Calcium-based coordination polymers from a solvothermal synthesis of HKUST-1 in 3D printed autoclaves

A mixed-metal 1D coordination polymer [CaCu(HBTC)₂(H2O)₈]_n (where H₃BTC – benzene-1,3,5-tric arboxylic acid) was obtained in a solvothermal synthesis of a well-known copper-containing metal–organic framework [Cu₃(BTC)₂(H₂O)₃]_n (HKUST-1) in autoclaves 3D-printed from commercial polypropylene. This material was a source of calcium ions, apparently, leaking from a colorant (calcium carbonate) promoted by glacial acetic acid as a modulator used to produce large single crystals of HKUST-1. This finding was confirmed by elemental analysis and a model experiment that resulted in a new calcium-based 1D coordination polymer [Ca(H₂BTC)₂(H₂O)₅]_n under the same solvothermal conditions with no copper or calcium salts put into a 3D-printed autoclave.     

Assessment of Noise Exposure of Sawmill Workers in Southwest,Nigeria

Economic wood processing employs the use of industrial machines for cutting, shaping, milling, and sawing timber, thereby leading to the generation of high levels of noise. Published data from empirical studies have categorized noise as an environmental hazard of global significance. Furthermore, noise exposure limits for different industries and all the industrial machines available has not been formally established as it presently exists in developed nations around the world. Therefore, this study assessed the daily exposure of sawmills workers to noise in Southwestern Nigeria. Reconnaissance surveys were first carried out in Osun, Oyo, Ondo, Ekiti, Lagos, and Ogun States to select sawmills that were fully operational and fit for the study. Two fully functional sawmills in two cities of each State were eventually selected for data collection, making a total of 24 sawmills, while the Circular Machines (CM), Planer Machines (PM), and Band-saw Machines (BM) were the machines in each sawmill considered. Two machines each of CM, PM, and BM were considered in each sawmill, making a total of forty-eight (48) machines each of CM, PM, and BM. Sound data were collected between 7 am and 7 pm each day for six days (between Monday and Saturday) using Extech 407732 sound level meter and all stabilized measurements were taken three times at different intervals. The data collected were in three different periods: Machine No-work Period (NP_m), Machine Idle Period (IP_m), and Machine Working Period (WP_m). A two–way Analysis of Variance (ANOVA) was carried out at P < 0.05 to determine whether there is a significant difference in the sound level average before and after the break, for both the idle and working periods of the three machines considered. This was also done to determine whether there is a significant difference between the sound level average of the results collected during idle and working periods of the three machines. Noise Pollution Levels (L_np) ranged from 83.20 dB (PM) to 107.65 (BM) and 93.42 (CM and PM) – 116.00 (BM) respectively, while IP_m also gave the least noise pollution level of 95.79 dB and WP_m gave the highest level of 102.88 dB. The results revealed that all the machines’ L_np values in the working period are more than the 90 dB acceptable limit the recommendation value of 90 dB while 89.6% of CMs, 75% of PMs, and 89.6% of BM had their L_np above 90 dB in the idle period respectively. The minimum and the maximum noise dose levels for IP_m, WP_m and overall are 0.09 (BM) and 2.37 (CM), 0.50 (CM), and 4.77 (PM) and 0.69 (BM) and 6.64 (PM) respectively. The study found out that the fundamental contributing factors to the high noise levels in sawmills are poor machine maintenance, use of old and obsolete machines, poor housekeeping strategy, limited space, workers’ negligence, lack of PPE, and lack of occupational safety training. The study recommends that proper workplace practices such as use of personal protective equipment, new and modern machines, training, and occupational safety programmes be implemented in the considered sawmills.     

Fabricating Dual-Atom Iron Catalysts for Efficient Oxygen Evolution Reaction: A Heteroatom Modulator Approach

Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear Fe^III₂Fe^II complex (denoted as Fe₃) within the channels, a well-defined nitrogen-doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of Fe^II by other metal(II) ions (e.g., Zn^II/Co^II) via synthesizing isostructural trinuclear-complex precursors (Fe₂Zn/Fe₂Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X-ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities.     

Functional zinc(II) phthalocyanines bearing Schiff base complexes as oxidation catalysts for bleaching systems

Oxidation catalysis is used to increase the performance of hydrogen peroxide in laundry bleach applications. Bleach catalysts provide cost‐effective, energy‐saving and environmentally friendly bleach systems yielding perfect stain removal at lower temperatures. This comparative study is based on the synthesis of bis[bis(salicylhydrazonephenoxy)manganese(III)] phthalocyaninatozinc(II) ( 2 ), bis[bis(salicylhydrazonephenoxy)cobalt(III)] phthalocyaninatozinc(II) ( 3 ) and bis[bis(salicylhydrazonephenoxy)iron(III)] phthalocyaninatozinc(II) ( 4 ) as tri‐nuclear complexes consisting of two Schiff base complexes substituting a zinc phthalocyanine. Complexion on the periphery to obtain complexes 2 , 3 , 4 was performed through the reaction of a Schiff base‐substituted phthalocyanine using MnCl₂?4H₂O, CoCl₂?6H₂O or FeCl₃?6H₂O salts in basic condition in dimethylformamide. Fourier transform infrared, ¹H NMR, ¹³C NMR, UV–visible, inductively coupled plasma optical emission and mass spectra were applied to characterize the prepared compounds. The bleach performances of the three phthalocyanine compounds 2 , 3 , 4 were examined by the degradation of morin as hydrophilic dye. The degradation progress in the presence of catalysts 2 , 3 , 4 /H₂O₂ combination in aqueous solution was investigated using an online spectrophotometric method. It was found that the catalysts 2 , 3 , 4 exhibited better bleaching performance at 25 °C than tetraactylethylethylenediamine as bleach activator used in powder detergent formulations for stain removal. Copyright © 2015 John Wiley & Sons, Ltd.     

基于突变级数法的福州市某区土壤重金属污染综合评价

以福州市某区土壤为研究对象,采用突变级数法对福州市某区土壤重金属污染进行评价,依据主成分分析对评价因子进行选择,整个评价指标体系避免了人为确定权重的主观性.结果表明:福州市某区土壤重金属污染目前整体呈现一个较为良好的态势,但有部分地区处于"病态"状况.距离该区中心较近的西客站、李园天桥、远洋以及于山、东街口到靠近郊区的燎原、三角埕、鼓山等地的污染的综合隶属值呈递增的趋势,表明距离城市中心越近的土壤重金属污染越为严重.     

上海黄浦江两支流河流甲烷含量研究

甲烷是一种重要的温室气体,虽然目前大气中含量远小于二氧化碳,但排放增长率却大于后者.研究区域为上海市黄浦江支流苏州河和淀浦河,通过实验数据对比城郊春夏的甲烷排放的差异,探讨甲烷产生的机制及其与环境因子的关系,这将有助于研究河流甲烷排放对于环境变化的影响.研究结果认为河流甲烷主要来源于水中沉积物,其产生与水质、温度等因素相关;同时甲烷摩尔浓度与硝酸根离子质量体积比存在负相关性,与铵根离子质量体积比和有机碳质量分数存在正相关性.     

A Shell-by-Shell Approach for Synthesis of Mesoporous Multi-Shelled Hollow MOFs for Catalytic Applications

Over the past two decades, advanced materials with hollow interiors have received significant attention in materials research owing to their great application potential across a vast number of technological fields. Though with great difficulty, multi-shelled hollow metal–organic frameworks (MSHMs) have also been successfully synthesized in recent years. Herein, a rational shell-by-shell soft-templating protocol has been devised to fabricate highly uniform multi-shelled hollow cobalt-imidazole-based MOF (ZIF-67). For the first time, it has become possible to endow mesoporosity to this new type of functional material (i.e., mesoporous MOFs). When used as carrier materials in catalytic reactions, in principle, these mesoporous MSHMs with high surface area not only improve the dispersity of metal nanoparticles (NPs), but also efficiently facilitate the mass diffusion of the reactions, resulting in enhanced catalyst activity. Moreover, the obtained MSHMs/M nanocomposites serve as base-metal bifunctional catalysts for one-pot oxidation-Knoevenagel condensation cascade reaction, in which the MSHMs itself serves as a pristine active catalyst in addition to its role of catalyst support. The results demonstrate that excellent multifunctional catalysts can be achieved via preparing intrinsically microporous bulk MOFs into extrinsically mesoporous MSHMs which possess many structural merits that conventional bulk MOFs do not have.     

Nano-sized Cu(II) and Zn(II) complexes and their use as a precursor for synthesis of CuO and ZnO nanoparticles: A study on their sonochemical synthesis,characterization, and DNA-binding/cleavage,anticancer, and antimicrobial activities

Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)₂] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2.     

A self-penetrating and chemically stable zinc (ii)-organic framework as multi-responsive chemo-sensor to detect pesticide and antibiotics in water

Guided by the self-penetrating features can improve the stability of metal organic frameworks (MOFs), an unprecedented 3D self-penetrated framework, {[Zn (tptc)_0.5(bimb)]·H₂O}_n ( NUC-6 , here NUC corresponding to North University of China), with 3D (4,4)-c {8⁶} net, was designed. Benefit from the high chemical stability and excellent luminescent property, NUC-6 can be act as an efficient multi-response chemo-sensor in detecting dichloronitroaniline pesticide and nitrofuran antibiotics in water with the detection limits are 116 ppb for DCN pesticide, 16 ppb for NFT antibiotic, and 12 ppb for NTZ antibiotic. Besides, the mechanisms of luminescence quenching were revealed from the viewpoint of internal filter effect (IFE) and photo-induced electron transfer (PET), implied by the optical spectroscopy and quantum chemical calculation. This work provides a promising strategy to design stable MOFs by improving the self-penetrating features and to expand their practical applications in the detection of organic pollutants in aqueous medium.     

Simultaneous Removal of Antibiotics and Heavy Metals with Poly(Aspartic Acid)-Based Fenton Micromotors

The discharge of diverse pollutants has led to a complex water environment and posed a huge health threat to humans and animals. Self-propelled micromotors have recently attracted considerable attention for efficient water remediation due to their strong localized mass transfer effect. However, a single functionalized component is difficult to tackle with multiple contaminants and requires to combine different decontamination effects together. Here, we introduced a multifunctional micromotor to implement the adsorption and degradation roles simultaneously by integrating the poly(aspartic acid) (PASP) adsorbent with a MnO₂-based catalyst. The as-prepared micromotors are well propelled in contaminated waters by MnO₂ catalyzing hydrogen peroxide. In addition, the catalytic ramsdellite MnO₂(R-MnO₂) inner layer is decorated with Fe₂O₃ nanoparticles to improve their catalytic performance, contributing to an excellent degradation ability with 90% tetracycline (TC) removal in 50 minutes by enhanced Fenton-like reactions. Combining the attractive adsorption capability of poly (aspartic acid) (PASP), the composite micromotors offer an efficient removal of heavy metal ions in short time. Moreover, the designed micromotors are able to simultaneously remove antibiotic and heavy metals in mixed contaminants circumstance just in single treatment. This multifunctional micromotor with distinctive decontamination ability exhibits a promising prospective in treating multiple pollutants in the future.