ; station B and station B2 downstream) were studied during 2011 and in January 2012 using voltammetry. Surface‒active substances (eq. 0.018 to 0.150 mg dm-3 Triton‒X‒100) and Cu complexing capacity (54‒680 nmol dm-3) showed the highest values in surface water layer in May 2011 (B) and in November 2011 (B2), associated with the highest dissolved (0.505‒ 1.530 mg C dm-3) and particulate (0.051‒0.725 mg C dm-3) organic carbon and phytoplankton biomass. Autochthonously produced OM did not cause hypoxia/anoxia during the investigated period. Brljan's lake water could be characterised as oligotrophic with occasionally elevated OM concentration depending on season and Krka River water regime.
有机质(OM)含量的增加伴随着缺氧/缺氧的发展和硫物种的出现是天然水体富营养化的指标。为了预测生物地球化学和生态变化,在2011年和2012年1月使用伏安法研究了布尔詹湖(克罗地亚喀斯特Krka河;B站和B2站下游)的特定OM成分。2011年5月(B)和11月(B2)地表水层中的表面活性物质(当量0.018至0.150 mg dm-3 Triton-X-100)和Cu络合容量(54至680 nmol dm-3)显示出最高值,与最高的溶解(0.505至1.530 mg C dm-3)和颗粒(0.051至0.725 mg C dm3)有机碳和浮游植物生物量有关。在研究期间,本地产生的OM不会引起缺氧/缺氧。Brljan的湖水可以被描述为贫营养的,根据季节和Krka河的水情,OM浓度偶尔会升高。
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引用次数: 4
First appearance of Mendeleev's periodic system of elements in Croatian chemistry textbooks 门捷列夫元素周期系统首次出现在克罗地亚化学教材中
IF 0.3 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2018-12-30 DOI: 10.5562/CCA3437
V. Flegar, S. Inić
The first reception of Mendeleev's periodic table of elements and its first mention and publication in Croatian chemistry textbooks is explored. First
对门捷列夫元素周期表的首次接受及其在克罗地亚化学教科书中的首次提及和出版进行了探索。第一
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引用次数: 0
Electrochemical Determination of Metallothioneins by the Modified Brdička Procedure as an Analytical Tool in Biomonitoring Studies 生物监测研究中用改进的Brdička方法电化学测定金属硫蛋白
IF 0.3 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2018-12-30 DOI: 10.5562/CCA3444
Tatjana Mijošek, M. Erk, V. Marijić, N. Krasnići, Zrinka Dragun, D. Ivanković
Present study aims to improve the modified Brdicka procedure of metallothionein (MT) quantification in a way to reduce the analysis duration. Therefore, scan rate of the voltammetric sweep was increased from 0.0052 V s–1 to 0.013 V s–1 by lowering the duration of one step potential from 0.5 s to 0.2 s, which resulted in 2.5 times faster voltammetric sweep. Research confirmed high accuracy and reliability of MT measurements, in both standard sample and samples of heat-treated cytosols of liver, gills and the intestine of European chub and liver of brown trout. The method was confirmed as fast and reliable electrochemical technique for quantification of MTs and this time- saving improvement is especially useful and applicable in different biomonitoring studies which require the analyses of numerous biological samples and high sample throughput.
本研究旨在改进金属硫蛋白(MT)定量的改良Brdicka方法,以缩短分析时间。因此,通过将一步电位的持续时间从0.5 s降低到0.2 s,伏安扫描的扫描速率从0.0052 V s–1增加到0.013 V s–2,从而使伏安扫描速度快2.5倍。研究证实了MT测量的高准确性和可靠性,无论是在标准样品还是热处理的欧洲胖鱼肝脏、鳃和肠道的细胞溶质样品中,还是在褐鳟的肝脏中。该方法被证实是一种快速可靠的MT定量电化学技术,这种节省时间的改进在需要分析大量生物样品和高样品通量的不同生物监测研究中尤其有用和适用。
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引用次数: 4
Benzimidazole Derivatives as Copper Alloy Corrosion Inhibitors 苯并咪唑衍生物作为铜合金缓蚀剂
IF 0.3 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2018-12-30 DOI: 10.5562/cca3450
Martina Mumelaš, H. O. Ćurković, D. Mikić, M. Hranjec, M. Cindrić
Seawater is a corrosive medium that adversely affects on the metallic structures. For that reason, it is often desirable to use some type of corrosion protection to extend the life of structures. The aim of this work was to examine the possibility of CuNi alloy protection in artificial seawater by four benzimidazole derivatives: 2-amino-5(6)nitrobenzimidazole, 2-amino-5-(6)-cyanobenzimidazole, 2-aminobenzimidazole, 2-amino-5(6)-(2-imidazolinyl)benzimidazole hydrochloride. The corrosion studies conducted by polarization measurements after 1 h of immersion in inhibitor solution showed that the most effective inhibitor is 2-amino-5(6)-nitrobenzimidazole. The electrochemical tests were also performed in time by the means of electrochemical impedance spectroscopy for the two most effective inhibitors. The surface of samples was analyzed by scanning electron microscopy and ATR-FTIR spectroscopy. It was concluded that the efficiency of studied inhibitors increases with prolonged exposure of the CuNi alloy to inhibitor solutions as well as with the increase of inhibitor concentration.
海水是一种腐蚀性介质,会对金属结构产生不利影响。出于这个原因,通常需要使用某种类型的腐蚀保护来延长结构的寿命。本工作的目的是研究四种苯并咪唑衍生物:2-氨基-5(6)硝基苯并咪唑、2-氨基-5-(6)-氰基苯并咪唑,2-氨基苯并咪唑和2-氨基5-(6)(2-咪唑基)苯并咪唑盐酸盐在人工海水中保护CuNi合金的可能性。在抑制剂溶液中浸泡1h后,通过极化测量进行的腐蚀研究表明,最有效的抑制剂是2-氨基-5(6)-硝基苯并咪唑。还通过电化学阻抗谱对两种最有效的抑制剂及时进行了电化学测试。通过扫描电子显微镜和ATR-FTIR光谱分析样品的表面。结果表明,所研究的抑制剂的效率随着CuNi合金长时间暴露于抑制剂溶液以及抑制剂浓度的增加而增加。
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引用次数: 1
Electrochemical and UV/VIS Study of L-Histidine and Its Complexes with Cobalt and Nickel L-组氨酸及其钴镍配合物的电化学及UV/VIS研究
IF 0.3 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2018-12-30 DOI: 10.5562/CCA3423
Martina Medvidović‐Kosanović, A. Stanković, Marija Jozanović, M. Drulak, Marina Ilić
In this work oxido-reduction properties of L-histidine were studied by cyclic and differential pulse voltammetry in a pH range from pH 4–10. The results have shown that L-histidine is not electroactive in a pH range from pH 4 to pH 9, while oxidation peak of L-histidine’s imidazole ring at pH 10 was detected with differential pulse voltammetry. It has been found that the oxidation peak current of L-histidine increased with the increase of its concentration in a solution. Adsorption of oxidation product of L-histidine on a glassy carbon electrode surface was also detected. Voltammetric techniques (cyclic and differential pulse voltammetry) and UV/VIS spectroscopy were used to study formation of L-histidine complexes with transition metals. It has been found that L-histidine formed octahedral complex with metal ion (Co2+ and Ni2+) in a 1 : 1 ratio.
在这项工作中,通过循环和微分脉冲伏安法研究了L-组氨酸在pH 4–10范围内的氧化还原性质。结果表明,L-组氨酸在pH4-pH9范围内不具有电活性,而用微分脉冲伏安法检测了L-组氨酸咪唑环在pH10时的氧化峰。研究发现,L-组氨酸在溶液中的氧化峰值电流随着其浓度的增加而增加。还检测了L-组氨酸氧化产物在玻碳电极表面的吸附。采用伏安法(循环和微分脉冲伏安法)和紫外/可见光谱法研究了L-组氨酸与过渡金属配合物的形成。已经发现L-组氨酸与金属离子(Co2+和Ni2+)以1∶1的比例形成八面体络合物。
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引用次数: 8
Reduced Graphene Oxide/α-Fe2O3 Fibres as Active Material for Supercapacitor Application 还原氧化石墨烯/α-Fe2O3纤维在超级电容器中的应用
IF 0.3 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2018-12-30 DOI: 10.5562/CCA3452
Gabrijela Radić, Ivan Šajnović, Željka Petrović, M. K. Roković
The composite hydrogel, composed of reduced graphene oxide and α-Fe2O3 fibres (rGO/α-Fe2O3), was successfully prepared by the hydrothermal procedure starting from GO and α-Fe2O3 nanofibres. According to the SEM and XRD results, α-Fe2O3 fibres are distributed between rGO sheets increasing the inter-sheet space. The rGO/α-Fe2O3 composite was tested as an active material in supercapacitor by means of cyclic voltammetry, galvanostatic charging/discharging and electrochemical impedance spectroscopy in 0.5 mol dm–3 Na2SO4. The obtained results confirmed a positive effect of the α-Fe2O3 addition on capacitive properties. Improved capacitive properties of the composite make this material suitable for supercapacitor application.
以氧化石墨烯和α-Fe2O3纳米纤维为原料,采用水热法制备了还原氧化石墨烯和α-Fe2O3纤维(rGO/α-Fe2O3)复合水凝胶。SEM和XRD结果表明,α-Fe2O3纤维分布在还原氧化石墨烯片间,片间空间增大。在0.5 mol dm - 3na2so4中,采用循环伏安法、恒流充放电法和电化学阻抗法对rGO/α-Fe2O3复合材料作为超级电容器活性材料进行了测试。所得结果证实了α-Fe2O3的加入对电容性能有积极的影响。该复合材料的电容性能得到改善,适合于超级电容器的应用。
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引用次数: 9
Production of Surface Active Organic Material and Reduced Sulfur Species During the Growth of Marine Diatom Cylindrotheca closterium 海洋硅藻生长过程中表面活性有机物和还原性硫的产生
IF 0.3 4区 化学 Q4 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2018-12-30 DOI: 10.5562/CCA3433
I. Ciglenečki, J. Dautović, Ana Cvitešić, G. Pletikapić
Electrochemical methods at the mercury electrode were used for monitoring production of surface active substances (SAS) and reduced sulfur species (RSS) during growth of marine diatom Cylindrotheca closterium isolated from the Adriatic Sea in the laboratory conditions. In the same culture samples, production of particulate and dissolved organic carbon (POC, DOC) was followed by high temperature catalytic oxidation method (HTCO). The culture growth curve obtained by microscopically counted phytoplankton cells showed an exponential growth phase that lasted 10 days, transition phase until 14 days and stationary phase until 21 days. In these time periods twofold increase of SAS and DOC was followed, while POC increased 41 times. Detail analyses of a.c. out of phase voltammetric curves recorded in original and in acidified phytoplankton culture samples indicate transformation of organic material during growth, from more anionic (negatively charged) to less anionic polymeric surface active material. In culture samples presence of non-volatile RSS were confirmed.
采用汞电极电化学方法,在实验室条件下监测亚得里亚海分离的海洋硅藻圆柱体生长过程中表面活性物质(SAS)和还原性硫物质(RSS)的生成。在相同的培养样品中,采用高温催化氧化法(HTCO)生产颗粒和溶解有机碳(POC, DOC)。通过对浮游植物细胞进行显微镜计数得到的培养生长曲线为10 d的指数生长期、14 d的过渡生长期和21 d的固定生长期。在这些时间段内,SAS和DOC增加了2倍,而POC增加了41倍。在原始和酸化浮游植物培养样品中记录的交流非相伏安曲线的详细分析表明,有机物质在生长过程中从更多的阴离子(带负电荷)转变为更少的阴离子聚合表面活性物质。在培养样品中证实了非挥发性RSS的存在。
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引用次数: 5
期刊
Croatica Chemica Acta
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