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1.
朱本占  张静  唐苗  黄春华  邵杰 《化学进展》2022,34(1):227-236
卤代醌是一类卤代芳烃类环境污染物的致癌中间体,也是在饮用水中新发现的氯化消毒副产物。我们最近发现卤代醌和 H2O2 或有机氢过氧化物体系可以不依赖过渡金属离子,而产生高活性的羟基/烷氧自由基和醌氧/醌碳自由基。目前尚不清楚这些卤代醌类致癌物和氢过氧化物共存能否诱导 DNA 产生氧化损伤和修饰,以及其潜在的分子机制是什么。我们的研究发现 DNA 在四氯-1,4-苯醌/H2O2体系中可被氧化产生 8-氧脱氧鸟苷、DNA 链断裂和三种甲基氧化产物,这些反应不依赖过渡金属离子,且由于卤代醌与 DNA 的嵌入作用而导致其氧化作用增强。其他卤代醌也观察到了类似的现象,而且通常比经典的 Fenton 体系更有效。我们进一步将研究从纯化的 DNA 扩展到了活细胞的基因组 DNA。同时还发现卤代醌和有机氢过氧化物(如叔丁基过氧化氢或在正常生理条件下产生的 13S-过氧羟基-9Z,11E-十八碳二烯酸(13-HPODE))共存时,可通过独特的醌氧自由基介导机制诱导 DNA 氧化生成致突变性更强的咪唑啉酮类产物 dIz。这些发现为解释普遍存在的卤代醌类致癌中间体和消毒副产物的潜在基因毒性、致突变性和致癌性提供了新思路。  相似文献   
2.
为进一步提高对偏硼酸钠电催化还原的效率,采用化学镀的方法,以铜片为基体,PdCl2乙醇胶体溶液为活化剂,乙醇为化学镀溶剂,制备了稀土复合电极La-Ni-B.并采用XRD、SEM、EDS方法对催化剂进行表征分析,结果表明稀土合金以纳米颗粒的形式附着在基体表面,所得合金膜是非晶态的.通过循环伏安法研究了复合电极La-Ni-B用于电解偏硼酸钠制备硼氢化钠的可行性.以硼氢化钠实际生产量为指标,探讨了直流、脉冲两种不同供电方式、脉冲电流频率、电解时间对电解行为的影响.结果表明稀土镧对电解偏硼酸钠有催化作用,以20 mL镀液制备的复合电极,在脉冲频率阳极时间T1=1 s,阴极时间T2=1 s时,最佳电解时间为4h.复合电极在重复使用3次的情况下,硼氢化钠产量降低15;,催化剂的重复使用性能良好.  相似文献   
3.
Borate is considered one of the most important additives for improving the fire-resistance of combustible polymers because of its smoke suppression, low toxicity, and good thermal stability. However, the size of prepared borate is usually in the micrometer range, which makes it difficult to disperse in a polymer matrix, thus hindering its use as fire-retardant material. The preparation and application of borate nanomaterial as flame retardant is considered an effective method. However, the preparation of barium borate nanomaterials as flame retardant has not been reported. In this paper, nanosheets and nanoribbons with different sizes for a new barium borate BaO·4B2O3·5H2O are prepared by hydrothermal method, and characterized by X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR), thermogravimetric analysis-differential scanning calorimetry (TG-DSC), and scanning electron microscope (SEM). The flame-retardant properties of polypropylene (PP)/BaO·4B2O3·5H2O composites are investigated by thermogravimetric analysis (TG), differential scanning calorimetry (DSC) thermal analysis methods and limited oxygen index (LOI) method. Considering the near TG mass losses and the near LOI values for PP with 10% prepared BaO·4B2O3·5H2O nanosheet and nanoribbon, their flame-retardant properties need to be further evaluated by non-isothermal decomposition kinetic method. The apparent activation energy for this decomposition reaction was obtained from the slope by plotting ln(β/Tp2) against 1/Tp according to Kissinger's model. With the reduction of TG mass loss, increased heat absorption in DSC under N2 atmosphere, increased apparent activation energy Ea for the thermal decomposition of PP/BaO·4B2O3·5H2O composite as well as increased LOI value, the flame-retardant performance of prepared BaO·4B2O3·5H2O samples with PP gradually improved from bulk to nanoribbon to nanosheet. This can be attributed to the decrease in the size of BaO·4B2O3·5H2O samples because the smaller sample size leads to improved dispersion and increased contact area with the polymer. The flame-retardant mechanism is discussed by analyzing the after-flame chars of the PP/BaO·4B2O3·5H2O composite in SEM images, which show that the char layer is more compact and continuous for the PP/BaO·4B2O3·5H2O nanosheet composite. The influence of loading BaO·4B2O3·5H2O nanomaterials on the mechanical properties of PP is also tested using a universal material testing machine, in which the PP/BaO·4B2O3·5H2O nanosheet composite has higher tensile strength. The PP/BaO·4B2O3·5H2O nanosheet composite has the best flame-retardant and mechanical properties, which is promising to be developed for the application as flame-retardant material.  相似文献   
4.
Discriminative detection of invasive and noninvasive breast cancers is crucial for their effective treatment and prognosis. However, activatable probes able to do so in vivo are rare. Herein, we report an activatable polymeric reporter (P-Dex) that specifically turns on near-infrared (NIR) fluorescent and photoacoustic (PA) signals in response to the urokinase-type plasminogen activator (uPA) overexpressed in invasive breast cancer. P-Dex has a renal-clearable dextran backbone that is linked with a NIR dye caged with an uPA-cleavable peptide substrate. Such a molecular design allows P-Dex to passively target tumors, activate NIR fluorescence and PA signals to effectively distinguish invasive MDA-MB-231 breast cancer from noninvasive MCF-7 breast cancer, and ultimately undergo renal clearance to minimize the toxicity potential. Thus, this polymeric reporter holds great promise for the early detection of malignant breast cancer.  相似文献   
5.
A rapid and sensitive method was developed and validated for the quantitative determination of xanthopurpurin (XPP) in rat plasma using ultra-performance liquid chromatography-electrospray ionization-Orbitrap mass spectrometry. XPP inhibits IgE production and prevents peanut-induced anaphylaxis. The XPP and emodin (internal standard) were determined in negative ion mode with m/z 239.0350 → 211.0400 and 269.0455 → 241.0507, respectively. The separation process was achieved using an ACQUITY UPLC HSS T3 column with acetonitrile and 0.1% formic acid in water (85:15). The linear range was 0.5–100 ng/mL, and the correlation coefficient (r2) was > 0.993. The inter-day and intra-day precision was within an acceptable range of 15%. The extraction recovery and matrix effect were 78.9–87.2% and 94.3–98.5%, respectively. Under different conditions, the XPP was stable in the range of 5.6–10.6%. This method was successfully applied to study the pharmacokinetics of XPP with an oral dose of 10.0 mg/kg and intravenous dose of 2.0 mg/kg in rats. The absolute oral bioavailability of XPP was 4.6%.  相似文献   
6.
Photothermal therapy (PTT) is an emerging noninvasive and precise localized therapeutic modality; however, it is deeply limited by its poor tumor accumulation, inadequate photothermal conversion efficiency, and the thermoresistance of cancer cells. Aimed at these shortcomings, tumor‐targeting nanoparticles (iRGD‐W18O49‐17AAG) comprising carboxyl‐group‐functionalized W18O49 nanoparticles, integrin‐targeting peptide iRGD, and HSP90‐inhibitor 17AAG are developed. The W18O49 nanoparticles act as excellent PTT carriers and computed tomography (CT) imaging contrast agents. The ring type polypeptide iRGD promotes the accumulation of nanoparticles in the tumour and further penetration into cancer cells. The introduction of 17AAG can inhibit the heat‐shock response and overcome the thermoresistance, thus increasing the curative effect of PTT and reducing the chance of tumor recurrence. The W18O49 nanoparticles can also be used to monitor and guide the phototherapeutic through CT and near‐infrared fluorescence imaging after modification with Cy5.5. In addition, superior biosafety is also indicated in both preliminary in vitro and in vivo assessments. The potential of iRGD‐W18O49‐17AAG in tumor targeting, dual modality imaging‐guided and remarkable enhanced PTT of gastric cancer with ignorable side effect both in vitro and in vivo, which may be further applied in clinic, is highlighted.  相似文献   
7.
The electrochemical nitrogen reduction reaction (NRR) offers an energy‐saving and environmentally friendly approach to produce ammonia under ambient conditions. However, traditional catalysts have extremely poor NRR performances because of their low activity and the competitive hydrogen evolution reaction. The high catalytic activity of nanoporous gold (NPG) and the hydrophobicity and molecular concentrating effect of the zeolitic imidazolate framework‐8 (ZIF‐8) were incorporated in the NPG@ZIF‐8 nanocomposite so that the ZIF‐8 shell could weaken hydrogen evolution and retard reactant diffusion. A highest Faradaic efficiency of 44 % and an excellent rate of ammonia production of (28.7±0.9) μg h?1 cm?2 were achieved, which are superior to traditional gold nanoparticles and NPG. Moreover, the composite catalyst shows high electrochemical stability and selectivity (98 %). The superior NRR performance makes NPG@ZIF‐8 one of the most promising water‐based NRR electrocatalysts for ammonia production.  相似文献   
8.
9.
研究了低功率超声(US, <38 W)对NaClO氧化非离子型碘代X射线造影剂—碘帕醇(IPM)的增强作用及机理, 考察了NaClO添加浓度和超声功率的影响, 分析并计算了体系中的主要活性物种及其贡献. 采用高效液相色谱/串联质谱(HPLC/MS/MS)对降解产物进行分析, 推测IPM的降解路径. 结果表明, 低功率US显著增强了NaClO对IPM的氧化效果, 在25 ℃, pH=5.8, NaClO浓度为0.12 mmol/L条件下, 10 mg/L IPM在60 min的降解率达到85.8%. 其中NaClO氧化、 HO·和活性氯自由基(RCSs)是US/NaClO增强IPM降解的主要原因, 自由基分析计算它们的贡献率分别为15.82%, 4.65%和79.53%. NaClO浓度在0~0.24 mmol/L范围内, IPM的降解率随NaClO浓度升高而增加, 60 min后降解率由4.75%增加到91.12%; 超声功率为28.5 W, 降解率达到最高. 在 15~45 ℃温度范围内, IPM的降解过程符合表观一级反应动力学, 反应活化能(Ea)为59.03 kJ/mol. HPLC/MS/MS共检测出5种中间产物, 结合密度泛函理论(DFT)计算结果, 初步推测了IPM在US/NaClO体系中的降解途径和机理.  相似文献   
10.
有机太阳能电池具有低成本、柔性和质量轻等优势, 是一种有应用前景的光伏技术, 受到人们的广泛关注. 有机太阳能电池的光敏活性层通常由p-型有机半导体(包括小分子和高分子)与n-型有机半导体(包括小分子和高分子)共混而成. 小分子给体/高分子受体型有机太阳能电池具有形貌热稳定性优异的特点, 值得深入研究. 本综述旨在总结小分子给体/高分子受体型有机太阳能电池的研究进展, 分别介绍了基于酰亚胺基、氰基和含硼氮配位键(B←N)的高分子受体的活性层材料体系的发展状况. 在器件性能方面, 通过分子设计、相分离形貌调控, 改善了小分子给体/高分子受体的匹配性, 将该类电池的能量转换效率从最初的0.29%提升至目前的9.51%, 为性能的进一步提升总结了经验; 在稳定性方面, 基于该体系形貌热稳定性优异的特点, 开发出高温耐受型有机太阳能电池器件. 最后, 展望了小分子给体/高分子受体型有机太阳能电池的未来发展方向和前景.  相似文献   
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