Mechanisms and reusability potentials of zirconium-polyaziridine-engineered tiger nut residue towards anionic pollutants

Access to fresh water,its availability,and its quality are a global challenge to humanity,largely due to human activities in the environment.Thus,global water security has been jeopardized,requiring urgent remediation to safeguard our very existence.Hence,a novel and facilely engineered zirconium and polyethylenimine adsorbent based on tiger nut residue (TNR) was prepared,and its adsorptive capabilities towards a model dyestuff and nutrient were invested through a batch adsorption method.The developed adsorbent,zirconium-polyethylenimine-engineered tiger nut residue (TNR@PEI–Zr) was characterised by scanning electron microscopy,Fourier-transform infrared spectroscopy,X-ray diffraction analysis,and X-ray photoelectron spectroscopy to understand its morphology and surface chemistry and predict its adsorption mechanism.TNR@PEI–Zr had a p H point of zero charge (pH_(zpc)) of 6.7.The introduction of salts inhibited the removal efficiency of Alizarin red (AR) and phosphate (PO_(4)^(3–)) in the order of HCO_(3)^(-)>SO_(4)^(2–)>Cl^(-).Increasing temperatures (293–313 K) favoured the adsorption process at pH 3.The Langmuir model suited the adsorption processes of both AR and PO_(4)^(3–),implying homogenous and monolayer removal of pollutants with a maximal capacity of 537.8 mg·g^(-1)and 100.5 mg·g^(-1)at a dose of 0.01 g,respectively.The rate-determining steps of AR and PO_(4)^(3–)followed a pseudo-secondorder kinetic model and were thermodynamically spontaneous with an increase in randomness at the solid-solution interface.The adsorbent’s recyclability was notable and outperformed most adsorbents in terms of removal efficiency.TNR@PEI–Zr was found to be stable,and its use in practical wastewater decontamination was effective,ecologically acceptable and free of secondary pollution problems.

Application of the Multi-Electrode in the Degradation of Alizarin Red Induced by Glow Discharge Plasma

This paper presents a novel set-up to be used in the degradation of dye, Various influencing factors, such as the voltage, the number of the anodes, and the catalytic action of Fe^2＋, were examined. Chemical oxygen demand （COD）, ultraviolet （UV）, FTIR absorption spectra, and atomic force microscopy （AFM） were used to monitor the degradation process. The results showed that the efficiency of degradation is raised by increasing the applied voltage, and is further improved when two or three anodes are used. Moreover, the use of Fe^2＋ ion can promote the degradation reaction and shorten the degradation time. So the multi-electrode instrument is more efficient in degrading the dye and should be further studied.

Use of calcein and alizarin red S for immersion marking of black rockfish Sebastes schlegelii juveniles

Black rockfish Sebastes schlegelii juveniles （30-40 mm total length） were immersed in a range of calcein （CAL） solutions at concentrations ranging from 50 to 250 mg/L and alizarin red S （ARS） solutions at concentrations ranging from 100 to 500 mg/L in filtered seawater （salinity 30） for 24 h. Fluorescent marks were detected in otoliths （sagittae, asteriscus）, scales, fin rays （dorsal, pectoral, ventral, anal, and caudal fin rays）, and fin spines （dorsal, ventral, and anal fin spines） after a 60-d growth experiment. With the exception of 50-100 rng/L CAL, acceptable marks were produced in the otoliths and fin spines by all concentrations of CAL and ARS. In particular, marks were clearly visible under normal light in the sagittae, asteriscus, and fin spines offish immersed in 200 500 mg/L, 300-500 rag/L, and 200-500 mg/LARS, respectively. Scales and fin rays had acceptable marks at much higher concentrations （≥50 mg/L CAL, ≥300 mg/L ARS for scales and ≥50 mg/L CAL,≥200 mg/L ARS for fin rays）. The mark quality was highest （i.e., acceptable marks were observed in all sampled structures after immersion marking） in fish immersed in 150-250 mg/L CAL or 300-500 mg/LARS. In addition, there was no significant difference in survival and growth of marked fish compared with controls 60 d post-marking （P〉0.05）.

Degradation of Alizarin Red by Hybrid Gas-Liquid Dielectric Barrier Discharge

A system based on dielectric barrier discharge （DBD） with improved discharge sta- bility and homogeneity was used for the degradation of Alizarin Red （AR）. This special structure of the DBD system is characterized by the high voltage electrode, which is covered with a quartz tube and partially immersed in water, and by directly using the water as the ground electrode. A transition was realized from the filamentary mode for the conventional structure of the DBD to the semi-homogeneous mode for such a configuration of the plasma discharge. The spectra of plasma are dominated by N2 molecular lines in the ultraviolet-A radiation region. Plasma degra- dation of AR in this system exhibited pseudo-first-order reaction kinetics. The degradation rate of AR reached 95% or so after 14 min treatment under favorable conditions. Alkaline conditions are favorable for the degradation of AR. The increase of conductivity of the solution, input power and usage of oxygen bubbling could enhance AR degradation.

The adsorptive properties of UiO-66 towards organic dyes: A record adsorption capacity for the anionic dye Alizarin Red S.

In order to decisively determine the adsorption selectivity of zirconium MOF(UiO-66) towards anionic versus cationic species, the adsorptive removal of the anionic dyes(Alizarin Red S.(ARS), Eosin(E), Fuchsin Acid(FA)and Methyl Orange(MO)) and the cationic dyes(Neutral Red(NR), Fuchsin Basic(FB), Methylene Blue(MB),and Safranine T(ST)) has been evaluated. The results clearly reveal a significant selectivity towards anionic dyes. Such an observation agrees with a plethora of reports of UiO-66 superior affinity towards other anionic species(Floride, PO_4^(3-), Diclofenac sodium, Methylchlorophenoxy-propionic acid, Phenols, CrO_4^(2-), SeO_3^(2-), and AsO_4^-). The adsorption process of ARS as an example has been optimized using the central composite design(CCD). The resultant statistical model indicates a crucial effect of both pH and sorbent mass. The optimum conditions were determined to be initial dye concentration 11.82 mg.L^(-1), adsorbent amount 0.0248 g, shaking time of 36 min and pH 2. The adsorption process proceeds via pseudo-second order kinetics(R^2= 0.999). The equilibrium data were fit to Langmuir and Tempkin models(R^2= 0.999 and 0.997 respectively). The results reveal an exceptional removal for the anionic dye(Alizarin Red S.) with a record adsorption capacity of400 mg·g^(-1). The significantly high adsorption capacity of UiO-66 towards ARS adds further evidence to the recently reported exceptional performance of MOFs in pollutants removal from water.

Determination of Epinephrine Using Poly(Neutral Red)Modified Carbon Fibre Microelectrodes by Anodic Stripping Voltammetry

Poly(neutral red) film modified carbon fibre microelectrodes offer substantial improvement in voltammetric sensitivity and selectivity towards epinephrine (EP). The poly(neutral red) film was electropolymerized by cycling the potential between -0.8 V and +0.8 V. The anodic stripping voltammetric response for EP was found to be dependent on accumulation time and potential. By using a poly(neutral red) film modified carbon fibre microelectrode with a 1 min preconcentration at -1.2 V in biological phosphate buffer solution (pH=7.4), a good linear relationship between the anodic stripping peak currents and EP concentrations was obtained in the range of 2.0×10 -7 ￣ 2.0×10 -5 mol/L. The detection limit was up to 9.0 ×10 -8 mol/L. Moreover, 400 times higher concentrations of vitamin C did not interfere with the measurement of EP. This method was used for determining EP concentrations in epinephrine hydrochloride injection solution with satisfactory results.

斑马鱼快速骨质疏松模型方法的建立与优化

目的本文通过比较常见斑马鱼骨质疏松(osteoporosis,OP)模型不同建立方法,优化建立一种快速、稳定、灵敏的造模方法。方法采用铁过载及泼尼松龙(prednisolone,Pred)诱导OP模型,观察骨形成情况及动物死亡率,分组为:空白对照组(Control组)、模型组(包括FAC组和Pred组)、阳性对照组(AC组)。铁过载诱导法采用枸橼酸铁铵(ammonium ferric citrate,FAC)为造模药物。Pred诱导法有Pred-3受精后天数(day post fertilization,dpf)法,造模时间为3~9 dpf;Pred-5 dpf法,造模时间为5~10 dpf;Pred撤药法,3 dpf开始造模,7~9 dpf每天撤去1/3造模药物。进而比较常用药物阿尔法骨化醇(alfacalcidol,AC)、骨化三醇(calcitriol,CA)、阿仑膦酸钠(alendronate,AL)抗OP效应,选择稳定、灵敏的阳性药,并进一步对不同染色方法及染色条件进行优化。结果FAC在500μg/mL剂量下未能观察到对骨形成的显著影响。骨节数及第一椎骨长度结果显示,与Control组比较,Pred-3 dpf诱导法Pred组均降低,具有显著性差异(P<0.01,P<0.05),但斑马鱼死亡率较高;Pred-5 dpf法无显著性差异;Pred撤药法Pred组均降低,具有显著性差异(P<0.01),且无死亡。给予AC、CA、AL后均具有抗OP作用,CA抗OP作用更为灵敏、稳定。茜素红(alizarin red,ARS)染色参数优化结果显示,染色浓度为0.02%,染色2 h,0.5%KOH和甘油分别以(3∶1,3 h)和(1∶1,14 h)洗涤条件为最佳。染色对比结果显示,钙黄绿素对骨节部位染色较为灵敏,ARS则对第一椎骨处染色较为灵敏。结论采用Pred撤药法可诱导建立快速、稳定、灵敏的斑马鱼OP模型,是研究OP的稳定可靠模型。

聚乙烯亚胺修饰的聚氨酯泡沫对甲基橙和茜素红的吸附性能研究

制备了聚乙烯亚胺修饰的聚氨酯泡沫(PEI-PUF),考察了合成条件对制备吸附剂性能的影响,研究了PEI-PUF对水溶液中甲基橙和茜素红的吸附性能。研究结果表明:平衡时间为60 min,准一级动力学模型能更好地描述PEI-PUF-30对甲基橙和茜素红的吸附动力学过程;在酸性条件下PEI-PUF-30对甲基橙和茜素红的吸附量较大,吸附量随着pH值的增加而降低,PEI-PUF-30对甲基橙在较宽的pH值范围内(pH<9.8)存在较高的吸附量;Freundlich模型对实验数据的拟合结果较好,PEI-PUF-30对甲基橙和茜素红的最大吸附量分别为128.28和98.76 mg·g^(-1),相比之下对甲基橙有更高的吸附亲和性;随着温度的升高,PEI-PUF-30对甲基橙和茜素红的吸附量增大,表明该过程为吸热反应。

催化动力学光度法测定痕量亚硝酸根

在冰乙酸介质中,利用亚硝酸根催化条件下,溴酸钾氧化茜素红的褪色反应,建立催化动力学光度法,对痕量NO_(2)^(-)进行测定.通过单因素实验得到了各种成分的加入量、反应温度和反应时间等最佳条件.结果发现,在反应体系中,茜素红浓度与NO_(2)^(-)含量之间线性关系良好,在0.02~0.14μg/mL范围内,线性回归方程为ln(A_(0)/A)=1.43 c NO_(3)^(-)(μg/mL)+0.00859,相关系数r^(2)为0.9970,检出限为5.25×10^(-3)μg/mL.该方法操作简单、稳定性好.

废白土炭去除印染废水过程中多染料竞争吸附的研究

以废白土资源化利用为出发点,将SBE通过缺氧高温煅烧制备成废白土炭(SBE@C)吸附剂,探究多染料竞争吸附的关系。考察不同热解温度对SBE@C吸附印染废水中三种染料(甲基橙、曙红Y和茜素红)的影响,并对热解前后的材料进行SEM、EDAX、BET、XRD、FTIR和XPS表征分析。结果表明,高温热解法使SBE表面残油被炭化,增大了比表面积和孔体积,从而提升了吸附容量;热解温度为800℃时,SBE@C对染料的吸附效能最佳;多元竞争吸附实验表明,三种染料之间均存在一定程度的竞争吸附,且多元污染过程均由化学吸附决定,符合颗粒内扩散模型;用NaOH溶液对SBE@C进行再生,四次循环后SBE@C对三种染料仍具有良好的吸附能力。

茜素红S对异齿裂腹鱼稚鱼标记效果研究

为探索茜素红S对异齿裂腹鱼稚鱼浸泡标记的适宜条件,采用半静态式水生生物急性毒性试验法确定茜素红S对异齿裂腹鱼稚鱼安全质量浓度,利用不同质量浓度的茜素红S溶液对45日龄的异齿裂腹鱼稚鱼浸泡不同时间,探究各试验组稚鱼死亡率、生长情况、标记效果和标记有效保存时间,确定茜素红S对异齿裂腹鱼稚鱼的适宜标记条件。试验结果表明:茜素红S对异齿裂腹鱼稚鱼24、48、72、96 h半致死质量浓度分别为225.85、147.72、139.21、137.66 mg/L,安全质量浓度为28.99 mg/L;0~125 mg/L的茜素红S溶液浸泡稚鱼24 h,质量浓度为75~125 mg/L稚鱼耳石标记效果可见,当茜素红S质量浓度为125 mg/L时,稚鱼死亡率显著升高(P<0.05);75 mg/L茜素红S浸泡稚鱼12~96 h,浸泡24~96 h稚鱼耳石标记效果可见,当浸泡时间为96 h时,稚鱼死亡率显著升高(P<0.05);在4个月的续养过程中,75 mg/L茜素红S溶液浸泡72~84 h,4个月后稚鱼耳石标记效果依旧可见。综合生长、存活率、染色效果及标记保存时间,建议采用75 mg/L茜素红S浸泡标记异齿裂腹鱼72~84 h。

茜素红S法标定氯化钡标准溶液不确定度评定

以茜素红S为指示剂,用基准试剂无水硫酸钠标定0.250 0 mol/L氯化钡。对标定过程中直接影响测定结果的不确定因素进行分析、量化,按照测量不确定度评定流程进行评定。通过标定氯化钡标准溶液浓度的过程评定,得出了测量不确定度的主要来源有基准试剂的纯度、试剂配制、样品称量、玻璃量器、滴定终点颜色判定;硫酸钠和氯化钡摩尔质量引入的不确定较小,可以忽略不计。

Rare Earth Stearates as Thermal Stabilizers for Rigid Poly(vinyl chloride)

A series of stearates with different rare-earth ion were investigated as thermal stabilizers for rigid PVC at 180 ℃ in air. Their stabilizing efficiency was based on measuring the rate of dehydrochlorination. The resulted revealed the higher stabilizing efficiency of the investigated rare-earth stearates as thermal stabilizers for rigid PVC compared with the thermal stabilizers for industry: calcium stearate, zinc stearate, butyl stannum mercaptide, phosphite esters, β-diketone and epoxidized sunflower oil. This was well illustrated by longer incubation period (T_S) values and lower rate of dehydrochlorination. The stable efficiency was affected by the nature of rare-earth element's individual electronic shell. The mechanism for the stabilizing effect of rare-earth stearates was proposed. The result was experimentally proved based on IR spectrum.

Roughness Control of Layer-by-Layer and Alternative Spray Films from Congo Red and PAH via Laser Light Irradiation

Films from congo red (CR) alternated with poly(allylamine hydrochloride), PAH, were prepared by layer-by-layer and alternative spray techniques. In order to investigate the change of roughness induced by laser light irradiation (532 nm), both kinds of films were characterized by using UV-visible spectroscopy and atomic force microscopy (AFM). At dif- ferent irradiation times, layer-by-layer, LbL, films showed small changes in the roughness and irregular behavior, whereas spray films exhibited higher and a regular decreasing of roughness with increasing irradiation time. The higher roughness of spray films as compared with the LbL ones was attributed to different formation mechanisms of the films. The decreasing of the roughness as a function of the irradiation time (exhibited by the spray films) was associated to surface relaxation due to the interplay between photoisomerization of congo red dye and the heating of the sample during the laser light irradiation. The results suggested that the alternative spray technique is the best choose to control of roughness of the films by using light irradiation.

基于中性红-碳纳米复合材料的化学修饰电极检测亚硝酸盐

为了实现亚硝酸盐的灵敏检测,利用溶液剥离法和水合肼还原法制备了MWCNT@rGONR复合材料,并通过SEM和XRD等测试手段进行材料表征。将制备的复合材料滴涂在玻碳电极表面,借助简单可控的电聚合方法将中性红修饰到电极上,最终制备了PNR/MWCNT@rGONR/GCE。采用计时电流法对NO_(2)^(-)进行定量检测,结果表明,氧化峰电流与亚硝酸盐浓度在1.0×10^(-7)~1.9×10^(-3)mol/L范围内呈良好的线性关系,检出限为7.1×10^(-8)mol/L(S/N=3);同时,所制备的复合电极表现出良好的选择性和重现性。用此复合电极对某石化循环冷水进行实际水样的测定,回收率为93.26%~97.42%,相对标准偏差低于5.32%,结果较为理想。

基于钴掺杂煤沥青基碳材料构建茜素红电化学传感器的研究

以煤沥青(CTP)为碳源、二氧化硅为模板、KOH强碱为活化剂、硝酸钴为钴源,采用高温碳化法制备煤沥青基钴掺杂多孔碳材料(Co-PC);将Co-PC作为电极修饰材料构建茜素红(AR)快速检测的电化学传感器;通过扫描电子显微镜(SEM)、电化学测试对材料性能进行分析。结果表明,在最佳条件下,浓度为5~200μmol/L范围内,传感器检测分析结果呈现较好的线性关系,检出限为0.013μmol/L(S/N=3),并且该传感器具有高稳定性、高灵敏度与极好的抗干扰性能等。Co-PC各种优异的性能为制备具有增强电化学活性的AR传感器提供了新的选择。

聚茜素红-羧基化多壁碳纳米管修饰电极测定花生壳中木犀草素的含量研究

基于羧基化多壁碳纳米管(C-MWCNT),利用聚茜素红(PAR)的电催化特性在玻碳电极(GCE)上电聚合制备了PAR/C-MWCNT/GCE电化学修饰电极,并对花生壳中木犀草素(Lut)的含量测定进行了方法建立和实际应用。采用SEM、XRD对电极表面修饰剂的形貌和组成进行表征。通过循环伏安法和差分脉冲伏安法探究了Lut在电极上的电化学行为。结果表明,pH 8.5的磷酸盐缓冲溶液中,Lut在该修饰电极上的响应电流是裸电极的3倍,具有良好的分析性能,检测Lut的线性范围为1~100μmol/L,线性方程为y=0.372 28x-0.016 75(R^(2)=0.993 3)。该电极具有制备简单、选择性好和线性范围宽的特点,测得花生壳中Lut的含量为8.514μmol/L,加标回收率为91%~98%,相对标准偏差为2.62%。

偏振光镜在大鼠肾脏草酸钙晶体组织学染色检测中的应用分析

目的探讨偏振光镜结合组织学染色在草酸钙结石模型大鼠肾脏组织中晶体与钙化晶体的最优检测效果。方法将38只草酸钙结石模型组和4只正常对照组大鼠肾脏的FFPE组织行4μm切片,经HE、Von Kossa、1%茜素红S(PH4.2)、0.2%茜素红S(PH8.3)四种染色后在偏正光镜、光镜下以晶体与钙化晶体的存在状态、双折射性作为评估指标进行分析。结果四种染色后光镜下模型组和对照组分别的晶体和草酸钙晶体的χ^(2)=138.8、P<0.001,χ^(2)=147.3、P<0.001;偏正光镜下的χ^(2)=126.9、P<0.001,χ^(2)=118.2、P<0.001。Von Kossa染色能确定模型组晶体和钙化晶体的阳性和对照组的阴性,HE染色仅能确定模型组晶体的阳性和对照组的阴性而无法确定模型组钙化晶体的阳性和对照组的阴性,2种茜素红S在晶体上均不着色呈假阴性而无法判断;由于HE和2种茜素红S染色均未能使晶体染色,故在偏正光镜下见晶体有显著的双折射光可确定模型组的草酸钙晶体阳性和未见双折射光从而确定对照组的阴性,同时在Von Kossa染色呈黑色颗粒或团块状区域在偏正光镜下呈暗黑色或暗红色,其内有见不完整、散在双折射光但不显著不能确定晶体和草酸钙的晶体为阳性。结论偏正光镜结合HE染色可确定草酸钙晶体,光镜下Von kossa染色可作为钙化晶体的验证方法,而茜素红染色在光镜下对草酸钙晶体染色观察无特异性。

以分光光度法测定复方样品中的壳聚糖含量

在pH 5 0的NaAc HAc缓冲液中茜素红与壳聚糖反应生成复合物 ,在 5 3 0nm处产生新的吸收峰 ,反应体系在 42 2nm和 5 3 0nm处吸光值变化与壳聚糖含量成线性关系 ,据此建立一种具有高选择性和高灵敏度的简便快速测定壳聚糖含量的分光光度法。确定了含量分析的条件 ,检测波长为 42 2nm ,线性方程 y =0 63 78-1 13 3 4x(R =-0 997) ,在 0～ 0 2mg/mL范围内呈现良好的线性关系 (R =0 997) ;平均回收率为 99 88%。测定了复方样品中壳聚糖的含量 ,并考察了干扰因素对测定的影响。采用该方法可检测复杂样品中微量的壳聚糖。

茜素红与壳聚糖的相互作用机理研究

应用光谱法研究在pH =5 0的反应体系中壳聚糖 (CTS)与茜素红 (AR)的结合反应 ,考察了反应体系中AR/CTS摩尔比、NaCl浓度及CTS的脱乙酰度对茜素红与壳聚糖相互作用的影响 .通过实验测得CTS对AR的最大结合数NE=4 78×10 3 ,理论模型预测最大结合数NC=4 73× 10 3 ,实验值与理论值一致 。