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Environmental implications of oxalic and malonic acids with tropospheric oxidants 草酸和丙二酸与对流层氧化剂对环境的影响
IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2024-05-30 DOI: 10.1002/poc.4639
Basheer Aazaad, Angappan Mano Priya, Rubini Subramani

Dicarboxylic acids (DCAs) are major players in the formation of secondary organic aerosols (SOAs) and climate change. DCAs have potential impact on human health and environmental issues ranging from local scale to global scale participate mainly in the cloud condensation. In this context, oxalic acid (OA) and malonic acid (MA) are the most dominant DCAs in the atmosphere. A full atmospheric degradation mechanism of OA and MA with the most reactive tropospheric oxidants, namely, OH, Cl and NO3 radicals, were studied using M06-2X, ωB97XD/cc-pVTZ and 6-311++G(2df,2p) level of theories. To evaluate the atmospheric influence, this study enables us to deep investigation of fate of OA and MA with respect to the mentioned radicals and their subsequent secondary reactions. The latter result in the formation of carbon dioxide (CO2), formic acid (HCOOH), which contributes to the formation of SOA and climate change. The reaction mechanism in this study was initiated through H-abstraction reaction, followed by dehydrogenation and decarboxylation reaction of both DCAs. The rate coefficients of OA, MA with OH, Cl and NO3 radicals are determined theoretically using variational transition state theory (VTST) with Eckart tunnelling method in the temperature range of 278–1000 K. At 298 K, the rate coefficient of OA with OH, Cl and NO3 are 2.48 × 10−15, 2.37 × 10−20, 6.16 × 10−23 in cm3 molecule−1 s−1, whereas MA with OH, Cl and NO3 are 9.76 × 10−14, 1.01 × 10−12 and 5.89 × 10−18 in cm3 molecule−1 s−1, respectively. Our present results shed light on the atmospheric implications of two DCAs and provide the significant insight for the atmospheric pathways.

二羧酸(DCA)是二次有机气溶胶(SOA)形成和气候变化的主要参与者。二羧酸对人类健康和环境问题具有潜在影响,影响范围从局部到全球,主要参与云的凝结。在这方面,草酸(OA)和丙二酸(MA)是大气中最主要的 DCAs。利用 M06-2X、ωB97XD/cc-pVTZ 和 6-311++G(2df,2p)理论水平,研究了 OA 和 MA 与对流层中最活跃的氧化剂(即 OH、Cl 和 NO3 自由基)在大气中的完全降解机制。为了评估大气的影响,本研究深入探讨了 OA 和 MA 与上述自由基的归宿及其随后的二级反应。后者的结果是形成二氧化碳(CO2)和甲酸(HCOOH),从而导致 SOA 的形成和气候变化。本研究中的反应机制是通过 H-萃取反应启动,然后是两种 DCAs 的脱氢和脱羧反应。在 278-1000 K 的温度范围内,采用变异过渡态理论(VTST)和 Eckart 隧道法对 OA、MA 与 OH、Cl 和 NO3 自由基的速率系数进行了理论测定。在 298 K 时,OA 与 OH、Cl 和 NO3 的速率系数分别为 2.48 × 10-15、2.37 × 10-20、6.16 × 10-23 in cm3 molecule-1 s-1,而 MA 与 OH、Cl 和 NO3 的速率系数分别为 9.76 × 10-14、1.01 × 10-12 和 5.89 × 10-18 in cm3 molecule-1 s-1。我们目前的研究结果揭示了两种 DCA 对大气的影响,并为大气路径提供了重要启示。
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引用次数: 0
Proton transfer theoretical study catalyzed by 5-chlorouracil 5-氯尿嘧啶催化的质子转移理论研究
IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2024-05-27 DOI: 10.1002/poc.4638
Liangyue Cheng

In this study, the density functional M06-2X/6-311++G(3df,3pd) method was employed to investigate the mutual isomerization reaction mechanism of 5-chlorouracil from diketone to diol under the catalysis of water, methanol, formic acid, and an electric field. Parameters such as reaction enthalpy, activation energy, activation Gibbs free energy, and proton transfer reaction rate were obtained. The computational results show that under the same conditions, formic acid demonstrates the best catalytic effect, while the influence of electric field catalysis on the reaction barrier is minimal.

本研究采用密度泛函 M06-2X/6-311++G(3df,3pd)方法研究了在水、甲醇、甲酸和电场催化下,5-氯尿嘧啶由二酮到二醇的相互异构化反应机理。得到了反应焓、活化能、活化吉布斯自由能和质子转移反应速率等参数。计算结果表明,在相同条件下,甲酸的催化效果最好,而电场催化对反应壁垒的影响最小。
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引用次数: 0
Addition reaction of azoles to acetone-d6: NMR and computational studies 唑类化合物与丙酮-d6的加成反应:核磁共振和计算研究
IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2024-05-22 DOI: 10.1002/poc.4612
Rosa M. Claramunt, Dionisia Sanz, Ibon Alkorta, José Elguero

The reactivity of imidazole, pyrazole, 1,2,4-triazole, 1,2,3-triazole, and tetrazole with acetone (propan-2-one) has been studied by 1H and 13C NMR using acetone-d6 as solvent at temperatures ranging from 173 to 300 K at 10 K intervals. Simultaneously, the reaction has been theoretically calculated at the B3LYP/6-311++G(d,p) level, and experimental and theoretical results have been compared. The equilibrium constants between azoles and adducts α,α-dimethyl-azole-methanol were analyzed, assuming that the straight part of the plots –R ln Ke vs. 1/T can be used to determine ΔH and ΔS. Calculated and experimental data are related, but the theoretical values are proportionally higher. The tautomerism of triazoles and tetrazole has been considered in order to discuss the reactions.

以丙酮-d6 为溶剂,在 173 至 300 K 的温度范围内,以 10 K 为间隔,通过 1H 和 13C NMR 研究了咪唑、吡唑、1,2,4-三唑、1,2,3-三唑和四唑与丙酮(丙-2-酮)的反应性。同时,在 B3LYP/6-311++G(d,p) 水平上对该反应进行了理论计算,并对实验结果和理论结果进行了比较。分析了偶氮和加合物 α,α-二甲基偶氮唑-甲醇之间的平衡常数,假定 -R ln Ke vs. 1/T 图的直线部分可以用来确定 ΔH 和 ΔS。计算数据和实验数据是相关的,但理论值按比例来说更高。为了讨论这些反应,我们考虑了三唑和四唑的同分异构现象。
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引用次数: 0
Molecular structure and conformational properties of triflamide derivatives in the gas phase—Part II: 6-Iodo-3-(triflamidomethyl)-4-triflyl-1,4,2,7-oxaazadisilepane and 2,2,4,4-tetramethyl-6,8-bis (triflyl)-3-oxa-6,8-diaza-2,4-disilabicyclo[3.2.2]nonane by gas-phase electron diffraction and theoretical calculations 通过气相电子衍射和理论分析三酰胺衍生物在气相中的分子结构和构象特性--第二部分:6-碘-3-(三酰胺基甲基)-4-三烯丙基-1,4,2,7-恶氮杂二ilepane 和 2,2,4,4-四甲基-6,8-双(三烯丙基)-3-氧杂-6,8-二氮杂-2,4-二硅杂双环[3.2.2]壬烷
IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2024-05-19 DOI: 10.1002/poc.4613
Bagrat A. Shainyan, Alexey V. Eroshin, Sergey A. Shlykov

6-Iodo-3-(triflamidomethyl)-4-triflyl-1,4,2,7-oxazadisilepane 1 and the product of its cyclization, 2,2,4,4-tetramethyl-6,8-bis (triflyl)-3-oxa-6,8-diaza-2,4-disilabicyclo[3.2.2]nonane 2, have been studied by gas-phase electron diffraction and DFT calculations. The conformational equilibrium in the gas phase was shown to include three and two conformers for 1 and 2, respectively, in contrast to only one conformer determined by single crystal X-ray diffraction. The structural analysis of the conformers was performed and the pathways of the conformational transitions were analyzed.

通过气相电子衍射和 DFT 计算研究了 6-碘-3-(三氟甲基)-4-三氟甲基-1,4,2,7-恶氮杂二ilepane 1 及其环化产物 2,2,4,4-四甲基-6,8-双(三氟甲基)-3-氧杂-6,8-二氮杂-2,4-二硅杂双环[3.2.2]壬烷 2。结果表明,1 和 2 在气相中的构象平衡分别包括三个和两个构象,而单晶 X 射线衍射测定的构象只有一个。对这些构象进行了结构分析,并分析了构象转变的路径。
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引用次数: 0
Molecular dynamics simulation study of post-transition state bifurcation: A case study on the ambimodal transition state of dipolar/Diels–Alder cycloaddition 后过渡态分岔的分子动力学模拟研究:双极性/Diels-Alder 环加成的伏过渡态案例研究
IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2024-05-03 DOI: 10.1002/poc.4611
Tatsuhiro Murakami, Yuya Kikuma, Daiki Hayashi, Shunichi Ibuki, Shoto Nakagawa, Hinami Ueno, Toshiyuki Takayanagi

The potential energy surfaces for the reactions of 1,3-butadiene with 2-hydroxythioacrolein and 2-aminoacrolein exhibit ambimodal transition states leading to both dipolar (4 + 3) and Diels–Alder (4 + 2) cycloaddition products, thereby demonstrating a post transition state bifurcation feature. We have investigated the bifurcation dynamics of these reactions using three molecular dynamics (MD) methods: quasi-classical trajectory, classical MD, and ring-polymer MD simulations. The trajectory calculations were performed with the semiempirical GFN2-xTB method with the element-specific parameters optimized to reproduce the density-functional theory calculations. The effect of water solvation was examined using an implicit solvation model, revealing significant differences in bifurcation dynamic between gas-phase and solution-phase reactions. Nuclear quantum effects were found to play a crucial role in the proton-transfer process from the (4 + 3) intermediate to the (4 + 3) product in the case of the 2-aminoacrolein reaction.

1,3 丁二烯与 2-hydroxythioacrolein 和 2-aminoacrolein 反应的势能面显示了导致双极(4 + 3)和 Diels-Alder (4 + 2)环加成产物的非模态过渡态,从而显示了过渡态后分岔特征。我们使用三种分子动力学(MD)方法研究了这些反应的分岔动力学:准经典轨迹、经典 MD 和环状聚合物 MD 模拟。轨迹计算采用半经验 GFN2-xTB 方法,并对特定元素参数进行了优化,以重现密度泛函理论计算结果。利用隐式溶解模型研究了水溶的影响,发现气相反应和溶液相反应的分岔动态存在显著差异。研究发现,在 2-氨基丙烯醛反应中,核量子效应在质子从 (4 + 3) 中间体转移到 (4 + 3) 产物的过程中发挥了关键作用。
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引用次数: 0
Comparative effects of proteases on performance, carcass traits and gut structure of broilers fed diets reduced in protein and amino acids. 蛋白酶对饲喂蛋白质和氨基酸含量减少的日粮的肉鸡的性能、胴体特征和肠道结构的比较影响
IF 2.7 4区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2024-05-01 Epub Date: 2024-05-31 DOI: 10.5187/jast.2023.e20
Alexandra L Wealleans, Roba Abo Ashour, Majdi A Abu Ishmais, Sadiq Al-Amaireh, David Gonzalez-Sanchez

This study aimed to evaluate the effect of supplementing different protease enzymes on growth performance, intestinal morphology, and selected carcass traits in broilers fed diets reduced 3.5% in crude protein (CP) and amino acids (AA). One thousand one-day-old Ross 308 broilers (41 g) were assigned to five dietary treatments with ten replicates of 20 birds each: a positive control (PC) diet formulated to meet Ross 308 AA requirements, a negative control (NC) diet reformulated to provide 3.5% lower CP and AA compared to PC, NC supplemented with a multi-protease (PR1) solution, containing 3 different coated proteases produced from Aspergillus niger, Bacillus subtilis and Bacillus licheniformis, NC supplemented with a serine protease (PR2) produced from Bacillus licheniformis, and NC supplemented with an alkaline protease (PR3) produced from Bacillus licheniformis. At slaughter, 40 birds per treatment were used to assess the effect of the different treatments on carcass traits. At 32 days, samples of the duodenum, jejunum, and ileum of 10 birds per treatment were collected for intestinal morphology evaluation. Birds fed PC and NC supplemented with multi-protease exhibited better (p < 0.05) feed efficiency compared to NC and NC supplemented with all the other protease enzymes. Multi-protease supplementation was linked to the highest (p < 0.05) carcass weight and yield. There were significant differences (p < 0.05) between treatments in all gut segments, with PC, PR1, PR2, and PR3 exhibiting longer villi height (VH) compared to NC. This study demonstrates that 3.5% reduction of CP and AA negatively affected for the overall period feed efficiency, carcass yield, and intestinal morphology. The supplementation of the multi-protease restored feed efficiency and improved carcass yield.

本研究旨在评估补充不同蛋白酶对饲喂粗蛋白(CP)和氨基酸(AA)含量降低 3.5% 的日粮的肉鸡生长性能、肠道形态和某些胴体性状的影响。将一千只一天龄的 Ross 308 肉鸡(41 克)分配到五个日粮处理中,每个处理有 10 个重复,每个重复 20 只鸡:阳性对照(PC)日粮,其配方符合 Ross 308 AA 要求;阴性对照(NC)日粮,其配方比 PC 日粮的 CP 和 AA 降低 3.与 PC 相比,NC 日粮的 CP 和 AA 低 3.5%;NC 日粮添加多种蛋白酶(PR1)溶液,其中含有黑曲霉、枯草芽孢杆菌和地衣芽孢杆菌生产的 3 种不同的包被蛋白酶;NC 日粮添加地衣芽孢杆菌生产的丝氨酸蛋白酶(PR2);NC 日粮添加地衣芽孢杆菌生产的碱性蛋白酶(PR3)。屠宰时,每个处理使用 40 只鸡来评估不同处理对胴体特征的影响。32天时,收集每个处理10只鸡的十二指肠、空肠和回肠样本,以进行肠道形态学评估。与NC和添加其他蛋白酶的NC相比,添加多种蛋白酶的PC和NC饲料效率更高(p < 0.05)。补充多种蛋白酶与最高的胴体重量和产量有关(p < 0.05)。与 NC 相比,PC、PR1、PR2 和 PR3 的绒毛高度(VH)更长。本研究表明,CP 和 AA 降低 3.5% 会对整个阶段的饲料效率、胴体产量和肠道形态产生负面影响。补充多种蛋白酶可恢复饲料效率并提高胴体产量。
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引用次数: 0
Mechanism of the desulfurization route of the reduction of SO2 on carbons. Dimerization of Disulfur and Tetrasulfur 碳上还原二氧化硫的脱硫途径的机理。二硫和四硫的二聚反应
IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2024-04-23 DOI: 10.1002/poc.4610
Eduardo Humeres, Marília Isabel Tarnowski Correia, Nito Angelo Debacher, Regina de F. P. M. Moreira

The desulfurization of carbons modified with SO2 was studied as a dispersion in boiling cyclohexane (81°C) using activated carbon (mAC) and graphene oxide (mGO), modified by SO2. The steady-state species in the carbon matrix after the catalytic reduction of SO2 was considered a trisulfane. For mAC, there was a burst of a sulfur species identified as S2 by UV spectrum with a maximum at 217 nm (εM at 217 nm = 2.56 × 103) that showed a second-order decay of absorbance with kS2 = 47.29 M-1·sec-1 (ΔG354= 18.1 kcal·mol-1). The product was postulated to be S4. No other consecutive reaction was observed because of the possible adsorption of S4 in the carbon matrix. The desulfurization of mGO was shown by XPS and the kinetics were a second-order decay up to 16 min (kS2= 18.41 M-1·sec-1;ΔG354= 18.8 kcal·mol-1) followed by a second-order increase of absorbance with kS4 = 3.84 M-1·sec-1 (ΔG354= 19.9), where the product showed a double maximum at 260-285 nm typical of S8. These results are consistent with a mechanism of consecutive thermodynamically favorable dimerizations of S2 and S4 and with the desulfurization mechanism that has been previously postulated.

利用经二氧化硫改性的活性炭(mAC)和氧化石墨烯(mGO),研究了经二氧化硫改性的碳在沸腾的环己烷(81°C)中分散的脱硫过程。在催化还原 SO2 后,碳基质中的稳态物质被认为是三硫烷。就 mAC 而言,在 217 纳米波长(217 纳米波长处的εM = 2.56 × 103)处出现了紫外光谱最大值(= 47.29 M-1-sec-1(= 18.1 千卡-摩尔-1))的硫物种猝灭,其吸光度呈二阶衰减(= 47.29 M-1-sec-1 = 18.1 千卡-摩尔-1)。推测产物为 S4。由于碳基质中可能吸附了 S4,因此没有观察到其他连续反应。XPS 显示了 mGO 的脱硫过程,其动力学是在 16 分钟内出现二阶衰减(18.41 M-1-sec-1;= 18.8 kcal-mol-1),随后吸光度出现二阶上升(= 3.84 M-1-sec-1;= 19.9),产物在 260-285 纳米波长处显示出典型的 S8 双最大值。这些结果与 S2 和 S4 连续发生热力学上有利的二聚化机理以及之前推测的脱硫机理相一致。
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引用次数: 0
A study of the global and local aromaticity of hetero[8]circulenes 杂[8]环烯的整体和局部芳香性研究
IF 1.8 4区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2024-04-11 DOI: 10.1002/poc.4609
Satewaerdi Helili, Ablikim Kerim

The topological resonance energy (TRE) method was used to investigate the aromaticity of hetero[8]circulenes in both their neutral and doubly charged ion states. The compounds varying stabilities in different charged states were explained in terms of the topological charge stabilization rule. The TRE-based aromaticity indices were compared with those obtained by the gauge-including magnetically induced currents (GIMIC) method. However, the lack of correlation between the TRE and GIMIC aromaticity indices, as well as the contradictory trends observed, suggest that further investigation is necessary to fully understand the aromaticity of hetero[8]circulenes. We employed the circuit resonance energy (CRE) method to assess local aromaticity. Our CRE results indicate that individual benzene or heterocyclic five-membered units within the molecule maintain their strong aromatic character and serve as the primary source of global aromaticity, both in their neutral and doubly charged ion states. Although our CRE results provide valuable insights, it is important to note that there are cases where the magnitude of local aromaticity predicted by the nucleus-independent chemical shift (NICS[0] and NICS[1]) indices does not align with our CRE results.

拓扑共振能(TRE)方法用于研究杂[8]环烯在中性和双电荷离子状态下的芳香性。根据拓扑电荷稳定规则解释了化合物在不同带电状态下的不同稳定性。将基于 TRE 的芳香指数与通过量规包括磁感应电流 (GIMIC) 方法获得的芳香指数进行了比较。然而,TRE 芳香指数与 GIMIC 芳香指数之间缺乏相关性,而且观察到的趋势相互矛盾,这表明有必要进行进一步研究,以全面了解杂[8]环烯的芳香性。我们采用了电路共振能量 (CRE) 方法来评估局部芳香性。我们的 CRE 结果表明,分子中的单个苯或杂环五元单元在中性和双电荷离子状态下都能保持其强烈的芳香特性,并成为全局芳香性的主要来源。尽管我们的 CRE 结果提供了有价值的见解,但必须注意的是,在有些情况下,核无关化学位移(NICS[0] 和 NICS[1])指数预测的局部芳香性大小与我们的 CRE 结果并不一致。
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引用次数: 0
The measurement of one-electron redox potentials of free radicals 测量自由基的单电子氧化还原电位
IF 1.8 4区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2024-04-05 DOI: 10.1002/poc.4608
Igor V. Khudyakov

The paper is devoted to the measurements of one-electron redox potentials of transient free radicals Eo. These values can be measured in the reversible redox reactions of radicals under investigation with a reference pair, which Eo is known. Several Eo of transient radicals are presented. The convenient and important objects for Eo measurement are quinone/semiquinone radical-anions. A general problem of measurement of thermodynamic properties of short-lived transients is discussed.

本文致力于测量瞬时自由基 Eo 的单电子氧化还原电位。这些值可在自由基的可逆氧化还原反应中通过已知 Eo 的参比对进行测量。本文介绍了几种瞬态自由基的 Eo。方便测量 Eo 的重要对象是醌/半醌自由基阴离子。讨论了测量短寿命瞬态热力学性质的一般问题。
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引用次数: 0
Computational studies on exothermic carbon–carbon bond cleavages 碳-碳键裂解放热计算研究
IF 1.8 4区 化学 Q2 CHEMISTRY, ORGANIC Pub Date : 2024-03-26 DOI: 10.1002/poc.4606
Athanassios Nicolaides, Hideo Tomioka

Structural aspects of single CC bond dissociation energies are examined and it is shown that in certain cases a negative bond dissociation energy (BDE) implies a very weak bond and an unstable species prone to bond breaking resulting in dissociation or structural rearrangement. It is proposed that, in such cases, a better quantitative indicator for the strength of the bond is the activation energy required for its fission. o-Phenelylene bis(nitrene) 1 is computed to have the most negative CC BDE for an observable species. Under cryogenic conditions, activation energy for the dissociation of this bond has been measured as only 2.8 kcal/mol, making it the weakest that we know of. An explanation based on the formation of two new bonds as responsible for this extremely weak bond is given.

研究了单 CC 键离解能的结构方面,结果表明,在某些情况下,负键离解能(BDE)意味着键非常弱,是一种不稳定的物质,容易断键导致离解或结构重排。根据计算,邻苯乙烯双(腈)1 在可观察到的物种中具有最负的 CC BDE。在低温条件下,该键解离的活化能仅为 2.8 kcal/mol,是我们所知的最弱的键。我们给出的解释是,这种极弱的键是由两个新键的形成造成的。
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引用次数: 0
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Journal of Physical Organic Chemistry
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