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PROCESS SAFETY PROGRESS · 2017 ·Vol. 37 ·期 3 ·355-361 · IF 0.812

Inherently safer design for synthesis of 3-methylpyridine-N-oxide

Min Hua,Min Qi,Xuhai Pan,Wendi Yu,Lu Zhang,Juncheng Jiang

Alkyl pyridine-N-oxide can decompose to pyridine which readily leads to explosion accident in air. Therefore, risk analysis and inherently safer design are necessary for this process. This article aims to study the thermal hazards of the process of 3-methylpyridine oxidized by hydrogen peroxide, and then the corresponding Inherently Safer Designs (ISDs) were proposed. The inherent hazards during the process were first qualitatively evaluated by Qualitative Assessment for Inherently Safer Design. Then, the reaction calorimeter was employed to analyze the thermal hazards of the target reaction. Meanwhile, the Integrated Inherent Safety Index methods were simplified to quantitatively estimate the level of inherent safety of the process. The results show that the potential risk of the process is 87.2% which is at the high risk level. Based on the hazard identification and assessment results, three ISDs, namely adding catalyst (ISD I), improving reaction condition (ISD II), and using a tubular (ISD III), were proposed to enhance the safety. Finally, combining comparative experiments with ISI methods, an effect evaluation model for ISD was established to verify the rationality of the ISDs. The results indicate that the reaction hazards are diminished when three ISDs are utilized in production process. The inherent safety level of the reaction is increased by 22.2%, 50.7%, and 31.8%, respectively. © 2017 American Institute of Chemical Engineers Process Process Saf Prog 37:355–361, 2018

CAS / MDL: 108-99-6
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Biomedical Materials · 2025 ·Vol. 20 ·期 2 ·025030 · IF 3.7

Analgesic effect of microneedle with 3-acetylaconitine for neuropathic pain

Juan Huang,Yanhui Li,Mengru Zhu,Jigang Luo,Zhuoyue Song,Shijie Li,Tao Liu,Chunzhi Tang,Nenggui Xu,Shihui Liu

Neuropathic pain is a worldwide problem that causes physical and psychological pain to many patients. 3-acetylaconitine (AAC) is a kind of non-narcotic analgesic with long-lasting action, non-tolerant and non-addiction. However, it has some cardiac toxicity and can easily cause toxic organ damage. To solve these problems, dissolvable microneedle (MN) patches were prepared and delivered subcutaneously through the skin barrier. The results showed that the solid dispersion made with AAC and polyvinyl pyrrolidone (PVP) effectively changed the solubility of AAC and improved its bioavailability. The MN shape was conical and the bending forces of AAC/PVP-MN were all approximately 1.2 N/needle, which was enough to penetrate the stratum corneum of the skin. Through the use of the neuropathic pain model (spared nerve injury) test, it was found that the soluble MN mediated AAC hypodermic delivery provided effective analgesic activity. Compared with the model group, AAC/PVP-MN could increase mechanical pain threshold and hind legs load-bearing capacity, reduce the inflammation in the body, and have certain protective effect to spinal cord neurons. This study provided an idea for the clinical treatment of neuropathic pain and also a new approach for the safe use of toxic drugs with a narrow range.

CAS / MDL: 989-38-8
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JOURNAL OF LOSS PREVENTION IN THE PROCESS INDUSTRIES · 2015 · IF 1.406

Thermal hazard assessment for synthesis of 3-methylpyridine-N-oxide

L. Zhang,W.D. Yu,X.H. Pan,J.J. Fang,M. Hua,F.M. Chen,J.C. Jiang

The exothermic oxidation of 3-methylpyridine with hydrogen peroxide was analyzed by Reaction Calorimeter (RC1e) in semi-batch operation. Heat releasing rate and heat conversion were studied at different operating conditions, such as reaction temperature, feeding rate, the amount of catalyst and so on. The thermal hazard assessment of the oxidation was derived from the calorimetric data, such as adiabatic temperature rise (ΔT ad ) and the maximum temperature of synthesis reaction (MTSR) in out of control conditions. Along with thermal decomposition of the product, the possibility of secondary decomposition under runaway conditions was analyzed by time to maximum rate (TMR ad ). Also, risk matrix was used to assess the risk of the reaction. Results indicated that with the increase of the reaction temperature, the reaction heat release rate increased, while reaction time and exotherm decreased. With the increase of feeding time, heat releasing rate decreased, but reaction time and exotherm increased. With the amount of the catalyst increased, heat releasing rate increased, reaction time decreased and exothermic heat increased. The risk matrix showed that when the reaction temperature was 70 °C, feeding time was 1 h, and the amount of catalyst was 10 g and 15 g, respectively, the reaction risk was high and must be reduced.

CAS / MDL: 1003-73-2 108-99-6
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RSC Advances · 2017 ·Vol. 7 ·期 3 ·1260-1265 · IF 3.108

3-Dimensional stable polyelectrolyte hollow capsules: preparation and spontaneous encapsulation

Y. D. Chen,J. J. Xu,Y. Wang,H. Chen,Q. J. Luo,X. D. Li,W. P. Zhu

In this study, by alternatively depositing a poly(styrene)-co-poly(acrylic acid)/poly(allylamine hydrochloride) multilayer on the poly(styrene sulfonate sodium) hybrid CaCO3 spherical templates, a series of size-controlled and low-dispersed polyelectrolyte capsules were obtained after the removal of hybrid templates. These polyelectrolyte capsules can retain their 3-dimensional spheric shape after being dried at room temperature. Through investigating the structure and key factors for the formation of novel capsules, formation mechanism of the 3-dimensional stable capsule wall was discussed. Further investigation showed that the dry capsules could spontaneously entrap water-soluble positively charged substances from the bulk solution into the capsule interior, just like the wet capsules.

CAS / MDL: 81-88-9
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ACS Omega · 2018 · IF 0

Hexamethylcucurbit[3,3]uril-Based Porous Supramolecular Assemblies and Their Adsorption Properties

Xin-Xin Wang,Fei-Yang Tian,Kai Chen,Yun-Qian Zhang,Zhu Tao,Qian-Jiang Zhu

In the present work, we selected hexamethylcucurbit[3,3]uril (Me6Q[3,3]) as a building block and obtained two Me6Q[3,3]-based porous supramolecular assemblies from neutral water (A) and aqueous HCl solutions (B), respectively. Both Me6Q[3,3]-based assemblies are constructed of Me6Q[3,3] molecules through the typical outer surface interaction of cucurbit[n]urils, as well as hydrogen bonding between latticed water molecules and portal carbonyl oxygens of Me6Q[3,3]. The assemblies present different porous structure features and exhibit different adsorption properties for eight common volatile organic compounds. However, the two porous assemblies exhibit similar adsorption properties for certain fluorophore dyes, including rhodamine B (G1), fluorescein (G2), and pyrene (G3), and form solid colored fluorescent compounds, some of which exhibit responses to the selected volatile organic compounds.

研究领域: 化学 · 材料科学
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2020 · IF 2.369

Solubility Determination and Modeling Analysis of exo-3,6-Epoxy-1,2,3,6-tetrahydrophthalic Anhydride in Mixture Solvents from 278.15 to 323.15 K

Yanmin Shen,Wenju Liu,Paifeng Shi,Zehua Bao

In this work, solubility of exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (ETA) was measured and discussed in acetone + ethanol, methyl acetate + ethanol, 1,4-dioxane + ethanol, and ethyl acetate + ethanol mixture solvents in a temperature range from 278.15 to 323.15 K by a gravimetric method under 0.1 MPa. Experimental results indicated that solubility increased with temperature increasing and declined with the mass fraction increasing of ethanol in four kinds of mixture solvents. The solvent effect and Hansen solubility parameter were adopted to discuss the solubility behavior of ETA in selected solvents. Modeling correlation solubility data about ETA indicated that the Jouyban–Acree–Apelblat model (J–A–A) was more suitable than the Jouyban–Acree–Van’t Hoff model (J–A–V) and Ma and Sun model in mixture solvents. Processing of the dilution crystallization in acetone + ethanol system was chosen to separate and purify ETA on the basis of the solubility and solvent characteristics.

研究领域: 化学工程 · 物理化学
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RESEARCH ON CHEMICAL INTERMEDIATES · 2022 ·Vol. 49 ·期 8 ·3381-3393 · IF 3.134

Synthesis of Mo–doped symbiotic mixture of Bi2WO6 and Bi6O6(OH)3(NO3)3·1.5H2O nanosheets with enhanced photocatalytic degradation for mustard gas simulator 2-CEES

Yang Haoguo,Guo Yijun,Han Shitong,Xi Hailing,Lin Huaxiang,Yuan Rusheng,Ding Zhengxin,Long Jinlin,Lin Qun

Mustard gas is a kind of erosive poison with great harm and used as a chemical weapon since World War. It has suggested that the photocatalytic technology is an effective method to eliminate it. Because the small difference in molecular structure between 2-CEES and Mustard gas, and the less toxic of 2-CEES, 2-CEES is often used as a simulator to evaluate the photocatalytic activity of catalysts. In this work, symbiotic mixture of Bi 2 WO 6 and Bi 6 O 6 (OH) 3 (NO 3 ) 3 ·1.5H 2 O nanosheets doped with Mo (Mo-B-B) have been synthesized by a facile hydrothermal treatment. The samples were characterized by XRD, DRS, XPS, SEM, TEM, Raman, and PL. The photocatalytic activity of the samples was evaluated by measuring the degradation of 2-CEES under visible light irradiation. The results showed that the doped Mo reduce the Eg of bare symbiotic mixture and improve the separation efficiency of photo-generated carriers that is beneficial to photocatalytic activity. The optimum amount of doped Mo is 5% that exhibits the best activity for degradation for 2-CEES.

CAS / MDL: 693-07-2
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FOOD CHEMISTRY · 2022 · IF 9.231

Characterization of a new (Z)-3:(E)-2-hexenal isomerase from tea (Camellia sinensis) involved in the conversion of (Z)-3-hexenal to (E)-2-hexenal

Cong Chen,Fei Yu,Xinli Wen,Shuna Chen,Kaixi Wang,Feiquan Wang,Jianming Zhang,Yuanyuan Wu,Puming He,Youying Tu,Bo Li

Two major green leaf volatiles (GLVs) in tea that contribute greatly to tea aroma, particularly the green odor, are (E)-2-hexenal and (Z)-3-hexenal. Until now, their formation and related mechanisms during tea manufacture have remained unclear. Our data showed that the contents of (E)-2-hexenal and (Z)-3-hexenal increased more than 1000-fold after live tea leaves were torn. Subsequently, a new (Z)-3:(E)-2-hexenal isomerase (CsHI) was identified in Camellia sinensis . CsHI irreversibly catalyzed the conversion of (Z)-3-hexenal to (E)-2-hexenal . Abiotic stresses including low temperature, dehydration, and mechanical wounding, did not influence the (E)-2-hexenal content in intact tea leaves during withering, but regulated the proportions of (Z)-3-hexenal and (E)-2-hexenal in torn leaves by modulating CsHI at the transcript level. For the first time, this work reveals the formation of (E)-2-hexenal during tea processing and suggests that CsHI may play a pivotal role in tea flavor development as well as in plant defense against abiotic stresses.

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APPLIED AND ENVIRONMENTAL MICROBIOLOGY · 2020 ·Vol. 86 ·期 19 · IF 4.016

3-Hydroxypyridine Dehydrogenase HpdA Is Encoded by a Novel Four-Component Gene Cluster and Catalyzes the First Step of 3-Hydroxypyridine Catabolism in Ensifer adhaerens HP1

Haixia Wang,Xiaoyu Wang,Hao Ren,Xuejun Wang,Zhenmei Lu

3-Hydroxypyridine (3HP) is an important natural pyridine derivative. Ensifer adhaerens HP1 can utilize 3HP as its sole sources of carbon, nitrogen, and energy to grow, but the genes responsible for the degradation of 3HP remain unknown. In this study, we predicted that a gene cluster, designated 3hpd, might be responsible for the degradation of 3HP. The analysis showed that the initial hydroxylation of 3HP in E. adhaerens HP1 was catalyzed by a four-component dehydrogenase (HpdA1A2A3A4) and led to the formation of 2,5-dihydroxypyridine (2,5-DHP). In addition, the SRPBCC component in HpdA existed as a separate subunit, which is different from other SRPBCC-containing molybdohydroxylases acting on N-heterocyclic aromatic compounds. Moreover, the results demonstrated that the phosphoenolpyruvate (PEP)-utilizing protein and pyruvate-phosphate dikinase were involved in the HpdA activity, and the presence of the gene cluster 3hpd was discovered in the genomes of diverse microbial strains. Our findings provide a better understanding of the microbial degradation of pyridine derivatives in nature and indicated that further research on the origin of the discovered four-component dehydrogenase with a separate SRPBCC domain and the function of PEP-utilizing protein and pyruvate-phosphate dikinase might be of great significance.IMPORTANCE 3-Hydroxypyridine is an important building block for the synthesis of drugs, herbicides, and antibiotics. Although the microbial degradation of 3-hydroxypyridine has been studied for many years, the molecular mechanisms remain unclear. Here, we show that 3hpd is responsible for the catabolism of 3-hydroxypyridine. The 3hpd gene cluster was found to be widespread in Actinobacteria, Rubrobacteria, Thermoleophilia, and Alpha-, Beta-, and Gammaproteobacteria, and the genetic organization of the 3hpd gene clusters in these bacteria shows high diversity. Our findings provide new insight into the catabolism of 3-hydroxypyridine in bacteria.

CAS / MDL: 5154-01-8
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PEST MANAGEMENT SCIENCE · 2019 ·Vol. 75 ·期 12 ·3273-3281 · IF 3.255

One-pot synthesis, structure and structure–activity relationship of novel bioactive diphenyl/diethyl (3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl)(arylamino)methylphosphonates

Bao-Lei Wang,Hong-Wei Zhu,Zheng-Ming Li,Xiao Zhang,Shu-Jing Yu,Yi Ma,Hai-Bin Song

BACKGROUND N -Pyridylpyrazole derivatives have received continuous attention in agrochemical research during the last decade owing to their remarkable insecticidal or fungicidal potentials. To look for novel heterocyclic agrochemicals for increasing production of agriculture, a series of novel α -aminophosphonate derivatives containing N -pyridylpyrazole moiety were synthesized. RESULTS The structures of the title compounds were confirmed via melting point, IR, 1 H NMR, 13 C NMR, 31 P NMR, HRMS and elemental analysis. The single crystal structure of diethyl (3-bromo-1-(3-chloropyridin-2-yl)-1 H -pyrazol-5-yl)(2,6-dimethylphenylamino)methylphosphonate (compound 12b) was first reported. Moreover, the bioassays displayed that the title compounds exhibited modest or weak insecticidal activities against oriental armyworm at 200 μg mL −1 . The first investigation on the fungicidal potential of chlorantraniliprole showed no significant activities towards the six tested fungi found in this study, however, most of the title compounds displayed apparent in vitro fungicidal activity against some plant fungi, in particular excellent activities towards Physalospora piricola . Compounds 11a and 11b had EC 50 values of 18.8 and 17.4 μg mL −1 , respectively, which were comparable with that of fungicide control triadimefon (EC 50 = 24.7 μg mL −1 ) against Physalospora piricola . In addition, some compounds exhibited modest in vivo control efficacy at 0.5 mg mL −1 towards Sclerotinia sclerotiorum (11b: 30.1(±1.8)%), Rhizoctonia cerealis (11a: 20.4(±2.1)%; 11b: 30.2(±2.2)%), and Erysiphe graminis (11a: 30.3(±1.8)%; 12d: 40.2(±0.9)%). CONCLUSION Compounds 11a, 11b and 12d could be promising new lead structures for the development and discovery of novel fungicides towards Physalospora piricola and Erysiphe graminis . The structure-activity relationship (SAR) analysis provided useful guidance and new understanding for the design of novel pyridylpyrazole-containing agrochemicals. © 2019 Society of Chemical Industry

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JOURNAL OF APPLIED POLYMER SCIENCE · 2024 · IF 2.7

Construction and tribological properties of poly acrylic acid-poly(3-(methacryloylamino)propyl) dimethyl(3-sulfopropyl)ammonium hydroxide hydrogel coatings embedded with SiO2 nanoparticles on Ti6Al4V substrate

Yaling Deng,Lei Nie,Yu Xu,Chenhong Gao,Zhe Wu

The development of highly effective bio-lubricant coatings for arthritis treatment is extremely demanded. Herein, inspired by the efficient lubrication of articular cartilage, acrylic acid (AA) with (3-(methacryloylamino) propyl) dimethyl (3-sulfopropyl) ammonium hydroxide (MPDSAH) hydrogel coatings containing nanoparticles on Ti6Al4V substrate were designed and fabricated via UV grafting technology. SiO 2 and SiO 2 grafted with PAA polymer brushes (SiO 2 -g-PAA) were separately doped into the PAA-PMPDSAH hydrogel. The PAA-PMPDSAH/SiO 2 -g-PAA exhibits good tensile and compressive properties compared with PAA-PMPDSAH/SiO 2 hydrogel, with an enhancement of 183.4% in tensile modulus and 60.8% in compressive modulus. The PAA-PMPDSAH/SiO 2 -g-PAA hydrogel coatings exhibit a low wear volume, 2.9 ± 0.16 × 10 6 μm 3 , representing a decline of 32.1% and 61.3% compared with the PAA-PMPDSAH and PAA-PMPDSAH/SiO 2 hydrogel coatings, respectively. The antiwear performance has obviously improved. The hydrophilic PAA polymer brushes prevent the agglomeration of nanoparticles and promote homogeneously dispersion within the hydrogel. The three-dimensional crosslinked network structure of hydrogel effectively protects the structural integrity of the polymer brushes, thereby facilitating enduring lubrication properties. This work provides a strategy for promising artificial joint lubrication in biomedical fields.

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Foods · 2024 ·Vol. 13 ·期 2 ·261 · IF 4.7

Effects of Endogenous Antioxidants in Camellia Oil on the Formation of 2-Monochloropropane-1, 3-diol Esters and 3-Monochloropropane-1,2-diol Esters during Thermal Processing

Shanshan Liu,Mingyue Shen,Jianhua Xie,Bohan Liu,Chang Li

2-Monochloropropane-1, 3-diol (2-MCPD) esters and 3-monochloropropane-1,2-diol (3-MCPD) esters, a class of substances potentially harmful to human health, are usually formed during the refining of vegetable oils under high temperature. The effects of endogenous antioxidants in vegetable oils on the formation of 2- and 3-MCPD esters is still unknown. In this study, the effects of endogenous antioxidants (α-tocopherol, stigmasterol and squalene) on the formation of 2- and 3-MCPD esters in model thermal processing of camellia oil were investigated. The possible formation mechanism of 2- and 3-MCPD esters was also studied through the monitoring of acyloxonium ions, the intermediate ions of 2- and 3-MCPD esters formation, and free radicals by employing infrared spectra and electron paramagnetic resonance (EPR), respectively. The results indicated that the addition of α-tocopherol had either promoting or inhibiting effects on the formation of 2- and 3-MCPD esters, depending on the amount added. Stigmasterol inhibited the formation of 3-MCPD ester and 2-MCPD ester at low concentrations, while promoting their formation at high concentrations. Squalene exhibited a promotional effect on the formation of 3-MCPD ester and 2-MCPD ester, with an increased promotion effect as the amount of squalene added increased. The EPR results suggested that CCl3•, Lipid alkoxyl, N3• and SO3• formed during the processing of camellia oil, which may further mediate the formation of chlorpropanol esters. This study also inferred that squalene promotes the participation of the free radical in chlorpropanol ester formation.Keywords:MCPD esters;endogenous antioxidants;camellia oil;mechanism

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