PAMAM树形分子对CaCO3结晶影响的研究

研究了不同端基的聚酰胺胺(PAMAM)树形分子对CaCO₃在水溶液中结晶的影响。分别利用傅立叶变换红外光谱(FTIR)、X-射线衍射(XRD)、扫描电镜(SEM)等测试手段对样品进行了分析。结果表明:没有树形分子存在时CaCO₃是粒径为10μm的菱形方解石晶体;端基为-COONa的树形分子存在时CaCO₃则是粒径为1～2μm的球形球霰石晶体;-COOCH₃端基PAMAM树形分子存在时得到的CaCO_{3相似文献}   

水溶性纳米Fe3O4-阿魏酸抗凝血材料的合成及性能

为提高具抗凝血性能的阿魏酸分子在水中的溶解性进而提高其药效,利用DBI(3,4-二羟基苯甲醛)、PEG(聚乙二醇4000)和纳米Fe₃O₄,采用接枝的方法制备了水溶性纳米Fe₃O₄-DBI-PEG-阿魏酸抗凝血杂化材料,用IR、¹H NMR、TG、SEM、TEM、VSM和粒度测试方法表征了产物。结果表明阿魏酸(FA)接枝在了经过DBI-PEG活化后的纳米Fe₃O₄氧化物表面。杂化材料具有良好的水溶性(溶解度大于10 mg·mL^-1)和顺磁性。抗凝血试验表明相同条件下杂化材料的抗凝血时间和复钙时间比阿魏酸要长,杂化材料的活化部分凝血活酶时间(APTT)和凝血酶原时间(PT)比空白组要长,杂化材料的抗凝血时间随浓度的增大而延长。     

Ti3C2Tx/MnO2正极在水系锌电池中的电化学性能

二氧化锰(MnO₂)材料具有比容量大、电极电位高、储量丰富以及价格低廉等优势,成为水系锌电池正极最受关注的一类材料,然而其仍然存在着结构稳定性差和电化学储存机理复杂的问题。因此,我们通过两步合成法制备了一种花苞状结构的MnO₂负载在Ti₃C₂T_x表面形成Ti₃C₂T_x/MnO₂复合材料,通过X射线粉末衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)对复合样品的结构、成分和形貌进行表征。通过将Ti₃C₂T_x/MnO₂复合材料作为正极,与锌负极匹配组装成水系锌电池,研究了其分别在2 mol·L^-1 ZnSO₄、2 mol·L^-1 ZnSO₄+0.1 mol·L^-1 MnSO₄、30 mol·L^-1三氟甲基磺酸四乙基铵(TEAOTf)+1 mol·L^-1三氟甲烷磺酸锌(ZnOTf)和3 mol·L^-1 ZnOTf四种电解液中的电化学性能。结果表明,Ti₃C₂T_x/MnO₂在2 mol·L^-1 ZnSO₄中的比容量较高,但循环稳定性很差。将TEAOTf盐和ZnOTf盐共溶于水中,设计了一种新型的含惰性阳离子的超高浓度盐包水电解液(30 mol·L^-1 TEAOTf+1 mol·L^-1 ZnOTf),不仅提高了Ti₃C₂T_x/MnO₂材料的可逆性,而且有效抑制了电极材料在循环过程中的溶解。     

三嵌段共聚物PAN-b-PEG-b-PAN的合成及其自组装行为的研究

利用原子转移自由基聚合(ATRP)制得了分子量可控、分子量分布窄的聚丙烯腈-b-聚乙二醇-b-聚丙烯腈P(AN-b-PEG-b-PAN)嵌段共聚物. 通过¹H NMR, FTIR, 凝胶渗透色谱(GPC)对所得产物的结构和分子量进行了表征并通过TG和DTA考察了该嵌段共聚物的热稳定性; 运用透射电子显微镜(TEM)、荧光探针技术和动态光散射(DLS)研究了P(AN)₂₇-b-P(EG)₄₅-b-P(AN)₂₇在溶剂水中胶束的形成、结构、形貌和胶束粒径. 结果表明, 三嵌段共聚物P(AN)₂₇-b-P(EG)₄₅-b-P(AN)₂₇的热稳定性较纯聚乙二醇P(EG)好, 且柔性链PEG的引入对嵌段共聚物的放热峰位置没有显著的影响. 当改变此嵌段共聚物溶液浓度时, 该嵌段共聚物会自组装成不同形状的胶束, DLS测量的胶束粒径大于TEM观察的结果, 其临界胶束浓度(cmc)约为4.46×10^－4 g•L^－1.     

二丁基硫醚的合成及其萃取分离钯、铂的研究

用Na₂S·9H₂O和1-溴丁烷合成了二丁基硫醚(简写为M)。以二丁基硫醚为萃取剂进行了钯、铂萃取分离的研究,并采用正交实验,得出了钯、铂分离的最佳条件为c_M=0.344 mol·L^-1,O/A=1∶1,t=6 min,c_H⁺=2 mol·L^-1。测得二丁基硫醚萃取钯的容量大于17 g·L^{-1相似文献}   

水溶性纳米Fe3O4-阿魏酸抗凝血材料的合成及性能

为提高具抗凝血性能的阿魏酸分子在水中的溶解性进而提高其药效,利用DBI(3,4-二羟基苯甲醛)、PEG(聚乙二醇4000)和纳米Fe₃O₄,采用接枝的方法制备了水溶性纳米Fe₃O₄-DBI-PEG-阿魏酸抗凝血杂化材料,用IR、¹H NMR、TG、SEM、TEM、VSM和粒度测试方法表征了产物。结果表明阿魏酸(FA)接枝在了经过DBI-PEG活化后的纳米Fe₃O₄氧化物表面。杂化材料具有良好的水溶性(溶解度大于10 mg·mL^-1)和顺磁性。抗凝血试验表明相同条件下杂化材料的抗凝血时间和复钙时间比阿魏酸要长,杂化材料的活化部分凝血活酶时间(APTT)和凝血酶原时间(PT)比空白组要长,杂化材料的抗凝血时间随浓度的增大而延长。     

纳米级TiO2粉体的制备研究——Ⅱ.絮凝剂及其浓度的影响

采用溶胶-凝胶-超临界流体干燥(SCFD)法制备纳米级TiO₂超细粉，详细考察了不同絮凝剂及其浓度对TiO₂织构和结构性质的影响。结果表明，利用强碱溶液作为絮凝剂，浓度为5 mol·L^-1是制备大孔高比表面TiO₂超细粉较为适宜的条件。     

纳米固体超强酸SO42-/Fe2O3的制备及其催化合成乙酸乙酯

将Fe₂O₃纳米粉体经一定浓度的H₂SO₄浸泡活化后制成纳米固体超强酸SO₄^2-/Fe₂O₃,将其用于催化合成乙酸乙酯以考察其活性。利用均匀设计分析了超强酸制备过程及酯化反应过程中各因素的影响,研究结果表明较好的制备条件是:H₂SO₄浓度:2.5mol·L^-1;浸泡时间:1h;活化温度:167℃;活化时间:1h,此时获得的固体超强酸SO₄^2-/Fe₂O₃的粒径小于50nm。当催化剂用量为冰乙酸质量的5%,n(乙醇)∶n(冰乙酸)为3∶1,反应3.5h后乙酸的转化率高于80%。该催化剂经H₂SO₄溶液浸泡、活化再生后可重新使用,推断出其酸强度H₀<-14.5。     

水热法可控制备铋铁系化合物材料

本文以Fe(NO₃)₃·9H₂O和Bi(NO₃)₃·5H₂O为反应原料,以NaOH为矿化剂, 利用水热方法制备出几种纯相的铋铁系化合物材料,通过调节NaOH的浓度范围可以很容易的控制铋铁系化合物的物相。在NaOH浓度为0.1~0.4 mol·L^-1区间,可以得到立方相的软铋矿Bi₂₅FeO₄₀,当NaOH浓度提高到0.8~2.0 mol·L^-1区间,可以得到六方钙钛矿结构的BiFeO₃,再提高NaOH浓度至8.0 mol·L^-1以上可以得到正交相的Bi₂Fe₄O₉,在NaOH浓度为12.0 mol·L^-1时可以获得纳米片状Bi₂Fe₄O₉。同时探讨了铋铁系化合物的生长机理。     

Co3O4纳米片的制备及其电化学电容性能

以配位超分子化合物为前驱物,通过液相氧化分解得到了六方形CoOOH纳米片,进而在空气中热处理制得了Co₃O₄纳米片。利用XRD、TEM、FESEM对CoOOH和Co₃O₄纳米片的结构和形貌进行了表征。电化学测试表明,Co₃O₄纳米片电极在6 mol·L^-1 KOH溶液中表现出良好的电化学电容特性,在电流密度为1 A·g^-1其单电极比容量可达到227 F·g^-1。     

Influence of sodium dodecyl sulfate on the phase transition of thermoresponsive hyperbranched polymer in water

The influence of sodium dodecyl sulfate(SDS) on the cloud point temperature(Tcp) of the aqueous solution of thermoresponsive hyperbranched polyethylenimine derivative HPEI-IBAm was studied systematically. When p H was below 8.5, HPEI-IBAm was positively-charged. Initially, the Tcp of HPEI-IBAm decreased significantly, followed by an obvious increase with the increase of SDS concentration. The lower the p H was, the higher the SDS concentration was required to achieve the minimum Tcp. When p H was above 8.5, HPEI-IBAm was neutral and raising the SDS concentration led to the gradual increase of Tcp. Compared to linear poly(N-isopropyl acrylamide)(PNIPAm), the Tcp of the current hyperbranched HPEI-IBAm was more sensitive to SDS. The thermoresponsive HPEI-IBAm/SDS complex was used as host to accommodate the non-polar pyrene in water. The lowest SDS concentration for effectively enhancing the solubility of pyrene in water was around 6.4 mmol·L~(-1). When HPEI-IBAm was present, the SDS concentration threshhold was decreased to about 0.31 mmol·L~(-1). Fluorescence technique with pyrene as the hydrophobic probe demonstrated that the SDS concentration of 7.2 mmol·L~(-1) was required to form the hydrophobic domain to accommodate pyrene guests without HPEI-IBAm, while only 0.2 mmol·L~(-1) of SDS was required in the presence of HPEI-IBAm.     

Ag/TiO2光催化还原硝酸氮

利用化学还原法制备不同Ag掺杂量TiO₂纳米催化剂,采用TEM、XRD、XRF和UV-Vis对催化剂进行表征。考察了催化剂在紫外光(254 nm)和可见光照射下还原初始浓度100 mgN·L^-1水相硝酸氮的活性和效果。重点考察了紫外光照射下Ag掺杂量、不同空穴捕获剂(甲酸、甲醇、乙酸、乙醇、草酸、草酸钠等)及甲酸浓度对硝酸氮还原的影响;对硝酸氮转化率和总氮去除率、形成亚硝酸氮、氨氮浓度及氮气选择性的影响。甲酸浓度为0.030 mol·L^-1、Ag掺杂量为1.0wt%时催化剂效果最佳。此时,硝酸氮、总氮的转化率分别为98.43%、78.13%;亚硝酸氮浓度为零,转化的硝酸氮中只有20.76%转化为氨氮,氮气选择性为79.24%。可见光下进行光催化还原反应时,硝酸氮转化率仅37.98%,但氮气的选择性较高。     

Synthesis and application of polythiophene-coated Fe3O4 nanoparticles for preconcentration of ultra-trace levels of cadmium in different real samples followed by electrothermal atomic absorption spectrometry

In this research, magnetic Fe₃O₄ nanoparticles were synthesised by co-precipitation method and modified with polythiophene (PT) to produce Fe₃O₄-PT nanoparticles for preconcentration and determination of cadmium (??) ion followed by electrothermal atomic absorption spectrometry. The results of FT-IR spectroscopy, EDX analysis and SEM images show that Fe₃O₄-PT nanoparticles were synthesised successfully. Different parameters such as sample pH, amounts of adsorbent, sample volume, extraction time, type and concentration of eluent and desorption time were completely investigated and optimum conditions were selected.

Under the optimum conditions, the calibration curve was linear in the range of 0.01–0.25 µg L^?1 of cadmium (??). The relative standard deviation was 4.7% (n = 7, 0.10 µg L^?1 Cd²⁺) and limit of detection was 3.30 ng L^?1. The accuracy of the proposed method was verified by the analysis of a certified reference material and spike method. Finally, the proposed method was applied for the determination of ultra-trace levels of cadmium (??) in different water and food samples.     

A Sensitive Surface‐enhanced Raman Scattering Method for Determination of Melamine with Aptamer‐modified Nanosilver Probe

The small nanosilver was prepared by the sodium borohydride procedure. The aptamer was used to modify nanosilver to obtain a nanosilver‐aptamer (AgssDNA) SERS probe for the determination of melamine. In pH 6.6 phosphate buffer solution and in the presence of NaCl, the AgssDNA probe specifically combined with melamine to release nanosilver particles that were aggregated to nanosilver clusters, which exhibited SERS effect at 240 cm^?1. When melamine concentration increased, the nanosilver clusters increased, and the SERS intensity at 240 cm^?1 increased. The increased SERS intensity ΔI_{240 cm?1} is linear to melamine concentration in the range of 6.3–403.6 μg·L^?1, with a detection limit of 1.2 μg·L^?1. This assay was applied to determination of melamine in milk, with satisfactory results.     

银-磷酸钛纳米复合膜的构建及其电化学生物传感

利用ITO基底上层层组装构建的多层内嵌银纳米粒子的磷酸钛薄膜固定了血红蛋白并且用于生物传感研究。由于银纳米粒子与磷酸钛膜的协同作用,实验中可以观察到Hb的直接电子传递。研究表明所制备的Hb-Ag-TiP/PDDA/ITO电极对H₂O₂响应迅速、稳定,检测限达3.3×10^-6 mol·L^-1。     

普鲁士蓝/CdS纳米复合物电致化学发光及其H2O2传感应用

通过一定体积比的CdS和普鲁士蓝(PB)胶体纳米溶液的简单混合,制备了PB/CdS纳米复合物。在共反应剂存在条件下,PB纳米粒子含量较低时,在ITO电极上CdS纳晶的电致化学发光(ECL)强度可以增强3倍左右。PB纳米粒子含量较高时,CdS纳晶的ECL强度则显著降低。详细讨论了PB纳米粒子对CdS纳晶ECL影响的机理。PB纳米粒子对CdS纳晶的ECL增强可用于H2O2传感。该传感器对H2O2响应的线性范围为3.3×10-8～6.5×10-3 mol.L-1(R=0.999 2),检测限为12 nmol.L-1(S/N=3),传感器具有良好的稳定性和重现性。     

Determination of Hydrogen Peroxide Using a Novel Sensor Based on Fe3O4 Magnetic Nanoparticles

Fe₃O₄ magnetic nanoparticles were synthesized by chemical co-precipitation with sodium citrate as a surfactant and were used with chitosan to construct a novel hydrogen peroxide sensor. The electrochemical behavior of hydrogen peroxide at the sensor was investigated by cyclic voltammetry. The composite film electrocatalyzed the reduction of hydrogen peroxide, and the peak current increased linearly with concentration from 1.00 × 10^?5 to 1.00 × 10^?3 mol · L^?1 (R = 0.9974) with a detection limit of 1.53 × 10^?6 mol · L^?1. This novel nonenzyme sensor provided good sensitivity, stability, and precision with potential applications.     

Properties and Extraction for [Ni(NH3)6]2+ of ATPS-a Formed by Aqueous Cationic–Anionic Surfactant Mixtures

The properties and extraction for [Ni(NH₃)₆]²⁺ of anionic aqueous two-phase systems (ATPS-a) that formed in mixtures of cetyltrimethylammonium bromide (CTAB) and excess sodium dodecyl sulfate (SDS) aqueous solutions were investigated. The results showed that the properties and extraction effects were strongly affected by the surfactant concentration, the temperature of system, and the mole fraction of surfactants. The increase of temperature induces narrower phase region and larger phase volume ratio. In addition, [Ni(NH₃)₆]²⁺ was extracted into the surfactant-rich phase with higher distribution coefficient when the liquid crystal had the birefringent properties. Moreover, the distribution coefficient can be improved through reducing the concentration of surfactant from 0.15 to 0.05 mol · L^?1 or increasing mole fraction of CTAB from 21.9% to 23.1%. The results showed that ATPS of cationic–anionic surfactants was efficient for [Ni(NH₃)₆]²⁺ extraction with distribution coefficients of 13.5 when the total surfactant concentration was 0.05 mol · L^?1, mole fraction of CTAB was 21%, and temperature was 34°C.     

Analysis of Carbamazepine in Tablet and Human Serum by Sweeping‐Micellar Electrokinetic Chromatography Method

Abstract

A sensitive and simple micellar electrokinetic chromatography (MEKC) method was developed for the determination of the antiepileptic drug carbamazepine (CBZ) using a sweeping on‐line concentration method with photodiode array detection. The effect of pH, concentration of the running buffer solution, organic modifier, applied voltage and injection time on the concentration efficiency and separation was investigated. An untreated fused‐silica capillary was used (50 cm; effective length, 40 cm, 75 µm i.d.) for the analysis. The background solution (BGS) was 50 mmol · L^?1 NaH₂PO₄ (pH 3.0) containing 100 mmol · L^?1 SDS and 20% acetonitrile (5.82 ms · cm^?1) with an applied voltage of ?20 kV at 25°C. Sample introduction was performed at 0.5 psi for 90 s with diode array detection at 214 nm. For the method, the calibration curve was linear over a range of 0.5–40 µg · mL^?1 for CBZ with a correlation coefficient of 0.998. The detection limit (S/N=3∶1) of CBZ was 0.10 µg · mL^?1. About 100‐fold improvement in concentration sensitivity was achieved in terms of peak height by the sweeping method compared to conventional injection method. The sweeping‐MEKC method has been successfully applied to the analysis of CBZ in tablet and human serum.     

超支化铬系催化剂的合成及乙烯齐聚性能研究

以正辛胺和十二胺为原料,分别制备了两种超支化PNP配体,通过引入金属铬活性位点的方法合成了具有不同烷基链长度的超支化PNP铬系催化剂.采用红外光谱(IR)、核磁共振磷谱(~(31)P-NMR)、核磁共振氢谱(~1H-NMR)、紫外光谱(UV)和质谱(MS)等表征方法证明合成催化剂的结构与理论结构预测相符.详细考察了催化剂用量、溶剂种类、反应条件以及配合物结构对乙烯齐聚性能的影响.实验结果显示,超支化PNP铬系催化剂在甲苯作溶剂,甲基铝氧烷(MAO)做助催化剂时表现出良好的催化乙烯齐聚性能,产物主要为低碳烯烃.在最佳条件下,催化活性最高可达到1.69×10~5 g·(mol Cr·h)~(-1),己烯和辛烯的选择性为43.3%以上.相同聚合条件下,其催化活性随着端基烷基链长度的增加而下降.