自支撑NH2-MIL-125/聚噁二唑复合正渗透膜的制备及性能

合成了高强度亲水性含羧基聚噁二唑材料(POD-COOH)和含氨基金属有机框架材料(NH₂-MIL-125), 以NH₂-MIL-125为填料, 与POD-COOH基体材料进行溶液共混, 并通过溶液浇铸法制备系列新型自支撑复合正渗透膜, 研究NH₂-MIL-125的引入对复合正渗透膜结构和性能的影响. 研究结果表明, 所制备的系列复合正渗透膜均呈致密结构, 且随着NH₂-MIL-125含量的增加, 复合膜的表面亲水性增加、 电负性增强, 并保持良好的机械性能. 以去离子水为进料液, 1.5 mol/L硫酸钠溶液为汲取液, 对上述自支撑复合膜进行正渗透性能测试, 发现由于消除了传统正渗透膜支撑层的内浓差极化现象, 该新型复合正渗透膜在分离过程中具有优异的正渗透性能.     

Lattice Distortion in Hollow Multi-Shelled Structures for Efficient Visible-Light CO2 Reduction with a SnS2/SnO2 Junction

Precise control of the micro-/nanostructures of nanomaterials, such as hollow multi-shelled structures (HoMSs), has shown its great advantages in various applications. Now, the crystal structure of building blocks of HoMSs are controlled by introducing the lattice distortion in HoMSs, for the first time. The lattice distortion located at the nanoscale interface of SnS₂/SnO₂ can provide additional active sites, which not only provide the catalytic activity under visible light but also improve the separation of photoexcited electron–hole pairs. Combined with the efficient light utilization, the natural advantage of HoMSs, a record catalytic activity was achieved in solid–gas system for CO₂ reduction, with an excellent stability and 100 % CO selectivity without using any sensitizers or noble metals.     

Excitation-Dependent Long-Life Luminescent Polymeric Systems under Ambient Conditions

Organic room temperature luminescent materials present a unique phosphorescence emission with a long lifetime. However, many of these materials only emit single blue or green color in spite of external stimulation, and their color tunability is limited. Herein, we report a rational design to extend the emission color range from blue to red by controlling the doping of simple pyrene derivatives into a robust polymer matrix. The integration of these pyrene molecules into the polymer films enhances the intersystem crossing pathway, decreases the first triplet level of the system, and ensures the films show a sensitive response to excitation energy, finally yielding excitation-dependent long-life luminescent polymeric systems under ambient conditions. These materials were used to construct anti-counterfeiting patterns with multicolor interconversion, presenting a promising application potential in the field of information security.     

Self-Assembly of Highly Stable Zirconium(IV) Coordination Cages with Aggregation Induced Emission Molecular Rotors for Live-Cell Imaging

The self-assembly of highly stable zirconium(IV)-based coordination cages with aggregation induced emission (AIE) molecular rotors for in vitro bio-imaging is reported. The two coordination cages, NUS-100 and NUS-101, are assembled from the highly stable trinuclear zirconium vertices and two flexible carboxyl-decorated tetraphenylethylene (TPE) spacers. Extensive experimental and theoretical results show that the emissive intensity of the coordination cages can be controlled by restricting the dynamics of AIE-active molecular rotors though multiple external stimuli. Because the two coordination cages have excellent chemical stability in aqueous solutions (pH stability: 2–10) and impressive AIE characteristics contributed by the molecular rotors, they can be employed as novel biological fluorescent probes for in vitro live-cell imaging.     

基于杂交链式反应的可视化免疫分析检测癌胚抗原

构建了基于杂交链反应的比色免疫分析方法,实现了对肿瘤标志物癌胚抗原的检测。在抗原-抗体的特异性结合作用下,在磁珠表面构建夹心式免疫复合物,进一步结合杂交链式反应(HCR)作为信号放大策略,将染料曙红Y嵌入至DNA长链中。在可见光的照射下,能使反应底液中的四甲基联苯胺(TMB)氧化,发生明显的颜色变化,由无色变为蓝色,且与癌胚抗原的浓度呈正相关性。在最优实验条件下,癌胚抗原的浓度在1 pg/mL^5 ng/mL范围内呈线性变化,检出限为1 pg/mL。     

加速溶剂萃取-磁固相萃取-高效液相色谱-串联质谱法测定水产品中10种氟喹诺酮类药物残留

养殖过程中的不合理使用和滥用使得水产品中氟喹诺酮抗生素残留累积量呈递增趋势,对人类的健康造成潜在的风险。建立高效、灵敏和可靠的水产品中氟喹诺酮类药物的同时分析方法十分重要。该研究建立了加速溶剂萃取-磁固相萃取-高效液相色谱-串联质谱法(ASE-MSPE-HPLC-MS/MS)测定水产品中沙拉沙星、氧氟沙星、恩诺沙星、丹氟沙星、洛美沙星、培氟沙星、环丙沙星、依诺沙星、诺氟沙星和双氟沙星残留的检测方法。采用室温自组装法,即在室温(25 ℃)下,将氧化石墨烯和零价纳米铁储备液快速涡旋混合,磁性分离收集沉淀物,得到GO@nZVI磁性复合材料。以扫描电镜、傅里叶变换红外光谱和X-射线衍射对磁性复合材料进行表征,结果显示GO@nZVI成功制备。该材料应用于MSPE净化中,ASE萃取温度为70 ℃,萃取溶剂为甲醇,萃取压力为10.34 MPa,静态萃取时间为5 min,循环萃取3次。萃取液浓缩后经MSPE有效净化后,采用Agilent ZORBAX Eclipse Plus C18色谱柱(100 mm×3.0 mm, 1.8 μm)梯度洗脱分离,MS/MS电喷雾正离子(ESI⁺)扫描、多反应监测(MRM)模式进行定量分析。氟喹诺酮的线性范围为1~100 μg/kg,线性相关系数(r²)均大于0.9995;目标物的检出限(S/N=3)为0.02~0.29 μg/kg,定量限(S/N=10)为0.07~0.98 μg/kg。所建方法成功用于黄鱼、草鱼、黑鱼、明虾和沼虾中氟喹诺酮的测定,在1倍、2倍、10倍定量限加标水平下得到的加标回收率为81.6%~105.8%,相对标准偏差(RSD)为4.2%~13.6%。研究表明,将ASE与MSPE有机结合,利用外部磁场实现萃取液的净化,无需离心和过滤操作,溶剂用量少,并且该方法所使用磁性萃取材料制备方法简单,具有自动化程度高、简便快速、方法灵敏度高、准确度高、重复性好等特点,可满足对水产品中FQs残留限量检测要求,具有实际应用前景。     

Crystal Structure of Scheelite-type LiTb(WO_4)_2 and Multi-color Emitting Properties Doped by Eu~(3+)

Single crystal of lithium terbium tungstate LiTb(WO4)2 has been grown by the flux method. The crystal structure was refined from single-crystal X-ray data. It crystallizes in tetragonal system, space group I41/a with a = 5.1749(9), c = 11.1953(19) ?, V = 299.81(12) ?~3, Z = 2, Mr = 661.56, Dc = 7.328 g/cm^3, F(000) = 560, μ(MoKα) = 49.94 mm^-1, R(F^2 > 2σ(F^2)) = 0.026 and wR(F^2) = 0.070. It features a typical scheelite-type structure composed of two-direction packing of isolated WO4 tetrahedra. Li and Tb atoms in the structure occupy the same crystallographic site. Moreover, a series of solid solution phosphors LiTb(1-x)Eux(WO4)2(x = 0.004~0.1) were synthesized by high temperature solid-state reactions. The phosphors could be effectively excited by a wavelength range from 379 to 487 nm, which matches well with the UV and near-UV LED chip. The emission color of the phosphor can be tuned from green, through yellow to red by simply adjusting the relative Eu³⁺ and Tb³⁺ concentration due to the Tb³⁺ to Eu³⁺ energy transfer.     

Magnetic,Photoluminescent and Semiconductive Properties of a Novel 4f-5d Bromide Compound (La6HgsBr26) [4(HgBr2)l (2Br)

An unprecedented 4f-5d material(La6Hg5Br26)[4(HgBr2)](2Br)(1)was syn-thesized by hydrothermal reactions and structurally characterized by single-crystal X-ray diffraction method.Complex 1 crystallizes in the Pbam space group of orthorhombic system with a=13.0980(10),b=13.6650(9),c=28.010(2)?,V=5013.4(6)?^3,Br36Hg9La6,Mr=5515.53,Z=2,Dc=3.613 g/cm^3,μ(MoKα)=29.457 mm^–1 and F(000)=4598.Compound 1 is characteristic of a two-dimensional(2D)layered structure.The photoluminescent measurements with solid-state samples reveal that compound 1 has a strong emission in the green region of light spectrum.It has remarkable CIE chromaticity coordinates of(0.2499,0.3589).A wide optical band gap of 3.41 eV is discovered by the solid-state UV/vis diffuse reflectance spectrum.The variable-temperature magnetic susceptibility obeys the Curie-Weiss law(cm=c/(T–q))with C=2.48 K and a negative Weiss constantθ=–169.07 K as revealed by the magnetic measurements,indicating the existence of an antiferromagnetic interaction in compound 1.     

Insight into Superior Visible Light Photocatalytic Activity for Degradation of Dye over Corner-truncated Cubic Ag2O Decorated TiO2 Hollow Nanofibers

Ag2O/TiO2 heterostructure has been constructed by loading corner-truncated cubic Ag2O on the TiO2 hollow nanofibers via an electrospinning-precipitation method. Compared to individual Ag2O and TiO2, Ag2O/TiO2 heterostructure exhibits obviously enhanced photocatalytic activity for the photodegradation of methyl orange(MO) under visible light irradiation. The composite with molar ratio of Ag2O to TiO2 at 4:10 exhibits the best photocatalytic performance with MO degraded 93% in 6 min. The superior activity is mainly attributed to the surface plasmon resonance(SPR) effect of metallic Ag in-situ produced during the photocatalytic process, which can favor electron transfer to the conduction band of TiO2. This leads to the efficient separation of photogenerated carriers, thus a superior photodegradation activity. Moreover, the energy band alignments of Ag2O/TiO2 heterostructure are calculated, which provides strong support for the proposed mechanism.     

多功能Fe3O4@SiO2 Janus颗粒

采用溶剂热法和溶胶-凝胶法制备了顺磁性Fe₃O₄@SiO₂颗粒,以Pickering乳液界面保护法实现颗粒表面分区获得Fe₃O₄@SiO₂ Janus颗粒,进一步选区复合生长Pt或Ag纳米颗粒制备Fe₃O₄@SiO₂-Pt和Fe₃O₄@SiO₂-Ag Janus颗粒.Fe₃O₄@SiO₂-Pt Janus颗粒的Pt一侧进行催化过氧化氢的反应,具有自驱动功能.因其顺磁性和两亲性,Fe₃O₄@SiO₂-Ag Janus颗粒能够作为磁响应颗粒乳化剂稳定油水乳液,并将Ag的催化功能引入界面.