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KOREA-AUSTRALIA RHEOLOGY JOURNAL · 2024 · IF 2.2

Flow-induced demixing of polyisoprene/poly(4-tert butyl styrene) with high dynamic contrast

Hong Zonghao,Wu Shilong,Chen Quan

This study places a focus on flow-induced demixing of polyisoprene (PI) and poly(4-tert butyl styrene) (PtBS) polymer blends with high dynamic contrast. The rheological response is governed by the more immobilized PtBS chains. In contrast, the dielectric response at low frequency reflects exclusively the normal mode of PI chains having type-A dipole parallel along the chain backbone. These features enable selective detection of the component dynamics of PtBS or PI chains under either the small amplitude oscillatory shear or the nonlinear steady shear through a combination of rheological and dielectric techniques. We find the Cox–Merz rule fails significantly for the PtBS/PI blends, which is attributed to flow-induced demixing when the shear rate is higher than the relaxation rate of PtBS chains and lower than that of PI chains. The flow-induced demixing is further supported by varying the molecular parameters of PtBS, copolymerizing PtBS with polystyrene, as well as by the rheo-dielectric measurements that show a broadening of the PI relaxation mode distribution. This demixing could be partly driven by the increased conformational entropy of the PI chains after segregation from the surrounding restrictive PtBS chains. Graphical abstract

CAS / MDL: 100-42-5 1746-23-2
研究领域: 高分子科学 · 材料科学 · 物理化学
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Biology-Basel · 2025 ·Vol. 14 ·期 6 ·655 · IF 3.5

Enhanced Lethal Effects of Combined P-tert-Butylcatechol and L-Lysine on Microcystis aeruginosa

Heyun Jiao,Gangwei Jiao,Ruitong Jiang,Yifei Shen,Peimin He,Liu Shao

Simple SummaryHarmful algal blooms caused byMicrocystis aeruginosathreaten aquatic ecosystems and human health. This study explores the combined effects of two natural allelochemicals, P-tert-butylcatechol (TBC) and L-lysine, in controllingM. aeruginosa. When combined at low concentrations (0.04 mg/L TBC + 1 mg/L L-lysine), they achieved over 90% growth inhibition within 96 h. The treatment damaged algal cell membranes, reduced photosynthetic efficiency, and triggered oxidative stress. Furthermore, intracellular and extracellular microcystin levels decreased significantly compared to untreated algae, minimizing ecological risks. These findings highlight the potential of the combination of TBC and L-lysine as a safe and cost-effective strategy for mitigating harmful algal blooms.Allelochemicals are recognized as promising algaecides due to their environmental safety. Para-tert-butylcatechol (TBC) and L-lysine exhibit significant potential in suppressing harmful algal blooms (HABs); however, their combined effects and algae inhibition mechanisms remain unelucidated. Therefore, this study systematically investigated the growth inhibition ofMicrocystis aeruginosaby TBC and L-lysine individually and in combination, while simultaneously examining their combined effects on algal growth, cell membrane integrity, photosynthetic activity, antioxidant responses, and microcystin production. The results revealed a significant interactive effect between TBC (0.04 mg/L) and L-lysine (1 mg/L), achieving over 90% growth inhibition within 96 h. The combined treatment significantly inhibitedM. aeruginosagrowth through impaired photosynthetic efficiency and elevated oxidative stress. Compared to the control group, the treatment group exhibited a continuous decline in chlorophyll-a content, phycobiliprotein levels,Fv/Fm, YII, α, and rETRmax, while phosphoenolpyruvate carboxylase (PEPC) activity decreased by 96.48% by day 8. And antioxidant enzymes, including superoxide dismutase (SOD) and reduced glutathione (GSH), showed a progressive increase in activity. In addition, the structure and integrity of the cell membrane ofM. aeruginosawere damaged after treatment, and the conductivity of the treatment groups increased continuously from 2.32 to 4.63 μs/cm. In addition, under combined treatment, intra- and extracellular microcystin levels initially increased (peaking at day 2) but sharply declined thereafter, becoming significantly lower than controls by day 8. These findings highlight the potential of combining TBC and L-lysine as an eco-friendly and cost-effective strategy for mitigatingM. aeruginosa-dominated harmful algal blooms.

CAS / MDL: 56-87-1
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2025 · IF 3.9

Apparent Kinetics Study and Continuous Synthesis of Di-tert-butyl Hydroperoxide in a Microreactor

Mingyue Li,Zhixiang Li,Gang Qian,Xuezhi Duan,Xinggui Zhou,Jing Zhang

Di-tert-butyl hydroperoxide (DTBP) is mainly used as a polymerization initiator, with an annual global market of ∼$30 million. Industrial production of DTBP is carried out via the acid-catalyzed peroxidation of tert-butanol (TBA) by H2O2 in batch reactors. Because of its highly exothermic and reactive nature, a dropwise feeding method is required, leading to a low production efficiency. In addition, the large liquid holdup in batch operations poses a significant safety risk of runaway reactions. Here, we report a highly efficient, continuous-flow approach for the production of DTBP in a microreactor system, achieving a DTBP selectivity of 96.5% and a DTBP yield of 93.6% at a TBA conversion of 97.0% within a residence time of 420 s. This performance outperforms conventional batch operations, which typically yield ∼92% DTBP and require several hours for feeding and reaction. The markedly enhanced production efficiency is owed to the improved heat-removal capacity of the microreactor, which eliminates the need for dropwise feeding and allows the reaction to safely proceed at higher temperatures. The microreactor system also exhibits precise temperature control during the apparent kinetics measurements for DTBP formation, with any thermal runaway-induced temperature rise remaining below 3 °C. Density functional theory calculations indicate a lower energy barrier for the second step (acid-catalyzed condensation to form DTBP) than for the first step (peroxidation of TBA to tert-butyl hydroperoxide), consistent with the trend in apparent activation energies from kinetic studies. These kinetic and mechanistic insights can guide the optimization of continuous-flow DTBP production with an enhanced efficiency and safety.

CAS / MDL: 127-09-3 7681-11-0
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Thermal safety upgrading: Batch-to-flow transition of acid-catalyzed tert-butyl peroxypivalate synthesis

Dan Wei,Kai Ma,Lei Ni,Ahmed Mebarki,Gang Fu,Juncheng Jiang

Traditional batch peroxyester synthesis processes pose a significant risk due to the presence of thermally unstable substances and highly exothermic nature of the reactions, highlighting the urgent need for a shift toward greener processes. With the aim to enhance safety of this process, a batch-to-flow transition was conducted, taking acid-catalyzed acylation of pivalic anhydride (PAn) with tert -butyl hydroperoxide (TBHP) to synthesize tert -butyl peroxypivalate (TBPP) as a case study. The acylation mechanism was investigated through density function theory calculation as well as in situ IR characterization. It was demonstrated that PAn first reacts with sulfuric acid to form pivalic acid sulfate, which subsequently undergoes nucleophilic attack by TBHP, yielding the corresponding peroxyester. The effects of process conditions, including reaction temperature, dosing rate, stirring rate and molar ratio, on thermal hazards in the semi-batch reactor was assessed. Under this mode, the processes which gained high yields (>90 %) showed unacceptable thermal runaway hazards. Then, the reaction was carried out under flow conditions. The process was optimized based on multi-objective Bayesian optimization. Through the batch-to-flow transition, it was showcased that the thermal runaway hazard could be reduced from severe (Class V) to moderate (Class II) along with a 74-fold increase in space-time yield. Furthermore, to distinguish the thermal risks quantitatively under different conditions in flow, a risk factor (R-factor) was proposed for the first time as a safety metric. With the application of R-factor, safety-oriented optimization in flow was made possible and sustainable synthesis processes could be realized.

CAS / MDL: 1538-75-6
研究领域: 化学工艺安全 · 流动化学 · 有机合成 · 反应工程 · 热分析 · 工艺优化
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Journal of Environmental Chemical Engineering · 2023 · IF 7.7

Visible-light-driven removal of 4-tert-butylphenol by coupled photoredox and enzyme catalysis

Weichao Xu,Yuxuan Yi,Kunhao Guo,Anming Li,Xuehan Zhang,Feng Guo

The combination of photocatalysis and enzyme catalysis makes many previously difficult or slow chemical reactions easy to realize. A novel [email protected] −C 3 N 4 biohybrid catalyst was successfully synthesized using a simple in situ synthesis method to remove 4- tert -butylphenol (4- t -BP). A series of characterization methods were used to investigate the structure, morphology, chemistry, and optical properties of biohybrid catalysts. [email protected] −C 3 N 4 has improved photogenerated electron-hole pair separation efficiency and charge carrier mobility , as well as photocatalytic activity, with a removal rate of 4- t -BP nearly 100% within 180 min. The catalyst recycling test revealed that the composite could maintain its high removal efficiency after 10 recyclings. Meanwhile, the photocatalytic mechanism investigation reveals that ∙O 2 − play critical roles in the removal of 4- t- BP by g−C 3 N 4 . A detailed examination of the mechanism and pathway of 4- t -BP removal by photoenzyme oxidation was also carried out. This biohybrid catalyst opened up a new avenue for the advancement of environmental protection technology .

研究领域: 环境科学 · 化学工程 · 材料科学 · 催化 · 环境技术
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JOURNAL OF ASIAN NATURAL PRODUCTS RESEARCH · 2015 · IF 0.913

Ginsenoside Rg1 relieves tert-Butyl hydroperoxide-induced cell impairment in mouse microglial BV2 cells

Dan Lu,Li-Hong Zhu,Xiao-Ming Shu,Chan-Juan Zhang,Jia-Yi Zhao,Ren-Bin Qi,Hua-Dong Wang,Da-Xiang Lu

Microglial activation plays an important role in neurodegenerative diseases associated with oxidative stress. tert-Butyl hydroperoxide (t-BHP), an analog of hydroperoxide, mimics the oxidative damage to microglial cells. It has been reported that ginsenoside Rg1 (G-Rg1), an active ingredient of Panax ginseng, has anti-stress and anti-inflammatory properties. The present study aims to investigate the ability of G-Rg1 to decrease the t-BHP-mediated cell damage of BV2 microglial cells. We performed flow cytometry assays to facilitate the detection of reactive oxygen species as well as Western blotting analyses and immunofluorescence assays using specific antibodies, such as antibodies against phospho-mitogen-activated protein kinases (p-MAPKs), phospho-nuclear factor-κB (p-NF-κB), B-cell lymphoma 2 (Bcl-2), Bcl-2-associated X (Bax), Caspase-3, autophagy marker light chain 3 (LC3), and Becline-1. We found that treatment with 50 μM G-Rg1 protected microglial cells against oxidative damage induced by 10 μM t-BHP.

CAS / MDL: 75-91-2
研究领域: 神经科学 · 药理学 · 细胞生物学
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ENERGY & FUELS · 2019 · IF 3.021

Hydroperoxide Formation and Thermal Oxidation of Methyl tert-Butyl Ether Oxidation at Low Temperature

Qiang Zhang,Mieko Kumasaki,Xiongmin Liu,Fan Ren,Yosuke Nishiwaki,Bo Wang,Satoshi Matsue

In this work, we investigated the thermal oxidation of methyl tert-butyl ether (MTBE) using a customer-designed mini-closed-pressure vessel test and quantitatively analyzed the hydroperoxides produced in the primary oxidation via iodimetry. Results showed that MTBE formed high levels of hydroperoxide (5053 ppm) in its autoxidation at 140 °C. While the temperature was lower than 110 °C, a known condition at which hydroperoxide was undetectable, MTBE maintained stability. One of the hydroperoxides isolated from MTBE oxidation products was identified as 1-tert-butoxymethyl hydroperoxide (TBMHP) according to liquid chromatography–mass spectrometry, 1H and 13C nuclear magnetic resonance spectroscopy, and Fourier transform infrared spectroscopy analysis. The thermal decomposition of TBMHP was assessed via differential scanning calorimeter (DSC). Results indicated that exothermic onset temperature (Tonset) and thermal decomposition heat (QDSC) of TBMHP were 108.10 °C and 1478.05 J·g–1, respectively. The activation energy of TBMHP with the Kissinger method was 76.23 kJ·mol–1. Moreover, DSC experiments were employed to study the primary oxidation of MTBE with different equivalence ratios, indicating that primary oxidation temperature (T0) of MTBE was 208.52 °C with the equivalence ratio of 0.05. Increasing the equivalence ratio led to a considerable decrease in T0.

研究领域: 化学 · 环境科学
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JOURNAL OF LOSS PREVENTION IN THE PROCESS INDUSTRIES · 2022 · IF 3.916

Reaction mechanism and process safety assessment of acid-catalyzed synthesis of tert-butyl peracetate

Yuying Zhang,Lei Ni,Hang Yao,Qiang Chen,Juncheng Jiang,Chi-Min Shu,Zhiquan Chen,Chenghao Li,Wen Zhu

Esterification during the synthesis of tert -butyl peracetate (TBPA) is highly exothermic. Since peroxides ( tert -butyl hydroperoxide TBHP and TBPA) are intrinsically thermosensitive, this synthesis process is potentially dangerous. In this work, the exothermic process and mechanism of TBPA synthesis using acetic anhydride (Ac 2 O) and TBHP under the catalysis of sulphuric acid (H 2 SO 4 ) were clarified by calorimetry , infrared spectroscopy, and high-performance liquid chromatography. To substantially alleviate the thermal risk of the reaction, and to feasibly select appropriate synthesis conditions for ensuring the process safety of the synthesized products, several sets of isothermal and isoperibol experiments were performed using calorimetry. The intermediates formed and concentration changes during the reaction were monitored using in-situ Fourier-transform infrared spectroscopy. Differential scanning calorimetry and adiabatic calorimetry were used to assess the thermal hazard of the materials during the synthesis process. The reaction mechanism was verified using density functional theory calculations. The results revealed that a controlled increase in exothermicity could be achieved by adding aqueous TBHP to Ac 2 O in semi-batch experiments in isothermal mode, and accordingly, the highest yield was 95.71%. Experiments combined with theoretical calculations revealed that the primary exothermic event was the TBPA formation reaction, and the removal of a large amount of water from TBHP prior to this is favourable for the reaction. The criticality classes of this reaction were of Grade 2.

CAS / MDL: 75-05-8 67-56-1
研究领域: 化学工程 · 安全科学 · 物理化学
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NEW JOURNAL OF CHEMISTRY · 2023 ·Vol. 47 ·期 33 ·15569-15578 · IF 3.3

Electrochemical determination of tert-butylhydroquinone by ZIF-67@TiO2 derived hierarchical TiO2/Co/NCNTs

Shengbiao Zheng,Jialong Fan,Feilong Yin,Jie Chen,Zhenzhen Hui,Jing Tang,Xuchun Wang,Jiahao Guo

A heterostructured TiO2/Co nanoparticle/N-doped carbon nanotube (TiO2/Co/NCNT) nanomaterial was derived from ZIF-67@TiO2 by calcination at high temperature in an Ar/H2 atmosphere. The obtained TiO2/Co/NCNT composite was made up of numerous dodecahedron-like boxes with twisting nanotubes on surfaces, modified on a glassy carbon electrode (GCE) for the electrochemical determination of tert-butylhydroquinone (TBHQ). The excellent electrocatalytic performance of TBHQ could be owing to the combination of multi-phase composition, fast electron transfer and the constructed Co/Ti multi-active sites. The TiO2/Co/NCNT sensor showed a broad linearity from 0.04 to 100 μM with a low detection limit of 4 nM, and possessed stability, anti-interfering ability and reproducibility. Finally, the analytical utility of the TiO2/Co/NCNT sensor was checked by detecting TBHQ in edible oil.

研究领域: 材料科学 · 分析化学
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JOURNAL OF HAZARDOUS MATERIALS · 2024 · IF 12.2

Nanozyme-integrated alcogel colorimetric sensor for rapid and on-site detection of tert-butyl hydroquinone

Shuai Liu,Hao Qu,Yu Mao,Lili Yao,Ling Yan,Baolei Dong,Lei Zheng

Tert -butyl hydroquinone (TBHQ) stand as one of the most widely used antioxidants in food and daily chemical products. Rapid and sensitive monitoring of TBHQ holds considerable importance in safeguarding human health due to its potential risks. In this study, we devised an alcogel-based colorimetric sensor enabling the portable and visual detection of TBHQ. The Ce-UiO-66 nanozyme exhibiting remarkable oxidase-like activity, was synthesized and characterized, facilitating the catalysis of TBHQ oxidation to 2- tert -butyl-1,4-benzoquinone (TBBQ). The ensuing chromogenic reaction between TBBQ and ethylenediamine produced a stable and colored product, serving as a reliable indicator for the rapid and specific detection of TBHQ. Building upon this discovery, a portable and low-cost colorimetric sensor was fashioned by integrating the nanozyme into κ -carrageenan alcogel, thereby enabling on-site TBHQ detection via a smartphone-based sensing platform. The colorimetric sensor exhibited a detection limit of 0.8 μg mL –1 , demonstrating robust performance across various matrices such as edible oils, cosmetics, and surface water. Recoveries ranged from 84.9 to 95.5%, with the sensor’s accuracy further validated through gas chromatography-mass spectrometry. Our study presents an effective approach to rapid and convenient monitoring of TBHQ, exhibiting good extensibility and practicability.

研究领域: 分析化学 · 食品科学 · 环境监测
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FOOD CHEMISTRY · 2024 · IF 8.5

Ratio-fluorescence detection of tert-butylhydroquinone based on non-conjugated polymer dots and gold nanoclusters

Bo Peng,Xueyan He,Chunjuan Wang,Fengxiang Du,Min Zhou,Shengguo Zhao,Yanjun Fang

A novel ratiometric fluorescent probe based on non-conjugated polymer dots (NCPDs) and gold nanocluster (AuNCs) was constructed to determine tert -butylhydroquinone (TBHQ). The probe exhibited dual emission peaks at 480 nm and 630 nm under 370 nm excitation. The fluorescence of AuNCs was quenched by TBHQ due to strong electrostatic interactions, whereas the emission of NCPDs increased. The ratio of fluorescence intensity at 480 nm to 630 nm (F 480 / F 630 ) was monitored as analytical signal response. The probe have been utilized for the detection of TBHQ with good linear relationship in the range of 0.2 to 60 μg/mL. The limit of detection (LOD) and the limit of quantitation (LOQ) were 0.048 μg/mL and 0.159 μg/L, respectively. Three levels of spiked-in TBHQ concentrations were obtained with recovery rates from 80 % to 102 %. The present study provided an effective ratiometric fluorescence method for selective screening of TBHQ in food samples.

研究领域: 分析化学 · 食品科学 · 材料科学
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Communications Biology · 2026 · IF 5.8

Extracellular vesicle-encapsulated GDF15 alleviates doxorubicin-induced cardiotoxicity via the SUB1/TERT/TPP signalling axis

Gu Qingqing,Chen Qianwen,Deng Ye,Deng Li,Huang Jianya,Wang Jingyi,Ji Yuan,Wang Ruxing,Wang Qingjie,Sun Ling

Doxorubicin (DOX) is a highly effective chemotherapeutic agent, but its clinical application is limited by cardiotoxicity. Mitochondrial dysfunction and apoptosis are key mechanisms underlying DOX-induced cardiomyopathy (DIC), while the role of telomerase reverse transcriptase (TERT) and its specific regulatory mechanisms remain unclear. An in vitro DOX-induced H9C2 cardiomyocyte injury model was established. TERT was overexpressed via adenoviral transfection or inhibited using BIBR1532. An in vivo mouse model of DOX-induced acute myocardial injury was constructed, with TERT expression regulated via intramyocardial adenoviral injection. Cardiac function was evaluated by echocardiography, and myocardial pathology was observed via staining. Additionally, exosome-encapsulated growth differentiation factor 15 (EXO-GDF15) was extracted and identified. Its regulatory mechanism on TERT was explored using DNA pull-down and luciferase reporter gene assays. Metabolomics was used to analyze the effect of TERT on mitochondrial metabolites in cardiomyocytes. TERT overexpression reduced DOX-induced apoptosis, increased mitochondrial membrane potential, and promoted autophagy in cardiomyocyte. In mice, TERT overexpression improved cardiac function and alleviated myocardial fibrosis, inflammation, and cardiomyocyte hypertrophy. Conversely, TERT inhibition exacerbated these injuries. EXO-GDF15 could be endocytosed by cardiomyocytes and alleviated DOX-induced myocardial injury by downregulating SUB1 to promote TERT transcription. Luciferase reporter assays showed that SUB1 binds to the BS4 site of the TERT promoter. Metabolomics showed that TERT increased the mitochondrial metabolite thiamine pyrophosphate (TPP) in cardiomyocytes, which alleviated myocardial injury by participating in the tricarboxylic acid cycle. EXO-GDF15 alleviates doxorubicin-induced cardiotoxicity via the SUB1/TERT/TPP signaling axis, thereby providing advanced insights for future DIC treatment.

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