Reactions in Nitroimidazole Triggered by Low‐Energy (0–2 eV) Electrons: Methylation at N1‐H Completely Blocks Reactivity

Low‐energy electrons (LEEs) at energies of less than 2 eV effectively decompose 4‐nitroimidazole (4NI) by dissociative electron attachment (DEA). The reactions include simple bond cleavages but also complex reactions involving multiple bond cleavages and formation of new molecules. Both simple and complex reactions are associated with pronounced sharp features in the anionic yields, which are interpreted as vibrational Feshbach resonances acting as effective doorways for DEA. The remarkably rich chemistry of 4NI is completely blocked in 1‐methyl‐4‐nitroimidazole (Me4NI), that is, upon methylation of 4NI at the N1 site. These remarkable results have also implications for the development of nitroimidazole based radiosensitizers in tumor radiation therapy.     

Observation of Unusual Molecular Diffusion Behaviour below the Lower Critical Solution Temperature of Water/2‐Butoxyethanol Mixtures by using Fluorescence Correlation Spectroscopy

The effect of solute affinity on solute diffusion in binary liquids well below the lower critical solution temperature (LCST) was studied by using fluorescence correlation spectroscopy. We measured the hydrodynamic radii of a hydrophobic and an amphiphilic fluorescent dye under systematic variation of the relative molar fractions of water/2‐butoxyethanol and, for comparison, of water/methanol mixtures, which do not show phase separation. We found that the apparent hydrodynamic radius of the hydrophobic dye almost doubled in water/2‐butoxyethanol, whereas it remained largely unchanged for the amphiphilic dye and in water/methanol mixtures. Our results indicate that the translational diffusion of solutes is influenced by transient local solution structures, even at temperatures well below the LCST. We conclude that, even far below LCST, different solutes can experience different environments in binary liquid mixtures depending on both the solute and solvent properties, all of which impact their reactivity.     

离子色谱法同时测定不同时段酸雨中17种离子

应用离子色谱法同时测定不同时段酸雨中17种离子的含量。样品经离心沉淀后,经0.45μm滤膜过滤,滤液供离子色谱分析。阴离子分离时用Shodex SI-52 4E阴离子色谱柱,并用3.6mmol·L-1碳酸钠-0.6 mmol·L-1碳酸氢钠缓冲溶液作为淋洗液;阳离子分离时用TSKGEL阳离子色谱柱,并用2mmol·L-1硝酸溶液作为淋洗液,采用电导检测器进行检测。17种离子均在一定的质量浓度范围内与其峰面积呈线性关系,方法的检出限(3S/N)在1.4~18.7μg·L-1之间。回收率在95.0%~105%之间,测定值的相对标准偏差(n=6)在1.7%~7.2%之间。     

离子色谱法测定合成气制烯烃产物中的C_1~C_6有机酸

采用离子色谱建立了合成气制烯烃(SGTO)水相产物和油相产物中C1~C6有机酸的测定方法。对分离条件进行了优化,使用标准样品测定了线性范围和工作曲线,考察了方法的精密度和准确度,确定了SGTO油相产物样品的碱洗条件,并对SGTO水相产物和油相产物样品进行了测定。结果表明:C1~C6有机酸的质量浓度在各自配制的质量浓度范围内呈现良好的线性关系,相关系数均大于0.99。标准溶液的回收率测定表明回收率在95.6%~104.3%之间,5次重复测定的相对标准偏差(RSD)在0.4%~3.6%之间,表明该方法具有良好的准确性和精密度。SGTO油相产物中的加标回收率在91.1%~96.8%之间,5次重复测定的RSD为0.7%~2.3%,准确性可以满足实际分析的需要。实际SGTO水相产物和油相产物中C1~C6有机酸的分析结果表明,SGTO水相产物中C2~C4有机酸含量较高,而SGTO油相产物中C4~C6有机酸含量较高。本研究对SGTO反应研究、催化剂制备、工艺优化以及设备材料的选择具有重要意义。     

原位漫反射傅里叶变换红外光谱研究锰铁基催化剂上低温选择性催化还原反应机理简

采用自蔓延燃烧法制备了Ti_0.9Mn_0.05Fe_0.05O_2-δ催化剂,运用原位漫反射傅里叶变换红外光谱对该催化剂的NO和NH₃稳态吸附以及NO和NH₃瞬态反应进行了详细地分析与讨论. 结果表明,相比于Lewis酸性位,150℃时Brönsted酸性位吸附的NH₃更具有SCR活性;与双齿硝酸盐和桥式硝酸盐相比,NO吸附产生的单齿硝酸盐是主要的中间物种;该SCR反应遵循Eley-Rideal和Langmuir-Hinshelwood机理,但以后者为主. 另外,O₂的存在有利于NO的氧化和配位态NH₃的活化.     

Toughening of polycarbonate through reactive melt blending: Effect of hydroxyl content and viscosity of hydroxyl-terminated polydimethysiloxane

In this study, four hydroxyl-terminated polydimethylsiloxanes(PDMSOH) with different viscosities and hydroxyl contents were used to improve the toughness of polycarbonate(PC) through reactive melt blending. A largely improved toughness of PC has been achieved, and the low temperature toughness of PC/PDMSOH blends could overtake that of PC homopolymer in much higher temperatures(e.g.-10 °C versus 23 °C). Moreover, it was found that the more the hydroxyl content, the less the PDMSOH was needed to reach the highest toughness, suggesting that equivalent molar ratio between the carbonyl group content of PC and the hydroxyl group content of PDMSOH was required for the toughening of PC. Ultraviolet spectrophotometry was used to analyze the possible reaction between PC and PDMSOH. Contact angle was measured to assess the change of interfacial interaction between PC and PDMSOH as change of viscosity and hydroxyl content. The formation of PC-co-PDMSOH copolymer was believed to be the key for the toughening effect. This work gives a profound recommendation of the optimum kind and dosage of PDMSOH which should be used to improve the toughness of PC and will find immediate industrial applications.     

硫脲络合–火焰原子吸收光谱法测定低硅铝合金中的银含量

采用硫脲络合–火焰原子吸收光谱法测定低硅铝合金中的银元素含量。实验探讨了酸度及硫脲用量对银测定的影响及铝合金中基体元素与共存元素对银元素分析线的干扰情况。结果表明:选用9%的盐酸和3%的硝酸溶解试样最好,加入5 mL 50 g/L硫脲溶液可消除氯离子对试验结果的影响,基体铝元素和其它共存元素不干扰银的测定。根据低硅铝合金中银元素的含量范围,合成系列标准溶液,建立工作曲线,工作曲线的线性范围为0.05%~0.50%。银元素含量为0.30%的样品测定结果的相对标准偏差为0.15%(n=8),标准加入回收率为96.8%~98.5%。该方法操作简便、重现性好、测量结果准确可靠。     

高频燃烧–红外吸收法测定低合金钢中的碳含量

采用高频红外碳硫分析仪测定低合金钢中的碳含量。分别考察了取样量、助熔剂种类、助熔剂用量对测量结果的影响。结果显示当取样量为400 mg、钨助熔剂用量为样品取样量的1.2倍时,测定低合金钢中的碳含量效果最好,测定结果的相对标准偏差为0.9%(n=10),加标回收率在97.5%~102.7%之间。     

Single-Atom Electrocatalysts from Multivariate Metal–Organic Frameworks for Highly Selective Reduction of CO2 at Low Pressures

Single-atom catalysts (SACs) are of great interest because of their ultrahigh activity and selectivity. However, it is difficult to construct model SACs according to a general synthetic method, and therefore, discerning differences in activity of diverse single-atom catalysts is not straightforward. Herein, a general strategy for synthesis of single-atom metals implanted in N-doped carbon (M₁-N-C; M=Fe, Co, Ni and Cu) has been developed starting from multivariate metal–organic frameworks (MOFs). The M₁-N-C catalysts, featuring identical chemical environments and supports, provided an ideal platform for differentiating the activity of single-atom metal species. When employed in electrocatalytic CO₂ reduction, Ni₁-N-C exhibited a very high CO Faradaic efficiency (FE) up to 96.8 % that far surpassed Fe₁-, Co₁- and Cu₁-N-C. Remarkably, the best-performer, Ni₁-N-C, even demonstrated excellent CO FE at low CO₂ pressures, thereby representing a promising opportunity for the direct use of dilute CO₂ feedstock.