Use of coaxial photocatalytic reactor (CAPHORE) in the TiO2 photo-assisted treatment of mixed E. coli and Bacillus sp. and bacterial community present in wastewater

This paper reports the photocatalytic disinfection of water contaminated by a mixture of Escherichia coli and Bacillus sp. as well as that of wastewater containing a larger microbial community. The photocatalytic reactions were carried out in a coaxial photocatalytic reactor called CAPHORE, using TiO₂ P-25 of Degussa. E. coli is more sensitive than Bacillus sp. to photocatalytic treatment. Bacterial inactivation was dependent on organic matter and dissolved oxygen (DO) concentration.

Of the bacterial community present in partially treated wastewater, E. coli appears to be more sensitive to the treatment than Enterococcus sp., coliforms (other than E. coli), and Gram-negative (other than coliforms). After photocatalytic treatment, no bacterial recovery of previous groups was observed for 24 h in the dark. However a very low bacterial inactivation rate was observed for the whole bacterial population present in wastewater and detected by non-selective media. The effective disinfection time (EDT), the time necessary for total inactivation of bacteria without re-growth in a subsequent dark period referenced at 24 h (or 48 h), was reached only for Enterococcus sp., and coliform groups. EDT₂₄ was not reached for the whole population.     

壳聚糖双胍盐酸盐络合碘制备及抑菌性能

以壳聚糖(CTS)和双氰胺为原料, 在一定温度下通过亲核加成合成壳聚糖双胍盐酸盐(CGH)衍生物, CGH与不同浓度的碘乙醇溶液制备改性壳聚糖的碘络合物(CGH-I₂)。用IR光谱、XRD、TG和DTG对衍生物进行表征, 通过碘量法测CGH与碘络合的质量比。碘含量分析表明:碘乙醇溶液浓度为0.02mol/L 时, CGH与碘络合的最大质量比为m(CGH):m(I₂)=1:0.46。抑菌性测试表明:CGH-I₂对大肠杆菌和金黄色葡萄球菌抑菌环直径分别为(18±1)mm和(21±1)mm, 敏感度均为高度敏感。     

化香果提取物体外抑菌活性研究

研究了化香果提取物对水产常见9种致病菌嗜水气单胞菌（Aeromonas hydrophila）、温和气单胞菌（Aeromonas sobria）、豚鼠气单胞菌（Aeromonas caviae）、维氏气单胞菌（Aeromonas veronii）、迟钝爱德华菌（Edwardsiella tarda）、副溶血弧菌（Vibrio parahaemolyticus）、鼠疫耶尔森氏菌（Yersinia pestis）、大肠杆菌（Escherichia coli）和金黄色葡萄球菌（Staphylococcus aureus）的抑菌活性。研究结果表明：化香果提取物对9种细菌均具有抑制作用,最小抑菌浓度为4.50 g/L。对每种细菌而言,抑菌效果随化香果提取物质量浓度的增加而增强,其中对大肠杆菌的抑制能力最强,IC₅₀值为0.035 g/L;金黄色葡萄球菌次之,IC₅₀值为0.053 g/L。对雌雄小鼠急性经口毒性试验结果表明化香果提取物对小鼠的急性经口半数致死量（LD₅₀值）分别为5 010和7 940 mg/kg体质量,表明化香果提取物属于实际无毒级。     

桑叶乙醇提取物的体外抗氧化与抑菌活性

采用索氏提取法对干桑叶进行提取,得到乙醇提取物,并对提取物的组分以及体外抗氧化活性和抑菌活性进行了测定。研究结果表明：桑叶乙醇提取物中含有多种有机物,主要包括酯类(82.85%)、烷烃类(6.31%)、芳烃类(1.62%)和醇类(0.21%)。桑叶乙醇提取物总还原力与浓度有显著的线性关系;对DPPH自由基和OH自由基都有良好的清除能力,半数抑制浓度(IC₅₀)分别为73.07和104.52 mg/L。桑叶乙醇提取物对枯草芽孢杆菌、金黄色葡萄球菌和大肠杆菌均具有一定的抑制作用,抑制效果为枯草芽孢杆菌＞金黄色葡萄球菌＞大肠杆菌,IC₅₀分别为4.824、6.806和14.382 g/L。桑叶乙醇提取物的抗氧化活性和抑菌活性随样品浓度的增大而增大。     

Photocatalytic inactivation of Escherischia coli: Effect of concentration of TiO2 and microorganism, nature, and intensity of UV irradiation

The efficiency of photocatalytic disinfection, used to inactivate Escherischia coli K12 under different physico-chemical parameters, was examined. The photocatalyst chosen was the semiconductor TiO₂ degussa P25 and the irradiation was produced by an HPK 125 lamp. The effect of titania concentration was investigated using two E. coli concentrations. The photocatalyst concentration ranged from 0.1 to 2.5 g/L. The evolution of E. coli inactivation as function of time was discussed depending on the E. coli and TiO₂ concentrations. The optimal concentration of the photocatalyst, 0.25 g/L, is lower than that necessary to absorb all photons and to degrade the organic compounds. Some hypotheses are presented to explain this behaviour. The effect of the different domains of UV light (UVA, UVB, and UVC) was also studied and modification of the light irradiation intensity is discussed. No bacteria photolysis was obtained with UVA but the use UVC had, on the contrary, a detrimental effect on bacteria survival. The addition of titania at a low concentration, 0.25 g/L, improved the inactivation of E. coli in the presence of UVA and UVB, but a detrimental effect was observed under UVC. The disinfection efficiency increases as a function of light intensity, whatever the photocatalytic conditions (different TiO₂ concentrations and different UV domains). No bacterial growth was observed after disinfection, whether the system contained titania or not.     

Efficient destruction of pathogenic bacteria with AgBr/TiO2 under visible light irradiation

The photocatalytic inactivation of pathogenic bacteria in water was investigated systematically with AgBr/TiO₂ under visible light (λ > 420 nm) irradiation. The catalyst was found to be highly effective for the killing of Escherichia coli, a Gram-negative bacterium, and Staphylococcus aureus, a Gram-positive bacterium. The decomposition of the cell wall and cell membrane was directly observed by TEM and further confirmed by K⁺ leakage from the inactivated bacteria. A possible cell damage mechanism by visible light-driven AgBr/TiO₂ is proposed. In addition, the effects of pH, inorganic ions on bacterial photocatalytic inactivation were investigated. The electrostatic force interaction of the bacteria–catalyst is crucial for the efficiency of disinfection. Moreover, AgBr/TiO₂ supported on porous nickel showed much higher bactericidal activity than fixed P25 TiO₂ under visible or near UV light irradiation.     

微孔聚丙烯膜表面壳聚糖季铵盐的共价修饰及其抗菌性能

为了赋予微孔聚丙烯膜（MPPM）抗菌能力,增强其抗污染性能,本文通过丙烯酸的光引发接枝聚合、壳聚糖与聚丙烯酸的酰胺化反应、壳聚糖胺基与2,3-环氧丙基三甲基氯化铵的开环加成,成功地在MPPM膜表面通过共价修饰技术构建了壳聚糖季铵盐修饰层。构建过程通过FTIR、XPS和荧光素二钠盐染色分析得到了证实。静态水接触角和吸水量实验结果表明,制得的修饰膜具有优异的表面润湿性和吸水性,吸水量可达11.23mg/cm²,为未修饰MPPM的1123倍。以大肠杆菌和金黄色葡萄球菌为代表,采用平板活菌计数法考察了修饰膜的抗菌性能和抗菌稳定性。研究结果表明,修饰膜具有良好的抗菌活性,对大肠杆菌的抗菌率可达98%,对金黄色葡萄球菌的抗菌率可达100%,且抗菌效果稳定,在水处理领域具有潜在的应用前景。     

载银TiO2/碳纳米管复合材料的制备及其催化杀菌性能

采用溶胶-凝胶法, 在450℃下煅烧制备载银TiO₂/碳纳米管纳米复合材料;采用XRD、SEM以及N₂吸脱附对样品的晶体结构及样品微观形貌进行表征;通过UV-vis漫反射光谱表征了复合材料对紫外可见光的吸收性能;以甲基橙为模型污染物, 评价了样品紫外光光催化降解甲基橙的活性, 以大肠杆菌和枯草芽孢杆菌为菌种, 采用抑菌圈法表征样品的杀菌性能。结果表明, 载银TiO₂/碳纳米管纳米复合材料比纯TiO₂纳米颗粒有更好的紫外光光催化活性, 其中掺碳纳米管(CNTs)1%(质量分数)的效果最好, 紫外光照射150min, 降解率达到76.5%;载银TiO₂/碳纳米管纳米复合材料比TiO₂纳米颗粒、Ag纳米粒子、CNTs(纯化处理后)的杀菌效果都要好很多, 其中掺CNTs 10%(质量分数)的样品的杀菌效果最好, 抑菌圈直径达到25.8mm。     

铋及钴掺杂TiO2陶瓷负载膜的制备及光催化性能

以钛酸四丁酯为钛源,Bi(NO₃)₃·5H₂O为铋源,Co(NO₃)₂·6H₂O为钴源,采用溶胶-凝胶法在陶瓷基片上分别制备了应用于固定式光催化反应器的Bi-TiO₂复合膜及Co-TiO₂复合膜。研究了涂膜方式及煅烧升温速率对膜表面形态的影响,并以甲基橙溶液为目标降解物,对比了旋涂法及浸渍提拉法制备的薄膜在不同升温速率下的光催化活性。通过热分析仪(TG-DSC)、X射线衍射仪(XRD)和扫描电镜(SEM)等测试手段分析了掺杂薄膜的结构。结果表明,采用旋涂法制备的薄膜与陶瓷基体结合较为紧密,而浸渍提拉法制备的薄膜催化活性较高。当煅烧温度为500 ℃,升温速率为10 ℃/min时,其对甲基橙的降解率较高。当摩尔比为0.010时Bi-TiO₂复合膜的催化活性较佳,100 min光降解甲基橙比率达到8.10%。钴或铋掺杂TiO₂均可提高TiO₂催化剂的光催化活性,Bi-TiO₂膜的催化活性优于Co-TiO₂膜。     

Effect of pH, inorganic ions, organic matter and H2O2 on E. coli K12 photocatalytic inactivation by TiO2: Implications in solar water disinfection

The effect of different chemical parameters on photocatalytic inactivation of E. coli K12 is discussed. Illumination was produced by a solar lamp and suspended TiO₂ P-25 Degussa was used as catalyst. Modifications of initial pH between 4.0 and 9.0 do not affect the inactivation rate in the absence or presence of the catalyst. Addition of H₂O₂ affects positively the E. coli inactivation rate of both photolytic (only light) and photocatalytic (light plus TiO₂) disinfection processes. Addition of some inorganic ions (0.2 mmol/l) like HCO₃⁻, HPO₄²⁻, Cl⁻, NO₃⁻ and SO₄²⁻ to the suspension affects the sensitivity of bacteria to sunlight in the presence and in absence of TiO₂. Addition of HCO₃⁻ and HPO₄²⁻ resulted in a meaningful decrease in photocatalytic bactericidal effect while it was noted a weak influence of Cl⁻, SO₄²⁻ and NO₃⁻. The effect of counter ion (Na⁺ and K⁺) is not negligible and can modify the photocatalytic process as the anions. Bacteria inactivation was affected even at low concentrations (0.2 mmol/l) of SO₄²⁻ and HCO₃⁻, but the same concentration does not affect the resorcinol photodegradation, suggesting that disinfection is more sensitive to the presence of natural anions than photocatalytic degradation of organic compounds. The presence of organic substances naturally present in water like dihydroxybenzenes isomers shows a negative effect on photocatalytic disinfection. The effect of a mixture of chemical substances on photocatalytic disinfection was also studied by adding to the bacterial suspension nutrient broth, phosphate buffer and tap water.     

Adhesion of microorganisms to polymer membranes: a photobactericidal effect of surface treatment with TiO2

The adhesion of Escherichia coli, Pseudomonas putida and Acinetobacter calcoaceticus cells to Microdyn-Nadir ultrafiltration membranes of various chemical nature: PS100 (polysulfone), P005 (polyethersulfone), C100 (regenerated cellulose) was studied. It was shown that an adhesiveness of the microorganisms to the membranes essentially depends on hydrophobic/hydrophilic properties of both the cells and membranes. In particular, it was found that the adhesion of relatively hydrophilic E. coli to membrane surfaces is essentially lower comparing with the adhesion of more hydrophobic P. putida, or A. calcoaceticus cells. In a turn the microorganisms attachment to more hydrophobic polyethersulfone and polysulfone membranes is higher than to hydrophilic cellulose one. It was shown that the volume fluxes of membranes with adhesive microorganisms dropped while samples were kept in contact with natural surface water due to increasing of cell number on membrane surface. In attempts to reduce membrane biofouling, TiO₂ particles were deposited on membrane surface with following ultraviolet (UV) irradiation at 365 nm. It was shown that due to photobactericidal effect the fluxes of surface modified membranes were 1.7–2.3 times higher comparing with those for control membrane samples (without TiO₂ deposition and UV treatment).     

改性黄腐酸/凹凸棒石复合材料的制备及其抑菌性能

黄腐酸(FA)具有抑菌消炎和促进动物生长的功效。为了进一步提升FA的广谱抑菌性,以凹凸棒石(APT)为载体,通过吸附法将FA负载于APT,同时进行十六烷基三甲基溴化铵(CTAB)改性。结果表明,FA和APT主要以静电吸附形式结合,CTAB的引入实现了FA/APT复合材料的电荷调控。复合材料对大肠杆菌和金黄色葡萄球菌的最小抑菌浓度(MIC)随着CTAB添加量的增加而减小;当CTAB添加量为15%(质量分数)时,其对大肠杆菌的MIC为1 mg/mL,对金黄色葡萄球菌的MIC为0.05 mg/mL。     

Structure,photocatalytic and antibacterial activity study of Meso porous Ni and S co-doped TiO_2 nano material under visible light irradiation

Undoped and Ni–S co-doped mesoporous TiO_2 nano materials were synthesized by using sol–gel method.The characteristic features of as prepared catalyst samples were investigated using various advanced spectroscopic and analytical techniques. The characterization results of the samples revealed that all the samples exhibited anatase phase(XRD), decreasing band gap(2.68 eV)(UV–Vis-DRS), small particle size(9.2 nm)(TEM), high surface area(142.156 m~2·g~(-1))(BET), particles with spherical shape and smooth morphology(SEM); there is a frequency shift observed for co-doped sample(FT-IR) and the elemental composition electronic states and position of the doped elements(Ni and S) in the TiO_2 lattice analyzed by XPS and EDX. These results supported the photocatalytic degradation of Bismarck Brown Red(BBR)achieved with in 110 min and also exhibited the antibacterial activity on Staphylococcus aureus(MTCC-3160), Pseudomonas fluorescence(MTCC-1688) under visible light irradiation.     

Efficient destruction of bacteria with Ti(IV) and antibacterial ions in co-substituted hydroxyapatite films

Hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂: HAP) was co-substituted with Ti(IV) and antibacterial ions (Ag⁺, Cu²⁺ or Zn²⁺) (HAPTiM), by coprecipitation and ion-exchange methods. Both HAPTiAg and HAPTiCu coated on porous spumous nickel film showed high efficiency for killing Escherichia coli and Staphylococcus aureus in the dark and under weak UVA irradiation, respectively. Moreover, their bactericidal activities were much higher than that of P25-TiO₂ film. The studies of ESR revealed that not only O₂⁻ was formed on HAPTiM, HAPTi, HAP and P25-TiO₂ films under weak UVA irradiation, but also at ambient temperature without light O₂⁻ was generated on HAPTiCu, HAPTiAg, and HAPTi. The redox couples of Cu⁰/Cu²⁺ and Ag⁰/Ag⁺ in the structure of HAPTiCu (Ag) caused the transfer of electron leading to the O₂⁻ generation under the above conditions. The higher bactericidal activities of HAPTiM were due to the synergy of the oxidation role of the O₂⁻ and the bacteriostatic action of antibacterial ions. The process of the damage of the cell wall and the cell membrane was directly observed by TEM, and further confirmed by the determination of potassium ion (K⁺) leakage from the killed bacteria.     

Photocatalytic activity of TiO2/ZSM-5 composites in the presence of SO4 ion

TiO₂/ZSM-5 composites were prepared from SiO₂ of rice husk ash and TiO₂ sol from hydrolyzed TiOSO₄ salt. The combined effect of these two materials greatly enhanced the photocatalytic decolorization of methylene blue dye solution. The instant decolorization of the dye solution in the dark by the composite, TiO₂/ZSM-5 (wt ratio 1:1), resulted from the combination of the adsorption by ZSM-5 zeolite and TiO₂ nano-particles, and of Na₂SO₄ salt adhering to the composite surface. As a strong flocculating agent, the SO₄²⁻ ion caused the precipitation of the dye onto the composite surface which consequently enhanced the photocatalytic decolorization of the dye under UV irradiation. The composite, TiO₂/ZSM-5 (wt ratio 1:5), completely decolorized the methylene blue dye in 2.5 h, giving an equivalent performance to that of TiO₂, P-25 powder.     

TiO2、ZnO和TiO2/ZnO三种氧化物粉体材料的抗菌性能对比

氧化物具有化学性质稳定、原材料丰富易得的优点,其作为抗菌材料日益受到关注。对氧化物的抗菌性能及影响因素开展深入研究,能够为新型抗菌材料的开发提供科学依据。通过溶胶-凝胶法制备出了TiO₂/ZnO复合粉体,并将其与TiO₂、ZnO进行对比,分别对它们的晶相结构、微观形貌和粒径进行了表征。利用大肠杆菌ATCC25922作为受试菌株,通过抑菌环试验和菌液接触试验对3种氧化物粉体材料的抗菌性能进行测试。考察了钛锌比、光照等条件对抗菌效果的影响。结果表明,所使用的TiO₂主要由锐钛矿相和金红石相组成,ZnO主要为六方纤锌矿相,制备出的TiO₂/ZnO则主要是锐钛矿型TiO₂在六方纤锌矿型ZnO的孔隙间沉积而成,这3种粉体材料的粒径由大到小分别为TiO₂/ZnO、TiO₂和ZnO。从抑菌环和菌液接触试验的结果可以看出,ZnO粉体材料的抗菌效果明显优于TiO₂粉体材料,ZnO和TiO₂/ZnO在黑暗条件下仍有良好的抗菌性能,但在可见光照射条件下抗菌效果更佳。ZnO含量是TiO₂/ZnO复合材料抗菌性能的关键因素。制备TiO₂/ZnO粉体材料时的煅烧温度对其抗菌性能没有明显影响。     

金银忍冬提取物的挥发性成分及抑菌活性分析

采用索氏提取法,以正己烷为溶剂,提取金银忍冬鲜叶和鲜花中的活性物质,通过气相色谱-质谱（GC-MS）法分析其挥发性化学成分并通过抑菌活性实验分析其抑菌活性。分析结果表明：金银忍冬鲜叶提取物中GC含量最高的化合物是（-）-异长叶醇（22.63%）,其次是2,7,10-三甲基-十二烷（10.48%）。金银忍冬鲜花提取物中GC含量最高的化合物是2,7,10-三甲基-十二烷（14.16%）,其次是邻苯二甲酸二丁酯（9.60%）。金银忍冬鲜叶提取物质量浓度为0.19 g/mL时,对金黄色葡萄球菌的抑制作用最明显,抑菌圈直径达到13.81±1.48 mm;金银忍冬鲜花提取物在质量浓度0.027 5~0.22 g/mL范围内,对大肠杆菌有较好的抑制作用。根据半数抑制浓度比较提取物对3种供试菌种的抑制能力,结果显示金银忍冬鲜叶及其鲜花提取物对3种实验菌的抑制效果顺序均为金黄色葡萄球菌>大肠杆菌>枯草芽孢杆菌。     

ω-氯甲基莰烯的高效快速合成及抑菌活性

以ω-乙酰氧甲基莰烯、乙酰氯、无水乙醇为原料,通过卤代反应,合成ω-氯甲基莰烯,通过FT-IR、¹H NMR、¹³C NMR和LC-HRMS等对产物进行了结构表征。研究结果表明：反应时间、反应物料比对卤代反应有较大的影响,在温度为30℃、n（ω-乙酰氧甲基莰烯）：n（乙酰氯）：n（无水乙醇）为1：2：2的条件下反应5 min,ω-乙酰氧甲基莰烯的转化率和ω-氯甲基莰烯产率分别高达97.5%和95.2%。微量肉汤二倍稀释法抑菌活性实验结果表明：ω-氯甲基莰烯能抑制细菌和真菌的生长,对4种细菌（大肠杆菌、肺炎克雷伯菌、金黄色葡萄球菌、枯草芽孢杆菌）的最低抑菌质量浓度（MIC）分别为125、62.5、15.63、250 mg/L,对3种真菌（白色念珠菌、热带念珠菌、黑曲霉）的MIC均为31.25 mg/L,抑菌活性明显高于莰烯、ω-乙酰氧甲基莰烯和ω-羟甲基莰烯,对白色念珠菌的抑菌活性与阳性对照品酮康唑相当。     

色氨酸辅助合成光催化活性增强的球形纳米TiO2

以L-色氨酸（L-Trp）为生物模板,采用简单水解及煅烧后制备了球形结构TiO₂纳米光催化剂。通过X射线衍射、扫描电子显微镜、红外光谱、紫外-可见漫反射光谱、光致发光光谱和N₂吸附-解吸等方法对制得的TiO₂纳米材料进行表征。在催化剂合成过程中,L-Trp作为生物模板发挥至关重要的作用,能够指导球形结构纳米TiO₂的形成。考察了不同煅烧温度下制备的TiO₂样品光催化活性,结果表明550℃时制备的TiO₂样品具有优异的光催化活性,紫外光照射30min对甲基橙溶液的降解率达到95%左右,主要是由于较大比表面积和球形结构的协同效应。光催化剂稳定性实验表明,所制备的TiO₂纳米材料可作为一种实用有效的光催化剂用于紫外光照射下降解有机染料。同时,对L-Trp辅助下球形结构TiO₂纳米颗粒的可能生长机理进行讨论。     

Absence of E. coli regrowth after Fe and TiO2 solar photoassisted disinfection of water in CPC solar photoreactor

Field disinfection of water in a large solar compound parabolic collector (CPC) photoreactor (35–70 l) was conducted at 35 °C by different photocatalytic processes: sunlight/TiO₂, sunlight/TiO₂/Fe³⁺, sunlight/Fe³⁺/H₂O₂ and compared to the control experiment of direct sunlight alone. Experiments were carried out using a CPC and natural water spiked with E. coli K 12. Under these conditions, total disinfection by bare sunlight irradiation was not reached after 5 h of treatment; and bacterial recovery was observed during the subsequent 24 h in the dark.

The addition of TiO₂, TiO₂/Fe³⁺ or Fe³⁺/H₂O₂ to the water accelerates the bactericidal action of sunlight, leading to total disinfection by solar-photocatalysis. No bacterial regrowth was observed during 24 h after stopping sunlight exposure. For some samples, the decrease of bacteria continues in the dark. A “residual disinfection effect” was observed for these samples before reaching the total inactivation. The effective disinfection time (EDT₂₄), defined as the treatment time required to prevent any bacterial regrowth during the subsequent 24 h in the dark, after stopping the phototreatment, was reached in the presence but not in the absence of different photocatalytic systems. EDT₂₄ was 2 h 30 min, 2 h and 1 h 30 min for sunlight/TiO₂, sunlight/TiO₂/Fe³⁺ and sunlight/Fe³⁺/H₂O₂ systems, respectively. The post irradiation events observed when the phototreated water is poured into an optimal growth medium are also discussed.