Noble Metals Can Have Different Effects on Photocatalysis Over Metal–Organic Frameworks (MOFs): A Case Study on M/NH2‐MIL‐125(Ti) (M=Pt and Au)

M‐doped NH₂‐MIL‐125(Ti) (M=Pt and Au) were prepared by using the wetness impregnation method followed by a treatment with H₂ flow. The resultant samples were characterized by powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), X‐ray absorption fine structure (XAFS) analyses, N₂‐sorption BET surface area, and UV/Vis diffuse reflectance spectroscopy (DRS). The photocatalytic reaction carried out in saturated CO₂ with triethanolamine (TEOA) as sacrificial agent under visible‐light irradiations showed that the noble metal‐doping on NH₂‐MIL‐125(Ti) promoted the photocatalytic hydrogen evolution. Unlike that over pure NH₂‐MIL‐125(Ti), in which only formate was produced, both hydrogen and formate were formed over Pt‐ and Au‐loaded NH₂‐MIL‐125(Ti). However, Pt and Au have different effects on the photocatalytic performance for formate production. Compared with pure NH₂‐MIL‐125(Ti), Pt/NH₂‐MIL‐125(Ti) showed an enhanced activity for photocatalytic formate formation, whereas Au has a negative effect on this reaction. To elucidate the origin of the different photocatalytic performance, electron spin resonance (ESR) analyses and density functional theory (DFT) calculations were carried out over M/NH₂‐MIL‐125(Ti).The photocatalytic mechanisms over M/NH₂‐MIL‐125(Ti) (M=Pt and Au) were proposed. For the first time, the hydrogen spillover from the noble metal Pt to the framework of NH₂‐MIL‐125(Ti) and its promoting effect on the photocatalytic CO₂ reduction is revealed. The elucidation of the mechanism on the photocatalysis over M/NH₂‐MIL‐125(Ti) can provide some guidance in the development of new photocatalysts based on MOF materials. This study also demonstrates the potential of using noble metal‐doped MOFs in photocatalytic reactions involving hydrogen as a reactant, like hydrogenation reactions.     

氧化亚铁硫杆菌的胞外电子传递研究

使用循环伏安、计时电流等电化学方法研究了氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans,At.f)的胞外电子传递机理.通过比较分别以亚铁离子和单质硫为电子供体培养的At.f的循环伏安曲线的还原峰可知,At.f具有胞外电子传递能力;恒压-0.4 V时,加入亚铁离子能够促进At.f的胞外电子传递;好氧条件比厌氧条件产生/变化的电流大1个数量级,说明At.f在好氧条件下具有较强的电化学活性.此外,采用X射线衍射、傅里叶变换红外光谱及扫描电子显微镜等对菌体的表面特征进行了分析.     

心衰标志物可视化联合检测方法研究

基于夹心免疫原理和表面免疫吸附模型,采用Image Pro Plus软件对硅片表面磁颗粒分布图像进行定量化处理,建立了硅片表面心衰标志物可视化联合检测方法。研究表明,该方法从抗体包被到获得检测结果不超过1 ｈ,操作简单,在单张硅片上可实现心衰标志物NT-proBNP和cTnI的联合检测。NT-proBNP和cTnI的最低检出限分别为21.8 pg/mL和0.034 ng/mL,检测范围分别为21.8~40000 pg/mL和0.034~50 ng/mL。83例不同程度心血管疾病患者的血清样本的检测结果与商品化免疫分析仪检测结果一致,相关系数r>0.98。因此,该快速免疫检测方法可以满足临床检测心衰标志物的需要。     

基于双功能单体的磁性双酚A印迹聚合物的制备及应用

以二氧化硅包覆的四氧化三铁为载体,双酚A(BPA)为模板分子,β-环糊精和4-乙烯基吡啶为二元功能单体,采用热聚合方法制备了对双酚A具有特异吸附性能的磁性印迹复合材料(mag-MIPs).采用透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)和振动样品磁强计(VSM)对该印迹复合材料进行了表征,并结合磁固相萃取(M-SPE)技术和高效液相色谱(HPLC)研究了其对双酚A的吸附行为,结果表明该印迹复合材料对双酚A具有良好的选择吸附能力.液相色谱检测结果表明,该磁性印迹复合材料可用于环境水样中双酚A的快速分离富集,回收率为90.51%~98.21%.     

基于亮蓝为显色剂的高酸度试纸

研究了色素亮蓝对氢离子浓度大于1 mol/L溶液的颜色响应及其变色机理,并将其作为显色剂应用于高酸度试纸的研发。 研究表明,固定于改性基纸上的亮蓝处于氢离子浓度为0.1~9.0 mol/L范围的介质溶液中时,其颜色变化表现出明显的酸度响应特征,即随着溶液酸度的提高,亮蓝逐渐由蓝色转化为蓝绿色、绿色、黄绿色直至黄色。 该响应具有普适性,不受无机酸的种类与氧化性强弱的影响。 采用分光光度法研究了溶液酸度对亮蓝光吸收特性的影响,提出其可能的变色机理。 以亮蓝为显色剂开发出高酸度试纸,该试纸可以直接检测溶液中0.1~9.0 mol/L范围内的氢离子平衡浓度,精确度为±1 mol/L。     

碘化1-甲基-2-异丙基(或丙基)-3-苯磺酰基咪唑啉的合成及基团转移反应

合成了新的四氢叶酸辅酶(THF)模型化合物碘化1-甲基-2-异丙基-3-苯磺酰基咪唑啉(5a)和碘化1-甲基-2-丙基-3-苯磺酰基咪唑啉(5b),研究了其反应性能.结果表明,化合物5与双官能团亲核体邻苯二胺或邻氨基苯酚反应,完全转移了4个碳的异丁基和正丁基单元,基于此探索了合成2-取代苯并咪唑及2-取代苯并唑的新方法;化合物5a与单官能团亲核体胺类反应部分转移了4个碳的异丁基单元,生成不同基团取代的N,N,N'-三取代乙二胺盐;化合物5a在Na BH4作用下可发生还原反应,在Na OH水溶液中可发生水解反应,也可与碳负离子基团(硝基甲基负离子或二腈基甲基负离子)发生亲核加成反应,生成了3类不同基团取代的N,N,N'-三取代乙二胺衍生物,探索了此类化合物的简易合成方法.这些反应模拟了四氢叶酸辅酶在生物体内转移一碳单元的功能,并将其扩展到4个碳原子单元,获得了可应用于有机合成的新方法和新试剂.     

甲氨蝶呤/层状双金属氢氧化物的性能调控及细胞生物实验研究

在乙醇-水混合体系中,以氨水为沉淀剂共沉淀合成了甲氨蝶呤/层状双金属氢氧化物(MTX/LDH)纳米复合物,采用控制水热处理时间的方式来调控其性能。利用X-射线衍射(XRD)、透射电镜(TEM)和红外光谱(FT-IR)等表征手段,对其结构及形貌进行了表征。研究表明:MTX分子以单层倾斜或垂直方式插入LDH层间,随着水热处理时间的不同,MTX在层间的倾斜角度发生了变化;水热处理时间对产物的结晶度、粒径和层间排列方式都有影响,当水热处理时间为12h时,得到的MTX/LDH纳米复合物的结晶度最高,单分散性最好。在磷酸缓冲液中考察了MTX/LDH纳米复合物的缓释性能,结果表明样品均呈现出良好的缓释性能,释放速率先快后慢。重点考察了这几种MTX/LDH纳米复合物作用于肺癌细胞A549的细胞生物实验,研究表明这几种复合物对肺癌细胞A549都具有良好的抑制作用,其效果与纳米复合物的单分散性和粒径有密切的关系,单分散性越好,粒径分布越均匀,对A549癌细胞的抑制效果越好。     

Preparation of novel curcumin‐imprinted polymers based on magnetic multi‐walled carbon nanotubes for the rapid extraction of curcumin from ginger powder and kiwi fruit root

A novel molecularly imprinted polymer based on magnetic phenyl‐modified multi‐walled carbon nanotubes was synthesized using curcumin as the template molecule, methacrylic acid as the functional monomer and ethylene glycol dimethacrylate as the cross‐linker. The phenyl groups contained in the magnetic imprinted polymers acted as the assisting functional monomer. The magnetic imprinted polymers were characterized by scanning electron microscopy, Fourier‐transform infrared spectroscopy and vibrating sample magnetometry. Adsorption studies demonstrated that the magnetic imprinted polymers possessed excellent selectivity toward curcumin with a maximum capacity of 16.80 mg/g. Combining magnetic extraction and high‐performance liquid chromatography technology, the magnetic imprinted polymer based on magnetic phenyl‐modified multi‐walled carbon nanotubes was applied for the rapid separation and enrichment of curcumin from ginger powder and kiwi fruit root successfully.     

A Ratiometric Luminescent Thermometer Co‐doped with Lanthanide and Transition Metals

Herein, we report the fabrication of a sensitive ratiometric and colorimetric luminescent thermometer with a wide operating‐temperature range, from cryogenic temperatures up to high temperatures, through the combination of lanthanide and transition metal complexes. Benefiting from the transition metal complex as a self‐reference, the lanthanide content in the mixed‐coordination complex, Eu_0.05(Mebip‐mim bromine)_0.15Zn_0.95(Mebip‐mim bromine)_1.9, was lowered to 5 %.     

Morphology Control of SrCO3 Crystals using Complexons as Modifiers in the Ethanol-water mixtures

Using SrC12-6H2O and Na2CO3 as the main raw materials and adding different complexons as modifiers with simple co-precipitation method, SrCO3 crystals with distinct morphologies like spherical, bundle-like, overlapping plate-like, hexagonal star-like, dumbbell-like, etc. can be synthesized in the ethanol-water mixtures. The samples were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and Fourier transform infrared spectrograph （FT-IR）. The interrelated effect mechanism is presented in the end. Results show that the modifier carboxyl groups play a significant role in controlling the SrCO3 crystal morphologies, which can alter the crystal growth unit （Sr^2＋） supply mode and induce the crystal formation with the morphologies matching their spatial configurations.