Recent Progress in Metal-Organic Framework Based Fluorescent Sensors for Hazardous Materials Detection

Population growth and industrial development have exacerbated environmental pollution of both land and aquatic environments with toxic and harmful materials. Luminescence-based chemical sensors crafted for specific hazardous substances operate on host-guest interactions, leading to the detection of target molecules down to the nanomolar range. Particularly, the luminescence-based sensors constructed on the basis of metal-organic frameworks (MOFs) are of increasing interest, as they can not only compensate for the shortcomings of traditional detection techniques, but also can provide more sensitive detection for analytes. Recent years have seen MOFs-based fluorescent sensors show outstanding advantages in the field of hazardous substance identification and detection. Here, we critically discuss the application of MOFs for the detection of a broad scope of hazardous substances, including hazardous gases, heavy metal ions, radioactive ions, antibiotics, pesticides, nitro-explosives, and some harmful solvents as well as luminous and sensing mechanisms of MOF-based fluorescent sensors. The outlook and several crucial issues of this area are also discussed, with the expectation that it may help arouse widespread attention on exploring fluorescent MOFs (LMOFs) in potential sensing applications.     

Micelle-sensitized constant-energy synchronous fluorescence spectrometry for the simultaneous determination of pyrene, benzo[a]pyrene and perylene.

The use of micellar media in constant-energy synchronous fluorescence spectrometry has been proposed. The influence of some aqueous micellar systems on the determination of pyrene, perylene and benzo[a]pyrene has been investigated. The presence of these micellar systems allows their determination in aqueous media, thus avoiding the use of an organic solvent, and greatly enhances the fluorescence signals. The combination of a constant-energy synchronous scanning technique and a micellar system provided a single spectrum for the simultaneous identification and quantitative determination of the three polycyclic aromatic hydrocarbons (PAHs). Further there was no energy transfer among them, making the measurement simple and fast. A constant-energy difference of 2800 cm(-1) was selected. The analytical characteristics of the proposed method in the presence of anionic micelles of sodium dodecylsulfate (SDS) were studied. The detection limits were at a level of ng ml(-1). Analysis of water samples from two different origins spiked with known amount of pyrene, perylene and benzo[a]pyrene also gave satisfactory results, and total average recoveries were greater than 97.1%.     

Unraveling the Mechanisms of the Excited-State Intermolecular Proton Transfer (ESPT) for a D-π-A Molecular Architecture

Precise revealing the mechanisms of excited-state intermolecular proton transfer (ESPT) and the corresponding geometrical relaxation upon photoexcitation and photoionization remains a formidable challenge. In this work, the compound (E)-4-(((4H-1,2,4-triazol-4-yl)imino)methyl)-2,6-dimethoxyphenol (TIMDP) adopting a D-π-A molecular architecture featuring a significant intramolecular charge transfer (ICT) effect has been designed. With the presence of perchloric acid (35 %), TIMDP can be dissolved through the formation of a HClO₄–H₂O–OH(TIMDP)–N(TIMDP) hydrogen-bonding bridge. At the ground state, the ICT effect is dominant, giving birth to crystals of TIMDP. Upon external stimuli (e.g., UV light irradiation, electro field), the excited state is achieved, which weakens the ICT effect, and significantly promotes the ESPT effect along the hydrogen-bonding bridge, resulting in crystals of [HTIMDP]⁺ ⋅ [H₂O] ⋅ [ClO₄]⁻. As a consequence, the mechanisms of the ESPT can be investigated, which distorted the D-π-A molecular architecture, tuned the emission color with the largest Stokes shift of 242 nm, and finally, high photoluminescence quantum yields (12 %) and long fluorescence lifetimes (8.6 μs) have achieved. These results not only provide new insight into ESPT mechanisms, but also open a new avenue for the design of efficient ESPT emitters.     

Zn_2SnO_4纳米材料制备及光致发光特性

以ZnO、SnO2和活性炭的混合物为原料,通过碳热还原热蒸发法无催化剂成功制备出Zn2SnO4纳米材料.借助X射线衍射仪(XRD)、拉曼光谱和扫描电子显微镜(SEM)对样品物相和形貌进行了表征,结果显示样品为面心立方结构的Zn2SnO4纳米链状棒,同时含有少量的ZnO物相.利用X射线光电子能谱(XPS)对Zn2SnO4样品表面各元素的化学状态及相互作用方式进行了测试,结果表明:样品中Zn和Sn分别是以+2价和+4价氧化态形式存在,其中Zn2p3/2电子有两个结合能,分别来自ZnO和Zn2SnO4,Zn2SnO4中Sn4+占据不同的格点位置.室温下光致发光谱(PL)结果显示,样品在紫外区域(320-450nm)和可见区域存在很强的发光带,其中紫外区域的宽发光带,经过高斯拟合可分为358和385nm两个发光峰,与同条件下制备得到的纯ZnO纳米材料发光谱比较,确认358nm发光峰是来自于Zn2SnO4的近带边复合发光.     

联萘酚在涂敷型淀粉衍生物手性固定相上拆分中的吸热保留及对映体洗脱顺序反转

在正相条件下,探讨了手性化合物联萘酚、联萘酚二醋酸酯、联萘酚二磺酸酯、二溴代联萘酚、氢化安息香以及萘普生在涂敷型淀粉衍生物手性固定相Lux Amylose-2上的拆分,考察了流动相中极性醇添加剂的种类及含量、柱温等对手性拆分及对映体洗脱顺序的影响。氢化安息香获得理想的拆分,分离度可达17.76;联萘酚二醋酸酯、联萘酚二磺酸酯和二溴代联萘酚得到基线或部分分离,分离度分别为3.43、2.56和1.47;萘普生未得到拆分。联萘酚拆分中观察到溶剂诱导及温度诱导对映异构体洗脱顺序反转的现象,R-联萘酚表现出少见的吸热保留特征。结合这些现象对手性识别机理进行了探讨。     

ZnO纳米线阵列的电沉积法制备及表征(英文)

利用直流电沉积方法在多孔氧化铝模板的孔洞中生成锌纳米线,在氧气氛围中,于800°C下氧化2h,将氧化铝中的锌氧化成氧化锌.本研究利用氧气氛围进行锌的氧化,大大提高了传统方法的氧化锌纳米线的制备效率.用场发射扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)和X射线衍射仪(XRD)对其形貌及成分进行表征和分析,结果表明,氧化铝模板的有序孔洞中填充了大尺寸、均匀连续的多晶态氧化锌纳米线.纳米线具有约1000:1的高纵横比,其长度等于氧化铝模板的厚度,直径约为80nm.光致发光(PL)光谱表明,氧化锌纳米线在504nm处有由于氧空位引起的较强蓝绿光发射.这为进一步研究ZnO/AAO组装体发学性质和开发新型功能器件提供了基础.     

A novel and selective spectral method for the determination of trace chlorine in water basing on the resonance scattering effect of rhodamine B-I(3) association nanoparticles

In Na₂HPO₄-citric acid buffer solution, Cl₂ can oxidize I⁻ to form I₂ and then it reacts with excess I⁻ to form I₃⁻. The I₃⁻ combines respectively with rhodamine dyes, including rhodamine B (RhB), butyl rhodamine B (b-RhB), rhodamine 6G (RhG) and rhodamine S (RhS), to form association particles which give stronger resonance scattering (RS) effect at 400 nm. The RS intensity of the RhB, b-RhB, RhG and RhS systems is proportional to chlorine concentrations in the range of 0.008-1.74, 0.019-1.33, 0.021-2.11 and 0.019-2.04 μg/mL Cl₂, respectively. The detection limits of the systems were 0.0020, 0.0048, 0.0063 and 0.0017 μg/mL, respectively. In them, the RhB system has good stability and high sensitivity, and has been applied to the analysis of chlorine in drinking water, with satisfactory results which is in agreement with that of the methyl orange (MO) spectrophotometry.     

Novel Substitution Reactions of 5-(4-Nitrophenyl)-10,15,20-triphenyl porphyrin with Nucleophilic Reagents

Substitution reactions of 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin (1)and its Ni(Ⅱ) complexe 2 with different nucleophilic reagents were studied for preparing asymmetric porphyrin. The reaction products are different with the nucleophilic reagents changing. Diporphyrin (3) was obtained when compound 1 reacted with sodium phenoxide or diphenoxide ion in DMF solution. Whereas the nitro group was reduced and 5-(4-amino-phenyl)-10,15,20-triphenylporphyrinato Nickel(Ⅱ) (4) was achieved when compound 2 reacted with above nuleophilic reagents in the same condition. The reductive product 5-(4-aminophenyl)-10,15,20-triphenylporphyrin (5) was also achieved when 1 reacted with mercaptoethanol or thiophene and lithium hydroxide. While the nitro group was substituted by cyanide anion and 5-(4-nitrilephenyl)-10,15,20-triphenylporphyrin (6) was achieved when 1 reacted with sodium cyanide.     

Table-Like Large Magnetocaloric Effect in the Misch Metal RSi Compound

Magnetic properties and the magnetocaloric effect(MCE)of the RSi(R=Ce,Pr,Nd)compounds made of Misch metal(MM)are investigated.Two transitions are found at 12K and 38K.Field variation generated large MCE and two peaks are found in the magnetic entropy change(△S)curves,which correspond to the two transition temperatures.The maximum values of the magnetic entropy changes(△S)are found to be-5.1 J/(kg·K)and-9.3 J/(kg·K)for the field ranges of 0-2 T and 0-5 T,respectively.The large AS as well as ultra-low price of MM make(MM)Si a competitive magnetic refrigerant candidate for low temperature in Eriksson cycle.