Reusable Polyacrylonitrile-Sulfur Extractor of Heavy Metal Ions from Wastewater

Mercury, lead, and cadmium are among the most toxic and carcinogenic heavy metal ions (HMIs), posing serious threats to the sustainability of aquatic ecosystems and public health. There is an urgent need to remove these ions from water by a cheap but green process. Traditional methods have insufficient removal efficiency and reusability. Structurally robust, large surface-area adsorbents functionalized with high-selectivity affinity to HMIs are attractive filter materials. Here, an adsorbent prepared by vulcanization of polyacrylonitrile (PAN), a nitrogen-rich polymer, is reported, giving rise to PAN-S nanoparticles with cyclic π-conjugated backbone and electronic conductivity. PAN-S can be coated on ultra-robust melamine (ML) foam by simple dipping and drying. In agreement with hard/soft acid/base theory, N- and S-containing soft Lewis bases have strong binding to Hg²⁺, Pb²⁺, Cu²⁺, and Cd²⁺, with extraordinary capture efficiency and performance stability. Furthermore, the used filters, when collected and electrochemically biased in a recycling bath, can release the HMIs into the bath and electrodeposit on the counter-electrode as metallic Hg⁰, Pb⁰, Cu⁰, and Cd⁰, and the PAN-S@ML filter can then be reused at least 6 times as new. The electronically conductive PAN-S@ML filter can be fabricated cheaply and holds promise for scale-up applications.     

Theoretical study on a kind of cyclization mechanism of boron trichloride and hexamethyldisilazane to form the borazine ring for SiBCN ceramics precursor

Borazine rings act as a pivotal part in siliconboroncarbonitride ceramics (SiBCN) for high-temperature stability and great resistance to crystallization. A detailed investigation of the ring formation mechanism will guide the design and synthesis of SiBCN to meet application requirements under extreme conditions. Boron trichloride (BCl₃) and hexamethyldisilazane (HN(SiMe₃)₂) are common raw materials for the synthesis of precursors for SiBCN. In this paper, quantum chemical calculation was used to study the cyclization reaction mechanism between BCl₃ and HN(SiMe₃)₂ to form trichloroborazine (TCBZ) at the MP2/6-31G (d,p) level of theory. We discussed the structure properties, reaction pathways, energy barriers, reaction rates, and other aspects in detail. The results show that BCl₃ and HN(SiMe₃)₂ alternately participate in the reaction process, accompanied by the release of trimethylchlorosilane (TMCS), and that the entire reaction shows an absolute advantage in terms of energy. In the Step by step reaction, lower reaction barriers are formed due to the introduction of BCl₃ with more heat released compared to that for the introduction of HN(SiMe₃)₂. The final single-molecule cyclization and TMCS elimination steps are found to be faster compared to all previous bimolecular reactions.     

Nanomaterials for radiotherapeutics-based multimodal synergistic cancer therapy

Over the past decade, numerous studies have attempted to enhance the effectiveness of radiotherapy (external beam radiotherapy and internal radioisotope therapy) for cancer treatment. However, the low radiation absorption coefficient and radiation resistance of tumors remain major critical challenges for radiotherapy in the clinic. With the development of nanomedicine, nanomaterials in combination with radiotherapy offer the possibility to improve the efficiency of radiotherapy in tumors. Nanomaterials act not only as radiosensitizers to enhance radiation energy, but also as nanocarriers to deliver therapeutic units in combating radiation resistance. In this review, we discuss opportunities for a synergistic cancer therapy by combining radiotherapy based on nanomaterials designed for chemotherapy, photodynamic therapy, photothermal therapy, gas therapy, genetic therapy, and immunotherapy. We highlight how nanomaterials can be utilized to amplify antitumor radiation responses and describe cooperative enhancement interactions among these synergistic therapies. Moreover, the potential challenges and future prospects of radio-based nanomedicine to maximize their synergistic efficiency for cancer treatment are identified.

     

Design of novel urogenital pharmabiotic formulations containing lactobacilli,salivaricin CRL 1328 and non-microbial compounds with different functionalities

Context: The administration of pharmabiotics is a promising alternative to antimicrobial drugs for the treatment and/or prevention of female urogenital infections.

Objective: To design pharmabiotic formulations including bioactive ingredients of microbial origin combined with non-microbial substances and then to evaluate the stability of the combinations during freeze-drying and storage.

Materials and methods: Different formulations including Lactobacillus gasseri CRL 1263, Lactobacillus salivarius CRL 1328, salivaricin CRL 1328 (a bacteriocin) and non-microbial compounds (lactose, inulin and ascorbic acid) were assayed, and the ingredients were freeze-dried together or separately. The formulations were stored in gelatin capsules at 4?°C for 360?d.

Results: The viability of lactobacilli was affected to different extents depending on the strains and on the formulations assayed. L. salivarius and ascorbic acid were successfully combined only after the freeze-drying process. Salivaricin activity was not detected in formulations containing L. gasseri. However, when combined with ascorbic acid, lactose, inulin or L. salivarius, the bacteriocin maintained its activity for 360?d. The selected microorganisms proved to be compatible for their inclusion in multi-strain formulations together with lactose, inulin and ascorbic acid. Salivaricin could be included only in a L. salivarius CRL 1328 single-strain formulation together with non-microbial substances.

Conclusions: This study provides new insights into the design of urogenital pharmabiotics combining beneficial lactobacilli, salivaricin CRL 1328 and compounds with different functionalities.     

Photopolymerization synthesis of polyacrylic acid dispersant with methoxysilicon end groups and its application in a nano‐SiO2 aqueous system

In order to improve the dispersity and stability of the nano‐SiO₂ aqueous system with high solid content, a kind of polyacrylic acid dispersant with methoxysilicon end groups (KH590‐PAA) was synthesized by photopolymerization of acrylic acid (AA) initiated with (3‐mercaptopropyl)trimethoxysilane (KH590). After adding KH590‐PAA into the nano‐SiO₂ aqueous dispersion system (20 wt% solid content), the viscosity and the curing time of the system were measured with a rotational viscometer and the inverted bottle method. Moreover, the dispersion mechanism of KH590‐PAA for the nano‐SiO₂ aqueous system was researched by measuring the adsorption capacity, the particle size and the zeta potential of the nanoparticles with a conductivity meter, dynamic light scattering, SEM and TEM, respectively. The results showed that the methoxysilicon groups in KH590‐PAA could react with hydroxyl groups on the surface of nano‐SiO₂ in the process of stirring, which enhanced the adsorption capacity of the dispersant and then increased the surface charge of the particles. Therefore, electrostatic repulsion and steric hindrance effects between the SiO₂ nanoparticles could be further enhanced by adding the KH590‐PAA dispersant, and then the nano‐SiO₂ aqueous system exhibited better dispersity and stability. Besides, the dispersion properties of SiO₂ nanoparticles in water were closely related to the addition amount and the molecular weight of the KH590‐PAA dispersant. © 2018 Society of Chemical Industry     

电喷雾质谱法示踪钨回收过程离子的转化路径

将环隙式离心萃取器(ACCs)与电喷雾飞行时间质谱(ESI-TOF-MS)相结合，在线监测了回收过程中的钨萃取行为(宏观)和钨形态的转化路径(微观)，发现宏观萃取反应和微观离子形态转化同时发生并相互补充。伯胺N1923萃取钨在144 s内即可达到萃取平衡，萃取率高达98%以上，同时，酸钨比n(H)/n(W)是一个关键变量，当酸钨比n(H)/n(W)=2.4时，全流程钨回收率超过93%。最后，得到了基于钨形态监测的萃取机理，同时，减少原料液中W1含量，增加W10含量，可有效提高钨回收效率。     

一种基于小字典不对等语料的跨语言词嵌入方法

双语词嵌入通常采用从源语言空间到目标语言空间映射,通过源语言映射嵌入到目标语言空间的最小距离线性变换实现跨语言词嵌入。然而大型的平行语料难以获得,词嵌入的准确率难以提高。针对语料数量不对等、双语语料稀缺情况下的跨语言词嵌入问题,该文提出一种基于小字典不对等语料的跨语言词嵌入方法,首先对单语词向量进行归一化,对小字典词对正交最优线性变换求得梯度下降初始值,然后通过对大型源语言(英语)语料进行聚类,借助小字典找到与每一聚类簇相对应的源语言词,取聚类得到的每一簇词向量均值和源语言与目标语言对应的词向量均值,建立新的双语词向量对应关系,将新建立的双语词向量扩展到小字典中,使得小字典得以泛化和扩展。最后,利用泛化扩展后的字典对跨语言词嵌入映射模型进行梯度下降求得最优值。在英语—意大利语、德语和芬兰语上进行了实验验证,实验结果证明该文方法可以在跨语言词嵌入中减少梯度下降迭代次数,减少训练时间,同时在跨语言词嵌入上表现出较好的正确率。     

Design and synthesis of side-chain optimized poly(2,6-dimethyl-1,4-phenylene oxide)-g-poly(styrene sulfonic acid) as proton exchange membrane for fuel cell applications: Balancing the water-resistance and the sulfonation degree

Side-chain optimized poly (2,6-dimethyl-1,4-phenylene oxide)-g-poly (styrene sulfonic acid) (PPO-g-PSSA) is designed with balanced water-resistance and sulfonation degree. The PPO-g-PSSA is synthesized by controlled atom-transfer radical polymerization (ATRP) from brominated poly (2,6-dimethyl-1,4-phenylene oxide) (PPO-xBr) and ethyl styrene-4-sulfonate and followed by hydrolysis. A series of PPO-g-PSSA are prepared possessing different bromination degree (x) of PPO-xBr and polymerization degree (m) of the side-chains and the water-resistances of the fabricated membranes are investigated. The results show that a PPO-g-PSSA at relatively low x (x < 0.2) and high m (m > 4) exhibits good balance between the water-resistance and the sulfonation degree. Namely, it displays suitable proton conductivity with compromised water-resistance. Moreover, a maximum ion exchange capacity (IEC) of 3.24 mmol g^?1 is reached without the sacrifice of water-resistance. In addition, PPO-g-0.08PSSA-13 and PPO-g-0.14PSSA-4 are chosen characterized by thermogravimetric analysis, proton conductivities and mechanical properties. At 90% RH, the optimized PPO-g-0.08PPSA-13 possesses a proton conductivity of 37.9 mS cm^?1 at 40 °C and 45.5 mS cm^?1 at 95 °C, respectively.