Cyclohexane‐1,3‐dione as a derivatizing agent for the analysis of aldehydes by micelar electrokinetic chromatography with diode array detection

Aldehydes are important compounds in a large number of samples, especially food and beverages. In this work, for the first time, cyclohexane‐1,3‐dione (CHD) was used as a derivatizing reagent aiming aldehyde (formaldehyde, acetaldehyde, propionaldehyde, and valeraldehyde) analysis by MEKC‐DAD. The optimized separation of the derivates was performed using a voltage program (+20 kV, 0–15 min.; +23 kV, 15–17 min.) at a temperature of 26°C, and using as the running buffer a mixture containing 100 mmol/L of sodium dodecyl sulfate and 29 mmol/L of sodium tetraborate at pH 9.2, with maximum absorbance at 260 nm. CHD was compared with two other derivatizing agents: 3‐methyl‐2‐benzothiazolinone hydrazone and phenylhydrazine‐4‐sulfonic acid. The CHD‐aldehyde derivatives were also characterized by LC‐MS. The calibration curves for all aldehydes had r² above 0.999 and LODs ranged from 0.01 to 0.7 mg/L. The optimized methodology was applied in sugar cane brandy (cachaça) samples successfully. CHD showed to be an alternative derivatization reagent due to its stability, aqueous solubility, high selectivity and sensitivity, reduced impurities, and simple preparation steps.     

Enhanced 1T′-Phase Stabilization and Chemical Reactivity in a MoTe2 Monolayer through Contact with a 2D Ca2N Electride

Among the widely studied 2D transition metal dichalcogenides (TMDs), MoTe₂ has attracted special interest for phase-change applications due to its small 2H-1T′ energy difference, yet a large scale phase transition without structural disruption remains a significant challenge. Recently, an interesting long-range phase engineering of MoTe₂ has been realized experimentally by Ca₂N electride. However, the interface formed between them has not been well understood, and moreover, it remains elusive how the presence of Ca₂N would affect the basal plane reactivity of MoTe₂. To address this, we performed density functional theory (DFT) calculations to investigate the potential of tuning the phase stability and chemical reactivity of a MoTe₂ monolayer via interacting with Ca₂N to form a van der Walls heterostructure. We found that the contact nature at the 2H-MoTe₂/Ca₂N interface is Schottky-barrier-free, allowing for the spontaneous electron transfer from Ca₂N to 2H-MoTe₂ to make it strongly n-type doped. Moreover, Ca₂N doping significantly lowers the energy of 1T′-MoTe₂ and dynamically triggers the 2H-to-1T′ transformation. The Ca₂N-induced phase modulation can also be applied to tune the phase energetics of MoS₂ and MoSe₂. Furthermore, using H adsorption as the testing ground, we also find that the H binding on the basal plane of MoTe₂ is enhanced after forming heterostructure with Ca₂N, potentially providing basis for surface modification and other related catalytic applications.     

Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis

The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity.     

三维非连续变形分析方法碰撞分析及其应用

将具有完备动力学理论的非连续变形分析(DDA)方法应用于块体碰撞研究。基于三维DDA(3D DDA)方法,按时步输出块体碰撞过程速度变化和接触嵌入量,进而得到块体碰撞恢复系数、冲量、冲击力。以此为参考指标,采用斜抛、面-面对心等碰撞模型,验证3D DDA方法模拟块体碰撞的有效性,并将3D DDA方法应用于多米诺骨牌倾倒、滚石边坡成灾及防护等算例分析,探讨了多米诺骨牌倾倒机制、滚石启动及运动行为、滚石灾害防护方案。结果表明:多米诺骨牌间距越大,同一块体被碰撞时间越迟,其最终稳定时间也越迟,与下一块体碰撞的动能越大;滚石运动呈侧向平动及转动三维运动特征,每一次碰撞,均引起动能、轨迹或状态的显著变化;滚石拦挡设施弹簧刚度越大,越先达到最大冲击力,最大冲击力随弹簧刚度的增加而减小;可结合树木阻挡效应,耗散滚石动能,降低滚石飞跃高度,使滚石灾害减轻或控制在防护范围以内。     

MALDI MSI Reveals the Spatial Distribution of Protein Markers in Tracheobronchial Lymph Nodes and Lung of Pigs after Respiratory Infection

Respiratory infections are a real threat for humans, and therefore the pig model is of interest for studies. As one of a case for studies, Actinobacillus pleuropneumoniae (APP) caused infections and still worries many pig breeders around the world. To better understand the influence of pathogenic effect of APP on a respiratory system—lungs and tracheobronchial lymph nodes (TBLN), we aimed to employ matrix-assisted laser desorption/ionization time-of-flight mass spectrometry imaging (MALDI-TOF MSI). In this study, six pigs were intranasally infected by APP and two were used as non-infected control, and 48 cryosections have been obtained. MALDI-TOF MSI and immunohistochemistry (IHC) were used to study spatial distribution of infectious markers, especially interleukins, in cryosections of porcine tissues of lungs (necrotic area, marginal zone) and tracheobronchial lymph nodes (TBLN) from pigs infected by APP. CD163, interleukin 1β (IL-1β) and a protegrin-4 precursor were successfully detected based on their tryptic fragments. CD163 and IL-1β were confirmed also by IHC. The protegrin-4 precursor was identified by MALDI-TOF/TOF directly on the tissue cryosections. CD163, IL-1β and protegrin-4 precursor were all significantly (p < 0.001) more expressed in necrotic areas of lungs infected by APP than in marginal zone, TBLN and in control lungs.     

纳米线组装叶片状三氧化钼的合成及其对三乙胺的气敏性能

通过溶剂热法制备了由一维纳米线自组装的叶状三氧化钼纳米材料，借助X射线衍射（XRD）、场发射扫描电子显微镜（FESEM）、透射电子显微镜（TEM）、高分辨透射电镜（HRTEM）、紫外-可见漫反射光谱（UV-Vis DRS）、热重-示差扫描量热（TG-DSC）、氮气吸附（N₂-sorption）等技术对材料进行了系统的组成和结构表征。结果表明，一维纳米线表面具有粗糙结构，且由一维纳米线组装的叶片状三氧化钼属畸变八面体中的正交晶系，其主要暴露的结晶面是（021）。此叶片状三氧化钼气敏材料在300℃的最佳工作温度下，对2.25 g·m^-3的三乙胺表现出优异的选择性、超高的灵敏度和较快的响应时间（5 s），甚至在浓度为4.5 mg·m^-3的检测标准下响应值仍可达到12.4。基于以上结构表征和性能测试结果，对叶片状三氧化钼的形成及三乙胺敏感机理进行了初步探讨分析。     

Mn2+、N2-共掺杂Zn2GeO4晶体电子结构和光学性质的研究

采用基于密度泛函理论的平面波超软赝势方法对本征Zn2GeO4，Mn2+掺杂Zn2GeO4，Mn2+/N2-共掺杂Zn2GeO4超晶胞进行了几何结构优化，计算了掺杂前后体系的晶格常数、能带结构、态密度和光学性质。结果表明，Mn离子掺入后，Mn离子3d轨道与O离子2p轨道之间有强烈的轨道杂化效应，掺杂系统不稳定，而Mn/N离子共掺后，Mn离子和N离子之间的吸引作用克服了Mn离子之间的排斥作用，能够明显地提高掺杂浓度和体系的稳定性。光学性质计算结果表明，Mn离子与N离子共掺杂能改善Zn2GeO4电子在低能区的光学跃迁特性，增强电子在可见光区的光学跃迁；吸收谱计算结果显示，Mn离子与N离子掺入后体系对低频电磁波吸收增加。     

Synthesis,crystal structure and conformational analysis of an unexpected [1,5]dithiocine product of aminopyridine and thiovanillin

The condensation reaction of 2‐mercapto‐3‐methoxybenzaldehyde with 3‐aminopyridine afforded an unexpected N‐alkylated [1,5]dithiocine instead of the N‐salicylideneaniline. The proposed mechanism for this condensation involves a strong intramolecular hydrogen bond between the thiol and the amine groups, leading to a second condensation. The corresponding product, i.e. 4,10‐dimethoxy‐13‐(pyridin‐3‐yl)‐6H,12H‐6,12‐epiminodibenzo[b,f][1,5]dithiocine methanol 0.463‐solvate, C₂₁H₁₈N₂O₂S₂·0.463CH₃OH, was characterized by single‐crystal X‐ray diffraction analysis. The supramolecular structure shows π–π stacking and S…S interactions in the crystal packing. Within the asymmetric unit, two geometries of the N atom are observed. Although a planar geometry should be expected, a pyramidal one is observed due to the crystal packing. The presence of the two geometries was further supported by density functional theory (DFT) calculations that show an electronic energy difference of less than 2 kJ mol^?1 between the two conformers.     

On a question of Thas on partial 3‐(qn + 1, q + 1, 1) designs

In this note, we answer a question of JA Thas about partial $3$‐ $\left(q^n+1,q+1,1\right)$ designs. We then extend this answer to a result about the embedding of certain partial $3$‐ $\left(q^2+1,q+1,1\right)$ designs into Möbius planes.     

A note on 3‐partite graphs without 4‐cycles

Let $C_4$ be a cycle of order 4. Write $ex\left(n,n,n,C_4\right)$ for the maximum number of edges in a balanced 3‐partite graph whose vertex set consists of three parts, each has $n$ vertices that have no subgraph isomorphic to $C_4$. In this paper, we show that $ex\left(n,n,n,C_4\right)\ge \frac{3}{2}n\left(p+1\right)$, where $n=\frac{p\left(p?1\right)}{2}$ and $p$ is a prime number. Note that $ex\left(n,n,n,C_4\right)\le \left(\frac{3\sqrt{2}}{2}+o\left(1\right)\right)n^{\frac{3}{2}}$ from Tait and Timmons's works. Since for every integer $m$, one can find a prime $p$ such that $m\le p\le \left(1+o\left(1\right)\right)m$, we obtain that $\underset{n\to \infty }{\lim }\frac{ex\left(n,n,n,C_4\right)}{\frac{3\sqrt{2}}{2}{n}^{\frac{3}{2}}}=1$.