Hydrothermal Synthesis and Study of Inorganic-Organic Hybrid Vanadate of Nickel(II) Coordination Complex with Pyrazine, Ni3(C4H4N2)3(V8O23)

Artículo científico: postprint

Sintesi hidrotermal bidezko titanio dioxidozko nanohodien lorpena

[EUS] Gaur egun nanozientzia zientzia eta teknologia arlo guztietara zabaldu da, gizarte garapenean eragin handia izan du. Ikerkuntza arlo guztietara zabaldu da ezinezkoak ziruditen erronkak argitu eta ezezagunak ditugun ezagutzak garatzeko asmoz. Lan honetan TiO2 nanohagatxoen sintesia burutu da metodo hidrotermala erabiliz. Sintesi baldintzek lortutako produktuaren egituran eta forman duten eragina kontuan harturik, sintesia gertatzeko ezinbestekoak diren pHa, tenperatura eta denbora aztertu dira. Ondoren, tratamendu kimiko eta termiko ezberdinen bidez konposizio eta egitura ezberdinak lor daitezkeela frogatu da. Bereziki, surfaktante eta pHaren arabera egitura ezberdinak lortzen direla ikusirik. Sintetizatutako laginen karakterizazioa burutzeko X izpien difrakzioa, transmisio bidezko mikroskopia elektronikoa, infragorri espektroskopia, eta termograbimetria teknikak erabili dira. Hauen bidez NaTi3O6·(OH)x·(H2O)y , (TiO2)x(H2O)y , anatasa eta rutilo faseak identifikatu dira, eta nanohagatxoen lodiera eta morfologia ezberdinak ikusi dira.

Síntese, caracterização e estudo da ação antituberculose e citotóxica de hidrazonas derivadas de isoniazida e de seus complexos de cobre(II) e gálio(III)

No presente trabalho é descrita a obtenção de hidrazonas derivadas de isoniazida e de seus complexos de cobre(II) e gálio(III) candidatos a protótipos de fármacos antituberculose e antitumoral. Para investigar o efeito da modificação química sobre as bioatividades do fármaco isoniazida, foram preparados cinco derivados hidrazônicos: 2-piridinocarboxaldeído isonicotinoil hidrazona (HPCIH, 1), 2-acetilpiridina isonicotinoil hidrazona (HAPIH, 2), 2-benzoilpiridina isonicotinoil hidrazona (HBPIH, 3), 2-piridinoformamida isonicotinoil hidrazona (HPAmIH, 4) e 2-pirazinoformamida isonicotinoil hidrazona (HPzAmIH, 5), sendo o composto HPAmIH (4) inédito. Análises de ponto de fusão, espectroscopia de infravermelho (IV), espectrometria de massas, ressonância magnética nuclear (RMN), análise elementar e termogravimetria confirmaram a obtenção e pureza das hidrazonas. Foi determinada ainda a estrutura de HPCIH (1) por difração de raios X de monocristal. Essas moléculas foram efetivas em inibir o crescimento de cepas de micobactérias Mycobacterium tuberculosis H37Rv (ATCC 27294) nas concentrações testadas, com exceção de HPzAmIH (5). As hidrazonas HAPIH (2) e HBPIH (3) foram os compostos orgânicos mais ativos (concentração inibitória mínima, CIM = 0,625 g/mL), apresentando atividade antimicobacteriana apenas duas vezes inferior à do fármaco isoniazida.Quanto à ação contra células tumorais, as hidrazonas HAPIH (2) e HBPIH (3) foram as mais potentes contra as linhagens OVCAR-8 (tumor de ovário - humano), HCT-116 (tumor de cólon - humano) e SF-295 (glioblastoma humano), com inibições de 34,98 a 98,63% do crescimento celular, na concentração de 5 g/mL, enquanto que a isoniazida não foi efetiva contra as linhagens estudadas. Para avaliar o efeito da coordenação a metais sobre a atividade farmacológica das hidrazonas, foram sintetizados os complexos de cobre(II) e gálio(III), sendo todos inéditos: [Cu(HPCIH)Cl2]∙H2O (6), [Cu(HAPIH)Cl2]∙H2O (7), [Cu2(HBPIH)2Cl2]Cl2∙4H2O(8), [Cu(HPAmIH)Cl2]∙H2O (9), [Cu(HPzAmIH)Cl2]∙H2O (10), [Ga(HPCIH)2](NO3)32H2O (11), [Ga(HAPIH)(APIH)](NO3)22H2O (12), [Ga(HPAmIH)(PAmIH)](NO3)22H2O(13) e [Ga(HPzAmIH)(PzAmIH)](NO3)2H2O (14). Os complexos foram caracterizados por espectroscopia de IV, análise elementar, condutivimetria, RMN e espectroscopia eletrônica. Em geral, os complexos também demonstraram ação contra M. tuberculosis, sendo que apenas para 6, 9, 10 e 14 foi verificada melhor atividade em relação às hidrazonas livres. Os complexos metálicos foram tanto quanto ou mais ativos contra as células tumorais OVCAR-8, HCT-116 e SF-295 do que as hidrazonas livres. Merecem destaque os complexos 79 e 12, que apresentaram inibição de crescimento celular de 72,2100%, na concentração de 5 g/mL. Os resultados demonstram portanto que em geral os compostos 114 são menos ativos do que a isoniazida contra M. tuberculosis, enquanto que a modificação química do fármaco, formando-se hidrazonas com posterior complexação cobre(II) e gálio(III) constituíram uma estratégia interessante na obtenção de compostos mais potentes contra células tumorais

Materiais tipo hidrotalcita contendo Cu como precursores de catalisadores para a redução de NO pelo CO

Dentre os óxidos de nitrogênio, o N2O é um gás do efeito estufa altamente nocivo. Devido ao potencial contaminante que este possui, torna-se importante a implementação de processos capazes de reduzir a sua emissão, bem como a dos NOx. Tradicionalmente, têm-se empregado catalisadores baseados em metais nobres, porém estes apresentam como principal desvantagem o elevado custo. Desse modo, sempre houve o interesse pelo uso de outros tipos de catalisadores e metais neste sistema de reação. Nesse contexto, na presente dissertação procurou-se sintetizar precursores de catalisadores tipo hidrotalcita Cu-AlCO3 e avaliar o seu desempenho na reação de redução do NO pelo CO, visando melhorar a atividade e a seletividade a N2. Foram estudados diversos parâmetros de síntese e diferentes composições. Os parâmetros mais influentes na síntese foram a relação molar H2O/(Al+Cu) e a temperatura de secagem do sólido, cujos melhores valores foram 434 e 25C, respectivamente. Testaram-se dois sólidos, o primeiro composto pela fase hidrotalcita quase pura e o segundo com uma clara mistura entre fases hidrotalcita e malaquita. As análises térmica e química revelaram presença da fase malaquita em ambos os materiais com porcentagens de 14 e 40%, respectivamente. Os resultados de difração de raios X indicaram a presença da fase CuO para os catalisadores provenientes da calcinação dos materiais tipo hidrotalcita, porém a espectroscopia Raman evidenciou a presença de Cu2O no catalisador proveniente do material com maior mistura de fases. Os ciclos redox mostraram uma melhora na redutibilidade dos catalisadores após um ciclo de oxidação-redução. Além disso, foi estudado o impacto do envelhecimento térmico a 900C por 12 h no desempenho dos catalisadores. Pelos resultados de teste catalítico os melhores desempenhos foram alcançados pelos catalisadores envelhecidos, contudo o catalisador proveniente do precursor mais puro apresentou-se melhor tanto novo como envelhecido em termos de menor rendimento de N2O. Uma comparação com catalisadores à base de metal nobre mostrou um bom desempenho dos catalisadores à base de cobre, com a vantagem destes apresentarem menor emissão de N2O em temperaturas menores

分子运动性预测顽拗性种子麻栎离体胚轴适宜贮藏条件初探

顽拗性种子在分类上分布广泛。由于顽拗性种子贮藏特性极为特殊，对脱水和低温均十分敏感，易受损伤，所以种子寿命很短，因此在植物种质资源保存领域，顽拗性种子的保存一直被列为重点研究课题，至今仍难以找到顽拗性种子的适宜贮藏条件，或该类种子保存通行的方法，仅推测长期保存顽拗性种子种质资源最有前途的方式是超低温保存，顽拗性种子资源保存是一个世界性难题。 本文试图使用分子运动性预测顽拗性种子离体胚轴的适宜贮藏条件。选用壳斗科植物麻栎种子为实验材料。应用电子顺磁共振波谱仪和自旋标记技术，以硝基氧探针CP为标记物，检测到室温下麻栎种子离体胚轴脱水过程中分子运动性的变化。含水量0.7 g H2O/g DW至0.64 g H2O/g DW范围是细胞质粘度的转折区域，低于这个含水量区域，细胞质粘度骤然上升，推测这个区域是室温下保存离体胚轴的适宜含水量下限。 通过变温电子顺磁测定，找到离体胚轴含水量在0.43 g H2O/g DW至1.02 g H2O/g DW范围内，分子运动性的临界温度和玻璃态相变温度所在区间。根据分子运动性随温度变化规律，预测含水量为0.69 g H2O/g DW的麻栎种子离体胚轴适宜贮藏温度约为-50 ℃。 根据EPR实验结果，将胚轴脱水，并根据实验条件选择不同温度进行低温贮藏验证实验，应用颜色观测法和TTC存活力鉴定法，初步验证分子运动性理论可以应用在顽拗性种子离体胚轴的低温贮藏研究中。 本研究说明顽拗性种子资源的保存有可能通过离体胚轴的低温贮藏实现，用分子运动性预测低温贮藏的适宜条件，很可能为上述问题的解决提供了有效的技术参数。

Role of transglutaminase-mediated cross-linking of protein in the temperature-dependent setting of Alaska pollack surimi

During the low temperature setting of fish paste, myosin heavy chain (MHC) is polymerized to cross-linked myosin heavy chain (CMHC), which is considered to occur by the action of endogenous transglutaminase (TGase). In this study the contribution of TGase on the setting of Alaska pollack surimi at different temperatures was studied. Alaska pollack surimi was ground with 3% NaCl, 30% h2o and with or without ethylene glycol bis (β-aminoethylether) N, N, N¹,N¹- tetra acetic acid (EGTA), an inhibitor of TGase. Among the pastes without EGTA, highest TGase activity was observed at 25°C but breaking force of the gel set at 25°C was lower than that set at 30°, 35°, and 40°C. Addition of EGTA (5m mol/kg) to the paste suppressed TGase activity at all setting temperatures from 20° to 40°C. Gelation of the pastes and cross-linking of MHC on addition of EGTA were suppressed completely at 20° and 25°C, partially at 30° and 35°C, and not at all at 40°C. The findings suggested that during the setting of Alaska pollack surimi TGase mediated cross-linking of MHC was strong at around 25°C but the thermal aggregation of MHC by non-covalent bonds was strong at above 35°C. Setting of surimi at 40°C and cross-linking of its MHC did not involve TGase.

干莲胚芽叶在萌发过程中叶绿体膜结构和功能的研究

本工作对莲胚芽叶在照光萌发后其叶绿体光合膜结构和功能的发育作了比较系统的研究。主要结果如下： （1）在萌发前的干莲胚芽叶叶绿体中就已存在有巨型基粒结构。经照光萌发后，巨型基粒逐渐松散，类囊体膜之间距离变大。巨型基粒解体。而后重新形成比原来巨型基粒片层少，片层间距较紧密的基粒。它的基质片层是在基粒片层形成基本完成之后开始发育的，即萌发八天之后，莲幼苗叶绿体才形成和其它高等植物成熟叶绿体类似的结构，具有基粒和基质片层的类囊体膜系统。 （2）对萌发后不同时期莲幼苗叶绿体膜多肽SDS-PAGE凝胶电泳分析表明，组成光系统Ⅱ捕光色素蛋白复合体的两个多肽，分子量分别为30 KD和27 KD的多肽含量变化很大。30 KD常会随发育时间的增长而减弱。而27 KD条带则逐渐增强。光系统Ⅱ捕光色素蛋白复合体在干莲胚芽叶叶绿体中以前体的形式存在，经照光萌发一段时间后，该复合体经过多肽含量的变化，叶绿素a、b相对含量的变化等过程，最后发育成熟的光系统Ⅱ捕光色素蛋白复合体。 （3）萌发前及萌发后不同时期对莲叶绿体的低温荧光发射光谱测定结果表明，未经萌发和照光萌发两天的莲叶绿体仅在681mm处有发射峰，而缺少732 nm处的发射峰。萌发到第四天时F732开始出现，并且随发育时间增长逐渐增强。F732/F683值逐渐上升，这说明PSI捕光色素系统的发育较PSⅡ是延后的，而且它的发育必须有可见光照射条件下才能进行。 （4）叶绿素a/b值和吸收光谱测试结果表明，莲胚芽叶在萌发后的发育过程中，其叶绿体叶绿素a/b值由干莲胚芽叶叶绿体的0.9逐渐上升，到萌发十天时接近正常成熟叶绿体的水平，其叶绿体在红光区的吸收峰，叶绿素b相对于叶绿素a逐渐减弱。 （5）干莲胚芽叶萌发过程中，其叶绿体的活体室温荧光动力学测定结果表明，在萌发四天后，Fv开始出现，Fv/Fo值随照光萌发时间增长而逐渐提高。从H2O → DCIP的电子传递速率的测定结果也证明PSⅡ光化学活性的出现和增强过程。 我们的结果表明，干莲胚芽叶叶绿体在萌发后经历了一条和其它高等植物差异很大的发育途径，我们的结果也证实了LHCP与基粒形成有密切联系。

光合放氧结构与机理的理论探索

光合放氧研究近十年来已有重要进展，但在该领域仍有很多重要问题待研究。本论文工作主要是对光系统氧化侧与光合放氧密切相关的组分的结构和性能进行理论和模拟研究，工作可概括如下： (一)、放氧中心结构和性能的探索。 1、对放氧中心Mn202单元与配体组氨酸、H2O和Cl等结合方式的理论研究显示：(a)、组氨酸和H20分子均可能与Mn202平面垂直，彼此保持较大的距离，且结合在不同的Mn离子上;(b)、2个H2O分子可能结合在不同Mn202单元上。 2、对Mn簇核心骨架的理论研究显示有必要引入新的Ca、Cl结合方式，以防止因两个Mn202单元线性化而导致2个H2O分子结合位点远离。 (二)、次级电子给体Tyr_z和Tyr_D的结构与功能。 对次级电子给体Tyr_z和Tyr_D进行精确量子化学研究显示：(a)、在中性条件下，Tyr_D和Tyr_z均只与组氨酸通过氢键作用;(b)、当失去电子后，结构发生明显变化，导致正电荷主要集中在组氨酸上，自由基主要集中在Tyr上;(c)、第三组分(H_20分子或羧基等)的引入使中性体系不容易给出电子;(d)、结合最新文献报导，推测Tyr_D~+和Tyr_z~+除与组氨酸作用外还可能分别与水和羧基作用。 (三)、原初电子给体的理论和模拟研究。 1、对紫细菌原初电子给体P_(870)的理论研究显示：(a)、双分子结构比单分子结构稳定;(b)、电荷分离之后，原初电子给体原有的空间结构不再是稳定的构型，它会向能量和化学活性均更低的构型转变。在光合细菌的原初电子给体P870中，这种转变可通过C3位的乙酰基旋转使其氧原子与另一个细菌叶绿素分子的镁原子相互作用使P870+•的总能量和化学活性明显降低。推测这种构型转变对于防止原初反应过程中的电荷重组、维持光能的高效转化有重要意义。提出了原初反应过程中结构动态变化的新观点，利用这一观点可对光合细菌原初反应动力学研究所观测到的慢过程及蛋白质微环境对原初电子给体和原初反应都有重要影响等实验现象给予较好的解释。 2、对光系统II原初电子给体P680的结构进行理论探讨，提出了两个叶绿素a分子平面间夹角为50.0±2.5°时能量最低的夹角模型。 3、采用N-甲基咪唑(C4H6N2)模拟生物体内的组氨酸，通过观测CCL4中的Chla与C4H6N2反应的吸收、CD和MCD光谱得到以下结论：(a)、在纯CCL4中，每个Chla处于5配位状态，Chla形成不对称的双聚体，彼此之间存在较强的偶合作用。提出两个Chla通过不等价的2个Mg-O配位键(O分别来自于C131位的酮基和C17位酯基的C=O)连接为紧密双体结构;(b)、当C4H6N2／Chla = 0.5和1时，其吸收、CD和MCD光谱均发生明显变化，两个Chla之间的偶合作用明显减弱，但此时仍为双聚体。推测C4H6N2首先取代原紧密双体结构中Mg-O酯键，进而取代Mg-O酮键，最后两个Chla分子通过两个Mg…O弱相互作用连接为松弛的双体结构，该模型与理论获得的P_(680)的结构相似。 在上述研究的基础上，提出了包括放氧中心外围配体和TyrZ在内的放氧中心结构新模型。在新结构模型中，2个H2O分子不对称地结合于“C”形结构开口端两个低价的Mn1II和Mn4III上，并保持较大距离;两个组氨酸的咪唑环通过N原子与两个高价的Mn2IV、Mn3IV结合;Cl结合于MB4TM，并与Ca相连;Ca通过O桥和COO-相连使两个Mn202单元保持特定空间构型。TyrZ通过组氨酸(D1-His190)与Mn簇作用。此外，新模型尝试着在O桥上引入质子。放氧中心结构及其邻近环境(包括TyrZ和TyrD)整体处于中性状态。 同时还提出了新的放氧机理，认为电子和质子的释放非同步进行，并首次明确提出两个水分子的不对称氧化和结构动态变化等观点。认为Ca在维持放氧中心的结构方面担负重要作用，C1与Mn离子之间的亲核作用变化是放氧中心结构变化的关键。

黄芩甙锌配合物药物用途

本发明公开了配合物黄芩甙锌在制备预防和治疗艾滋病的药物中的应用，其结构式见图1，分子式为ZnC23O13H20(1-3.5)H2O。黄芩甙与黄芩甙锌均能抑制HIV-1感染细胞与正常细胞间的融合，但黄芩甙锌的细胞毒性低于黄芩甙，对HIV-1的治疗指数(TI)高于黄芩甙，其治疗效果比黄芩甙好。

肝素钠树脂精制工艺的研究

利用D254树脂可以将原始粗品肝素钠的效价提高到179. 8 U SP U öm g, 进一步纯化可得201. 5 U SP U öm g 的精品, 其H2O 2 用量(1. 5% ) 和氧化时间(24 h) 均少于传统工艺, 产品光吸收和收率(85. 8% ) 最优。

Growth window and possible mechanism of millimeter-thick single-walled carbon nanotube forests.

Our group recently reproduced the water-assisted growth method, so-called "SuperGrowth", of millimeter-thick single-walled carbon nanotube (SWNT) forests by using C2H4/H2/H2O/Ar reactant gas and Fe/Al2O3, catalyst. In this current work, a parametric study was carried out on both reaction and catalyst conditions. Results revealed that a thin Fe catalyst layer (about 0.5 nm) yielded rapid growth of SWNTs only when supported on Al2O3, and that Al2O3 support enhanced the activity of Fe, Co, and Ni catalysts. The growth window for the rapid SWNT growth was narrow, however. Optimum amount of added H2O increased the SWNT growth rate but further addition of H2O degraded both the SWNT growth rate and quality. Addition of H2 was also essential for rapid SWNT growth, but again, further addition decreased both the SWNT growth rate and quality. Because Al2O3 catalyzes hydrocarbon reforming, Al2O3 support possibly enhances the SWNT growth rate by supplying the carbon source to the catalyst nanoparticles. The origin of the narrow window for rapid SWNT growth is also discussed.

A high performance oxygen storage material for chemical looping processes with CO2 capture

Chemical looping combustion (CLC) is a novel combustion technology that involves cyclic reduction and oxidation of oxygen storage materials to provide oxygen for the combustion of fuels to CO2 and H2O, whilst giving a pure stream of CO2 suitable for sequestration or utilisation. Here, we report a method for preparing of oxygen storage materials from layered double hydroxides (LDHs) precursors and demonstrate their applications in the CLC process. The LDHs precursor enables homogeneous mixing of elements at the molecular level, giving a high degree of dispersion and high-loading of active metal oxide in the support after calcination. Using a Cu-Al LDH precursor as a prototype, we demonstrate that rational design of oxygen storage materials by material chemistry significantly improved the reactivity and stability in the high temperature redox cycles. We discovered that the presence of sodium-containing species were effective in inhibiting the formation of copper aluminates (CuAl2O4 or CuAlO 2) and stabilising the copper phase in an amorphous support over multiple redox cycles. A representative nanostructured Cu-based oxygen storage material derived from the LDH precursor showed stable gaseous O2 release capacity (∼5 wt%), stable oxygen storage capacity (∼12 wt%), and stable reaction rates during reversible phase changes between CuO-Cu 2O-Cu at high temperatures (800-1000 °C). We anticipate that the strategy can be extended to manufacture a variety of metal oxide composites for applications in novel high temperature looping cycles for clean energy production and CO2 capture. © The Royal Society of Chemistry 2013.

Thermogravimetric study on the hydration of reactive magnesia and silica mixture at room temperature

The synthesis of magnesium silicate hydrate (MSH), which has wide applications in both construction and environmental fields, has been studied for decades. However, it is known that the characteristics of magnesia (MgO) vary significantly depending on their calcination conditions, which is expected to affect their performance in the MgO-SiO2-H2O system. This paper investigated the effect of different MgO and silica sources on the formation of magnesium silicate hydrate (MSH) at room temperature. The hydration process was studied by mixing commercial reactive MgO and silica powders with water and curing for 1, 7 and 28 days. The hydration products were analysed with the help of X-ray diffraction (XRD) and thermogravimatric analysis (TGA). The results showed the continuous consumption of MgO and the existence of MSH and brucite and other minor phases such as magnesite and calcite. It is found that the Mg and Si sources have significant effect on the hydration process of MgO-SiO2-H2O system. The reaction degree is controlled by the availability of dissolved Mg and Si in the solution. The former is determined by the reactivity of MgO and the latter is related to the reactivity of the silica as well as the pH of the system. © 2013 Elsevier B.V. All rights reserved.

Characterization of light and heavy hydrated magnesium carbonates using thermal analysis

Upon heating, hydrated magnesium carbonates (HMCs) undergo a continuous sequence of decomposition reactions. This study aims to investigate the thermal decomposition of various commercially produced HMCs classified as light and heavy, highlight their differences, and provide an insight into their compositions in accordance with the results obtained from thermal analysis and microstructure studies. An understanding of the chemical compositions and microstructures, and a better knowledge of the reactions that take place during the decomposition of HMCs were achieved through the use of SEM, XRD, and TG/differential thermal analysis (DTA). The quantification of their CO 2 contents was provided by TG and dissolving the samples in HCl acid. Results show that variations exist within the microstructure and decomposition patterns of the two groups of HMCs, which do not exactly fit into the fixed stoichiometry of the known HMCs in the MgO-CO2-H2O system. The occurrence of an exothermic DTA peak was only observed for the heavy HMCs, which was attributed to their high CO2 contents and the relatively delayed decomposition pattern. © 2013 Akadémiai Kiadó, Budapest, Hungary.

Detection of the hepatotoxic microcystins in 36 kinds of cyanobacteria Spirulina food products in China

Gel filtration chromatography, ultra-filtration, and solid-phase extraction silica gel clean-up were evaluated for their ability to remove microcystins selectively from extracts of cyanobacteria Spirulina samples after using the reversed-phase octadecylsilyl ODS cartridge for subsequent analysis by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). The reversed-phase ODS cartridge/silica gel combination were effective and the optimal wash and elution conditions were: H2O (wash), 20% methanol in water (wash), and 90% methanol in water (elution) for the reversed-phase ODS cartridge, followed by 80% methanol in water elution in the silica gel cartridge. The presence of microcystins in 36 kinds of cyanobacteria Spirulina health food samples obtained from various retail outlets in China were detected by LC-MS/MS, and 34 samples (94%) contained microcystins ranging from 2 to 163 ng g(-1) (mean=1427 ng g(-1)), which were significantly lower than microcystins present in blue green alga products previously reported. MC-RR-which contains two molecules of arginine (R)-(in 94.4% samples) was the predominant microcystin, followed by MC-LR-where L is leucine-(30.6%) and MC-YR-where Y is tyrose-(27.8%). The possible potential health risks from chronic exposure to microcystins from contaminated cyanobacteria Spirulina health food should not be ignored, even if the toxin concentrations were low. The method presented herein is proposed to detect microcystins present in commercial cyanobacteria Spirulina samples.