Tools for an enhanced solvent properties screening in the early stages of pharmaceutical process development

The objective of this research was the implementation of tools for the evaluation of solvents trough property screening in the early stages of process development. An important feature of the tools is that the implementation of indexes, scores, or weights is avoided. Information already available from the literature was stored in a database in order to turn raw data into decision making information. As a result, a solvent radar chart, a solvent representation table, and a solvent telescopying tool were developed in an ASP.NET application. The synthesis of Propranolol was used as study case in order to explore the selection of solvents in the early stages of process development. The replacement of diethyl ether was possible in the extraction step, while solvent choices were detected for potential telescoping for extraction and crystallisation steps. Solubility was found as a critical parameter in telescoping analysis. The methodology proposed enhanced the view towards a more holistic perspective and a more robust solvent screening process. As a consequence, the next steps into solvent evaluation and process development can be reduced.     

Trends of chemical speciation profiles of anthropogenic volatile organic compounds emissions in China, 2005–2020

This study estimates the detailed chemical profiles of China＇s anthropogenic volatile organic com- pounds （VOCs） emissions for the period of 2005-2020. The chemical profiles of VOCs for seven activity sectors are calculated, based on which the Photochemical Ozone Creation Potential （POCP） of VOCs for these sectors is evaluated. At the national level, the VOCs species emitted in 2005 include alkanes, alkenes and alkynes, aromatic compounds, alcohols, ketones, aldehydes, esters, ethers and halocarbons, accounting for 26.4wt.%, 29.2wt.%, 21.3 wt.%, 4.7 wt.%, 5.4 wt.%, 1.7 wt.%, 2.1 wt.%, 0.7 wt. % and 2.2wt.% of total emissions, respectively. And during 2005-2020, their mass proportions would respec- tively grow or decrease by - 34.7%, -48.6%, 108.5%, 6.9%, -32.7%, 7.3%, 65.3%, 100.5%, and 55.4%. This change would bring about a 13% reduction of POCP for national VOCs emissions in the future. Thus, although the national VOCs emissions are expected to increase by 33% over the whole period, its ozone formation potential is estimated to rise only by 14%. Large discrepancies are found in VOCs speciation emissions among provinces. Compared to western provinces, the eastern provinces with a more developed economy would emit unsaturated hydrocarbons and benzene with lower mix ratios, and aromatic compounds except benzene, oxidized hydrocar- bons and halocarbons with higher mix ratios. Such differences lead to lower POCP of VOCs emitted in eastern provinces, and higher POCP of VOCs emitted in western provinces. However, due to the large VOCs emissions from Chinese eastern region, the ozone forma- tion potential of VOCs emission in eastern provinces would be much higher than those in western provinces by about 156%-235%.     

Solid-Phase Microextraction As A Tool for Studying Volatile Compounds in Frog Skin

Solid-phase microextraction (SPME) is an effective technique for studying frog volatile secretions. Its primary advantage is in its application to sampling live animals. the ability to sample an organism over an extended period allows changes in an individual's chemical signature to be determined. the presence of eucalyptol in the skin secretion of Ewing's tree frog, Litoria ewingi, was used to assess the effectiveness of SPME in sampling frog volatiles. Rapid sample times coupled with the polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre provided the best signal/noise ratio for the majority of frog volatiles analysed, and importantly resulted in the least amount of stress to the animals involved.     

土荆芥挥发油对豌豆根边缘细胞的诱导和胁迫作用

为探讨化感胁迫对根边缘细胞的诱导效应,实验采用悬空气培养法培养豌豆(Pisum sativum L.)露白种子,在保留根边缘细胞和去除根边缘细胞状态下,选取相对根长、根边缘细胞数量及死亡率、果胶甲基酯酶（PME）等指标研究了豌豆根边缘细胞对不同剂量土荆芥挥发油化感作用的响应。结果表明：1）与对照相比,随着挥发油处理剂量增加,根的伸长被显著抑制（P<0.05）。2）每个处理时间内,随着土荆芥挥发油剂量增加,根边缘细胞数量整体表现出先增加后减少的趋势,在低剂量2μL处理中达极大值。3）土荆芥挥发油诱导豌豆根边缘细胞死亡,随着处理时间的延长和处理剂量的增加,这种毒害效应程度加剧,除去边缘细胞实验组中10μL挥发油处理24 h时,根边缘细胞死亡率达到100%。在较低剂量挥发油作用下,保留根边缘细胞组的根边缘细胞死亡率高于去除根边缘细胞组,而在高剂量挥发油处理情况则相反。4）在同一处理时间,随挥发油剂量增加,各处理组PME活性持续升高,去处边缘细胞组处理24 h后不同剂量处理皆显著高于对照,而根边缘细胞数量总体表现先增加后减少。综合以上结果,保留根边缘细胞的根尖根边缘细胞的数量减少量较少,说明根边缘细胞能缓解土荆芥挥发油的化感胁迫;去除根边缘细胞组的PME活性升高较多,表明土荆芥化感胁迫诱导了根边缘细胞的产生。     

外加碳源水淹条件下高硫土壤中铜的迁移转化

采用高硫低有机质酸性重金属污染土壤,通过研究外加碳源水淹条件下各层土壤中酸可挥发性硫化物(AVS)的产生以及各剖面层中Cu的总量分布、Cu在孔隙水中的浓度及存在形态的变化情况,探讨了水淹土壤中的AVS对Cu迁移转化的影响.结果表明,外加碳源水淹条件下,硫酸根被还原,产生的大量AVS可促使水相中游离活性Cu向惰性较高的硫化物结合态和残渣态转化而被固定;不同深度土壤中AVS产生情况不同,其含量由深层向浅层递增,并在顶层大量聚集,由此导致孔隙水中的Cu²⁺浓度由土壤深层向浅层递减,这种垂直浓度梯度差,趋动活性态Cu由深层向浅层的垂直迁移,在AVS大量富集的表层中形成丰富的铜硫化物沉淀,使土壤表层中惰性态铜及总量累积增加,底层活性铜及总量下降,从而使铜的生态风险和生物风险降低.     

Optimized porous clay heterostructure for removal of acetaldehyde and toluene from indoor air

Adsorption is the most widely used technology for the removal of indoor volatile organic compounds (VOCs). However, existing adsorbent-based technologies are inadequate to meet the regulatory requirement, due to their limited adsorption capacity and efficiency, especially under high relative humidity (RH) conditions. In this study, a series of new porous clay heterostructure (PCH) adsorbents with various ratios of micropores to mesopores were synthesized, characterized and tested for the adsorption of acetaldehyde and toluene. Two of them, PCH25 and PCH50, exhibited markedly improved adsorption capability, especially for hydrophilic acetaldehyde. The improved adsorption was attributed to their large micropore areas and high micropore-to-mesopore volume ratios. The amount of acetaldehyde adsorbed onto PCH25 at equilibrium reached 62.7 mg·g⁻¹, eight times as much as the amount adsorbed onto conventional activated carbon (AC). Even at a high RH of 80%, PCH25 removed seven and four times more of the acetaldehyde than AC and the unmodified raw PCHs did, respectively. This new PCH optimized for their high adsorption and resistance to humidity has promising applications as a cost-effective adsorbent for indoor air purification.     

燃烧过程中煤氮热迁移特性研究进展

燃烧过程中煤氮的热迁移特性决定着NOx的生成与最终排放量,并对控制和治理燃煤过程中NOx污染具有重要指导意义。将煤氮的热迁移过程分为挥发分氮及焦炭氮2个不同热迁移路径进行讨论,归纳了在燃烧过程中挥发分氮及焦炭氮热迁移的特性及相关影响因素。最后提出了"定量解析煤氮热迁移过程"这一国际学术难题的研究突破口。     

上海市青浦区大气挥发性有机化合物的特征

在2012年11~12月和2014年5~10月对上海市青浦区大气中58个VOCs物种进行了连续监测.结果表明,青浦区VOCs总体浓度水平较低,烷烃是其中含量最高的物种,百分含量为41.64%,其次为芳香烃25.66%、烯烃15.21%、乙炔7.71%.总VOCs的月变化特征表现为11月最高,10月最低;日变化特征表现为明显的双峰分布.通过OH消耗速率和臭氧生成潜势(OFP)计算,评估了VOCs的化学反应活性.结果表明,上海市青浦区大气VOCs的化学反应活性较强,且与VOCs浓度具有良好的一致性.OH消耗速率贡献最大的物种是烯烃56.92%和芳香烃45.24%,OFP贡献最大的物种是烯烃29.19%和芳香烃40.82%;对臭氧生成贡献最大的关键活性物种是乙烯、异戊二烯、甲苯、间/对二甲苯及丙烯等物质.利用化学质量平衡(CMB)模型分析了VOCs的来源,结果显示,上海市青浦区大气中VOCs主要有6个来源,分别是汽车尾气排放、LPG泄漏、涂料和溶剂挥发、植物排放、生物质燃烧、工业排放,其贡献率分别为43%、5%、16%、3%、14%、7%.     

污泥厌氧发酵液燃料电池的性能及电子供体分析

采用剩余污泥厌氧发酵液为阳极燃料、铁氰化钾溶液为阴极电子受体,成功启动了双室微生物燃料电池(MFC).考察了厌氧发酵过程中剩余污泥上清液中各种挥发性脂肪酸(VFAs)含量的变化,研究分析了污泥厌氧发酵液燃料电池的产电过程、燃料消耗及电子供体. 结果表明,污泥厌氧发酵液中乙酸含量最高(约占总VFAs的50%),异戊酸和丙酸含量次之(分别约占总VFAs的18%及15%),正丁酸和异丁酸含量较少(均低于总VFAs的10%),正戊酸含量最低(低于总VFAs的1%);MFC实现了250h稳定电压输出(0.65±0.05V),库伦效率为9.09%;阳极总化学需氧量(TCOD)、溶解性化学需氧量(SCOD)、VFAs均呈现整体下降趋势, TCOD和SCOD的去除率分别为74.9%和86.4%; VFAs的完全消耗伴随着反应器产电性能迅速变差,表明VFAs是主要电子供体;在MFC产电过程中, VFAs的消耗与产生同时存在,消耗总体快于产生;各种VFAs消耗快慢依次为:乙酸>正丁酸>丙酸>正戊酸>异戊酸>异丁酸.     

Influencing mechanism of high solid concentration on anaerobic mono-digestion of sewage sludge without agitation

High-solids anaerobic digestion of sewage sludge was a promising process, but high solid concentration negatively influenced methane production. The influencing mechanism was systematically analyzed in this study through a series of static anaerobic digestion experiments at total solids (TS) contents of 3%–15%. The results showed that TS 6% was the boundary between low-solids and high-solids anaerobic digestion, and the accumulative methane yield decreased exponentially when TS increased from 6% to 15%. The performance of anaerobic digestion was directly determined by the efficiency of mass transfer, and the relation between methane yield and sludge diffusive coefficients was well described by a power function. Thus, the increasing TS resulted in an exponential increase in sludge viscosity but an exponential decrease in diffusive coefficient. The blocked mass transfer led to the accumulation of volatile fatty acids (VFAs) and free ammonia. Acetic metabolism was the main process, whereas butyric and propionic metabolisms occurred at the initial stage of high-solids anaerobic digestion. The concentration of VFAs reached the maximum at the initial stage, which were still lower than the threshold influencing methanogens. The concentration of free ammonia increased gradually, and the methanogenesis was inhibited when free ammonia nitrogen exceeded 50 mg·L⁻¹. Consequently, the deterioration of high-solids anaerobic digestion was related to the blocked mass transfer and the resulting ammonia accumulation.