磷酸铜微纳米材料的制备及其光热转换性能的研究

发布时间：2018-03-03 11:49

本文选题：磷酸铜　切入点：光热转换　出处：《青岛科技大学》2017年硕士论文　论文类型：学位论文

【摘要】：光热转换材料是能够将光能转换为热能的材料,目前主要应用于太阳能光热转换及肿瘤光热治疗两个领域。由于可见光谱区和红外光谱区的能量分别占据了太阳光总辐射能量的约50%和43%,且可见光与近红外光对生物组织的穿透能力更强,更容易实现深层癌组织的高效杀伤,因此能够响应可见光-近红外光的光热转换材料是这两个领域的研究热点。基于过渡金属铜离子3d电子的d-d跃迁,本文设计并成功制备了一种新型的可见光-近红外光响应的磷酸铜(copper phosphates,Cu POs)光热转换材料,该材料能够强烈吸收400-1200 nm波段的可见光和近红外光能量,并将该波段的光能高效转换为热能。在此基础上,本文对所制备的磷酸铜光热转换材料进行了光热转换效率的测试及光热转换机理的研究,并探索了该材料在太阳能光热海水淡化和肿瘤光热治疗中的应用。具体研究内容主要包括以下几个方面:1、磷酸铜新型光热转换材料的制备、光热转换性能及机理研究。(1)通过水热法和溶剂热法合成了形貌分别为片状、花球状和球状的三种磷酸铜。其中片状磷酸铜为厚度约2 nm、长度和宽度几十到几百纳米不等的薄片;花球状磷酸铜为直径约3-5μm,具有多级结构的花球状微米颗粒;球状磷酸铜为粒径140-160 nm的球形纳米颗粒。(2)使用波长为808 nm的近红外光对上述三种不同形貌的磷酸铜材料进行了光热转换性能的测试,计算了其对808 nm近红外光的光热转换效率。研究了微观形貌对所制备材料光热转换性能的影响,结果表明,这三种不同形貌的磷酸铜材料对808 nm近红外光的光热转换效率?1分别为30.85%、41.8%和34.6%,其中花球状磷酸铜由于具有多级结构,光线入射后能够在纳米片“花瓣”之间多次反射、折射,从而表现出比片状和球状磷酸铜微纳米材料更加优异的光吸收能力和光热转换性能。(3)通过对磷酸铜微纳米材料固体漫反射光谱的研究,计算了磷酸铜的禁带宽度,提出了基于Cu~(2+)中3d电子d-d跃迁的光热转换机理。2、磷酸铜光热转换材料在太阳能光热海水淡化中的应用研究。(1)选取对808 nm近红外光光热转换效率最高的花球状磷酸铜与低表面能材料聚二甲基硅氧烷(polydimethylsiloxane,PDMS)进行复合,制得具有自漂浮性能的Cu POs-PDMS光热膜片。借助砂纸的粗糙表面,进一步提高了光热膜片的憎水性,制得与水的表观接触角为124.0o的Cu POs-PDMS膜片,实现了该光热膜片在水面的自漂浮,成功地将光照下磷酸铜所产生的热量集中于空气-水界面处,进而加速了水分在空气-水界面处的蒸发。(2)以质量分数为3.5%的Na Cl水溶液为模拟海水,使用功率密度为1000W/m2的模拟太阳能光源,研究了Cu POs-PDMS光热膜片对水蒸发速率的影响。结果表明,在功率密度为1000 W/m2的模拟太阳能光源照射条件下,Cu POs质量分数为40%的有孔Cu POs-PDMS膜片能够将模拟海水的水蒸发速率提升至1.01 kg·m-2·h-1,光热转换效率?2达63.6%,是未使用光热材料条件下的1.71倍,充分表明Cu POs-PDMS光热膜片能够有效提高太阳能光热海水淡化的效率。3、磷酸铜光热转换材料在肿瘤光热治疗中的应用研究。以粒径较小、易于实现细胞吞噬的球状磷酸铜纳米颗粒为光热治疗剂,以人宫颈癌细胞(HeLa细胞)为细胞模型,研究了该材料在肿瘤光热治疗中的应用。结果表明,将HeLa细胞与浓度为125μg/m L的球状磷酸铜共培养2 h,并经功率密度为0.1 W/cm2和0.3 W/cm2的808 nm激光照射5 min后,细胞存活率可由光照前的86.9%分别下降至77%和40%左右,说明球状磷酸铜作为光热治疗剂能够将808 nm近红外光的能量有效转换为热量来杀死癌细胞。4、磷酸铜微纳米材料的过氧化物酶模拟活性研究。本文发现所制备的磷酸铜微纳米材料除了具有优异的光热转换性能以外,还具有过氧化物酶模拟活性。(1)以3,3',5,5'-四甲基联苯胺(TMB)-H_2O_2反应体系为模型,研究了磷酸铜微纳米材料的过氧化物酶模拟活性。结果发现,所制备的磷酸铜材料能够如天然过氧化物酶一样催化TMB与H_2O_2之间的氧化还原反应,加速反应体系的显色反应,证明该材料具有过氧化酶模拟活性。pH值对磷酸铜的模拟酶活性具有显著影响,当反应介质的pH约为3.2时,其模拟酶活性最强。(2)利用磷酸铜的过氧化物酶模拟活性,以磷酸铜微纳米材料代替天然过氧化物酶为催化剂,实现了水溶性导电聚噻吩(PEDOT)的仿酶绿色合成。(3)采用鲁米诺化学发光法,研究了磷酸铜微纳米材料具有过氧化物模拟酶的机理。结果表明,只有在H_2O_2存在的条件下,磷酸铜才能够使得鲁米诺产生化学发光,这说明磷酸铜是通过催化H_2O_2分解产生可氧化鲁米诺的氧自由基,进而表现出过氧化物酶模拟活性的。(4)利用磷酸铜的过氧化物酶模拟酶活性,研究了磷酸铜在氧化应激癌症治疗中的应用。HeLa细胞在与125μg/m L的磷酸铜纳米球共培养2 h后其细胞增殖率约为86.9%,而在继续与1.25 m M的H_2O_2共培养2 h后,其细胞增殖率下降为49.8%,说明HeLa细胞吞噬的磷酸铜纳米颗粒能够在细胞内通过分解H_2O_2产生氧自由基的方式来有效杀伤癌细胞。该方法与光热治疗联用,可进一步提高对癌细胞的杀伤效率。
[Abstract]:The conversion material is able to convert light energy to heat the material, mainly used in solar energy conversion and tumor photothermal therapy in two areas. Due to the visible region of the spectrum and infrared region energy respectively occupy the total solar radiation energy of about 50% and 43%, and the visible light and near infrared spectra of biological tissue penetrating ability a stronger, more easily achieve efficient killing deep cancer tissue and therefore can respond to visible and near infrared photothermal conversion material is a hot research field. The two D-D transition metal 3D based on the design of copper phosphate and a visible model was prepared successfully by near infrared response the (copper phosphates, Cu POs) the conversion material, the material can strongly absorb 400-1200 nm visible light and near infrared energy, and the energy band, is converted to heat. On this basis, the copper phosphate prepared by photothermal conversion material of photothermal conversion efficiency and testing mechanism of photothermal conversion and explored the application of the material in the solar thermal desalination and cancer photothermal therapy. The specific research includes the following aspects: 1, copper phosphate conversion model material preparation, thermal properties and mechanism research. (1) by hydrothermal and solvothermal synthesis were respectively three phosphoric acid copper flake, curd like and spherical. The sheet copper phosphate for thickness of about 2 nm, slice length and width of tens to hundreds of nanometers; copper phosphate. The bouquet is about 3-5 m in diameter, with a multi-level structure of ball flower shaped micron particles; spherical copper phosphate for spherical nanoparticles with particle size of 140-160 nm. (2) the use of near infrared wavelength is 808 nm for the three kinds of different morphologies of the copper phosphate Materials for the photothermal conversion performance test, the calculation of 808 nm near-infrared photothermal conversion efficiency. Study the effect of microstructure on the prepared materials, photothermal conversion performance results show that the three different morphologies of copper phosphate materials of 808 nm near-infrared photothermal conversion efficiency was 30.85%? 1. 41.8% and 34.6%, including copper phosphate with globular flower like hierarchical structure, the incident light can in the nano petal between multiple reflection, refraction, thus showing convergence ability and photothermal conversion absorption properties than flake and spheroidal copper phosphate micro nano materials with more excellent light. (3) through the research on micro nano copper phosphate solid diffuse reflectance spectra, the band gap copper phosphate was calculated based on Cu~ (2+) 3D D-D electronic transitions of photothermal conversion mechanism of.2 copper phosphate conversion material in solar thermal desalination The application of research. (1) the selection of the 808 nm near infrared photothermal conversion efficiency of the highest ball flower shaped copper phosphate and low surface energy materials two polydimethylsiloxane (polydimethylsiloxane, PDMS) compound, prepared with self floating performance Cu POs-PDMS rough surface with sandpaper. Thermal diaphragm, further improves the hydrophobicity of thermal the diaphragm was prepared with water, the apparent contact angle is Cu POs-PDMS 124.0o to realize the self diaphragm, the diaphragm floating on the surface of the heat, successfully light copper phosphate heat generated by the focus on the air / water interface, and then accelerate the evaporation of moisture in the air / water interface. (2) with the mass fraction of water Na 3.5% Cl solution for simulated seawater, using power density for simulation of solar 1000W/m2 light source, the effects of Cu POs-PDMS on thermal diaphragm water evaporation rate. The results show that the power density of 1000 W/m2 Simulation of solar light irradiation under the condition of Cu, the mass fraction of POs was 40% Cu POs-PDMS with a hole in the diaphragm can simulate the water evaporation rate will increase water to 1.01 kg - m-2 - H-1, the thermal efficiency of up to 63.6%? 2, is 1.71 times without the use of photothermal material under the condition of Cu shows that POs-PDMS can effectively improve the thermal diaphragm the efficiency of.3 solar thermal desalination, application of copper phosphate conversion material in tumor photothermal therapy. With smaller particle size, easy to realize the phagocytosis of globular phosphate copper nanoparticles as photothermal therapeutic agent in human cervical cancer cells (HeLa cells) cell model, studies the application of the material in tumor photothermal therapy in. The results showed that the HeLa cells and the concentration of spherical copper phosphate 125 g/m L were cultured for 2 h, and the power density of 808 nm laser irradiation of 0.1 W/cm2 and 0.3 W/cm2 after 5 min, the cell survival rate by Light in front of 86.9% decreased to 77% and 40%, indicating the spherical copper phosphate as photothermal therapeutic agent can 808 nm near infrared energy efficient conversion of heat to kill cancer cells.4, peroxidase activity of simulated copper phosphate micro nano materials. In this paper, it was found that copper phosphate prepared by micro nano materials has excellent photo thermal conversion properties, but also has simulated peroxidase activity. (1) 3,3', 5,5'- four methyl benzidine (TMB) -H_2O_2 reaction system as a model of peroxidase copper phosphate micro nano materials simulation activity. The results showed that the copper phosphate material prepared to oxidation such as natural peroxidase TMB and H_2O_2 like catalytic reduction reaction, accelerate the chromogenic reaction reaction system, proved that the peroxidase activity of.PH material simulation simulation on the enzyme activity of copper phosphate has significant effect with, When the reaction medium pH is about 3.2, its strongest simulation activity. (2) simulated by peroxidase activity copper phosphate, phosphate copper micro nano materials to replace natural peroxidase as catalyst, the water soluble conducting polythiophene (PEDOT) biomimetic synthesis of green (3) by Lumino chemical. Study on the chemiluminescence method, copper phosphate micro nano materials with mechanism of mimetic peroxidase. The results showed that only in the presence of H_2O_2, copper phosphate can make Lumino produce chemiluminescence, which is catalyzed by copper phosphate H_2O_2 decomposition to produce oxygen free radicals can oxidize Lumino, and then demonstrate the simulation of peroxidase activity. (4) simulated enzyme activity using peroxidase copper phosphate, were studied using.HeLa cell copper phosphate on oxidative stress in the treatment of cancer in copper phosphate nanoparticles and 125 g/m L 2 h after co culture of the fine The cell proliferation rate is about 86.9%, while in the co cultured with 1.25 m M to 2 H_2O_2 after h, the cell proliferation rate decreased to 49.8%, indicating phosphate copper nanoparticles of HeLa cell phagocytosis in cells through the decomposition of H_2O_2 can produce oxygen free radicals to effectively kill cancer cells. The method and thermal therapy use, can further enhance the cancer cell killing efficiency.

【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36

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