Characteristics and chemical reactivity of biogenic volatile organic compounds from dominant forest species in the Jing-Jin-Ji area,China

Background:Biogenic volatile organic compounds(BVOCs)play an essential role in tropospheric atmospheric chemical reactions.There are few studies conducted on BVOCs emission of dominant forest species in the Jing-Jin-Ji area of China.Based on the field survey,forest resources data and the measured standard emission factors,the Guenther model developed in 1993(G93)was applied in this paper to estimate the emission of BVOCs from several dominant forest species(Platycladus orientalis,Quercus variabilis,Betula platyphylla,Populus tomentosa,Pinus tabuliformis,Robinia pseudoacacia,Ulmus pumila,Salix babylonica and Larix gmelinii)in the Jing-Jin-Ji area in 2017.Then the spatiotemporal emission characteristics and atmospheric chemical reactivity of these species were extensively evaluated.Results:The results showed that the total annual BVOCs emission was estimated to be 70.8 Gg C·year^(−1),consisting 40.5%(28.7 Gg C·year^(−1))of isoprene,36.0%(25.5 Gg C·year^(−1))of monoterpenes and 23.4%(16.6 Gg C·year^(−1))of other VOCs.The emissions from Platycladus orientalis,Quercus variabilis,Populus tomentosa and Pinus tabulaeformis contributed 56.1%,41.2%,36.0% and 31.1%,respectively.The total BVOCs emission from the Jing-Jin-Ji area accounted for 61.9% and 1.8%in summer and winter,respectively.Up to 28.8% of emission was detected from Chengde followed by Beijing with 24.9%,that mainly distributed in the Taihang Mountains and the Yanshan Mountains.Additionally,the Robinia pseudoacacia,Populus tomentosa,Quercus variabilis,and Pinus tabulaeformis contributed mainly to BVOCs reaction activity.Conclusions:The BVOCs emission peaked in summer(June,July,and August)and bottomed out in winter(December,January,and February).Chengde contributed the most,followed by Beijing.Platycladus orientalis,Quercus variabilis,Populus tomentosa,Pinus tabulaeformis and Robinia pseudoacacia represent the primary contributors to BVOCs emission and atmospheric reactivity,hence the planting of these species should be reduced.

Research Progress on Removal of Oxygenatesin Fischer-Tropsch Oil by Adsorption

The oxygen-containing compounds in Fischer Tropsch synthetic oil greatly affect the downstream deep processing of hydrocarbons,and effective removal is required.Com-pared to traditional removal technologies such as hydrogenation deoxygenation,solvent extraction,and extraction distillation,adsorption deoxygenation technology has the advantages of low cost,mild operating conditions,easy removal and recovery,and mini-mal impact on oil quality.Therefore,adsorption deoxygenation technology has devel-oped rapidly in various removal processes and has become a research hotspot in the cur-rent Fischer Tropsch oil deoxygenation.Adsorbents are the core of adsorption deoxygen-ation technology.Therefore,this article briefly introduces the adsorption mechanism and summarizes the research progress of adsorbents widely used in recent years,such as silica gel,alumina,molecular sieves,and metal organic frameworks,in adsorbing oxygen-containing compounds in Fischer Tropsch synthetic oils.And provide reference sugges-tions for further adsorption and deoxygenation directions in the future.

Species profile and reactivity of volatile organic compounds emission in solvent uses,industry activities and from vehicular tunnels

A survey was conducted of the volatile organic compounds(VOCs)released from sources of solvent use,industry activities and vehicle emissions in Guiyang,a capital city of China.Samples were collected by canisters and analyzed by GC-MS-FID.The species profiles of VOCs emitted from sources were obtained.Results showed that xylenes,ethylbenzene,acetone and dichloromethane were the characteristics species for painting,2-propanol and ethyl acetate for printing,α-pinene for solid wood furniture manufacturing,and 2-butanone for biscuit baking.These characteristics species could be as tracers for the sources respectively.In most of samples from the solvent use,the benzene/toluene(B/T)ratio was less than 0.3,indicating that the ratio could be as the indicator for tracing the solvent use related sources.The results also suggested that the toluene/xylene(T/X)ratio be as the indicator to distinguish the VOCs sources of painting(<2)from the printing(>2).Aromatics contributed the most to ozone formation potential(OFP)of most painting and non-paper printing sources,and oxygen-containing VOCs(OVOCs)were major species contributing to OFP of the sources from food production and paper printing.The OFP of the VOCs emissions from vehicle in tunnels and from other manufactures were dominated by both aromatics and alkenes.Theα-pinene could explain 56.94%and 32.54%of total OFP of the VOCs sources from filing cabinet and solid wood furniture manufacturing,which was rarely been involved in previous studies of VOCs source profiles,indicating that the species of concern for VOCs sources are still insufficient at present.

Adsorption thermodynamics and kinetic investigation of aromatic amphoteric compounds onto different polymeric adsorbents

The adsorption behavior ofp-aminobenzoic acid and o-aminobenzoic acid onto the different polymeric adsorbents was systematically investigated as a function of the solution concentration and temperature. Experimental results indicated that the equilibrium adsorption data of the four polymeric adsorbents fitted well in the Freundlich isotherm. The adsorption capacity of multi-functional polymeric adsorbent NJ-99 was the highest, which might be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of aminobenzoic acid. The adsorption capacity of o-aminobenzoic acid onto any adsorbent was higher than p-aminobenzoic acid. Thermodynamic studies suggested the exothermic, spontaneous physical adsorption process. Adsorption kinetics results showed that the adsorption followed the pseudo-second-order kinetics model and the intraparticle mass transfer process was the rate-controlling step.

Thermodynamic study of adsorption of phenolic compounds onto Amberlite XAD-4 polymeric adsorbents and its acetylized derivative MX-4

Adsorption equilibrium isotherms of phenolic compounds, phenol, p cresol, p chlorophenol and p nitrophenol, from aqueous solutions by Amberlite XAD 4 polymeric adsorbent and its acetylized derivative MX 4 within temperature range of 283 323K were obtained and fitted to the Freundlich isotherms. The capacities of equilibrium adsorption for all four phenolic compounds from their aqueous solutions increased around 20% on the acetylized resin, which may be contributed to the specific surface area and the partial polarity on the network. Estimations of the isosteric enthalpy, free energy, and entropy for the adsorption process were reported.

ADSORPTION BEHAVIOR OF PHENOLIC COMPOUNDS ONTO POLYMERIC ADSORBENTS MODIFIED WITH 2-CARBOXYBENZOYL GROUPS

Two hypercrosslinked polymeric adsorbents （ZH-01 and Amberlite XAD-4 resin） were employed to remove three kinds of phenolic compounds including phenol, 4-nitrophenol and 2,4-dinitrophenol from aqueous solutions. The study was focused on the static equilibrium adsorption behavior, the column dynamic adsorption and desorption profiles. The Freundlich model gave a perfect fitting to the isotherm data. The adsorbing capacities for these three compounds on ZH-01 were higher than those on Amberlite XAD-4 within the temperature range 288-318 K, which was attributed to the large micropore area and 2-carboxybenzoyl functional groups on the network of ZH-01 resin. The adsorption for phenol and 4- nitrophenol on ZH-01 was a physical adsorption process, while for 2,4-dinitrophenol it was a coexistence process of physical adsorption and chemisorption＇s transitions. The column test showed the advantages of ZH-01 in the dynamic adsorption processes of phenolic compounds. Being used as the desorption reagent, sodium hydroxide solution showed an excellent performance.

THERMODYNAMIC STUDY OF ADSORPTION OF PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTION BY A WATER-COMPATIBLE HYPERCROSSLINKED POLYMERIC ADSORBENT

Equilibrium data for the adsorption of phenolic compounds, i.e., phenol, p-cresol, p-chlorophenol and p- nitrophenol from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent (NJ-8) within temperature range of 283-323 K were obtained and correlated with a Freundlich-type of isotherm equation, so that equilibrium constants KF and n were obtained. The capacities of equilibrium adsorption for all the four phenolic compounds on the NJ-8 from aqueous solutions are around 2 times as high as those of Amberlite XAD-4, which may be attributed to the unusual micropore structure and the partial polarity on the network. The values of the enthalpy (always negative) are indicative of an exothermic process, which manifests the adsorption of all the four phenolic compounds on the two polymeric adsorbents to be a process of physical adsorption. The negative values of free energy change show that the solute is more concentrated on the adsorbent than in the bulk solution. The absolute free energy values of adsorption for NJ-8 are always higher than those for Amberlite XAD-4, which indicates that phenolic compounds are preferentially adsorbed on NJ-8. The negative values of the adsorption entropy are consistent with the restricted mobilities of adsorbed molecules of phenolic compounds as compared with the molecules in solution. The adsorption entropy values of phenolic compounds for NJ-8 are lower than those for Amberlite XAD-4, which means the micropores of NJ-8 require more orderly arranged adsorbate.

Structure-activity relationships of oxime compounds as flotation collectors by DFT calculations

The relationships between the structure of oxime compounds(R^(1)R^(2)C=NOH,R^(1)/R^(2)=alkyl groups) with different substituents and their corresponding flotation performances were studied. The analyses of density functional theory(DFT) calculations illustrated that the introduced phenyl group at the R^(1) position could enhance the acidity,while the heptyl group could effectively increase the hydrophobicity and benefit van der Waals interactions. Meanwhile,the introduced amino group at the R^(2) position could provide cationic sites to interact with negatively charged surfaces of minerals, while the introduced hydroxyl group could provide additional action sites to form stable chelates with metal ions. Based on the structure-activity relationships, structural optimization was carried out to obtain three efficient collectors, which possessed superior flotation separation performances, proving the effectiveness of the structural modification to oxime compounds in this work.

Application of a Quartz Crystal Microbalance (QCM) System Coated with Chromatographic Adsorbents for the Detection of Olive Oil Volatile Compounds

A sensor based on the technique of a piezoelectric quartz crystal microbalance (QCM) is analyzed for the detection of six organic volatile compounds with high olive oil sensory significance, such as hexanal, acetic acid, Z-3-hexenyl acetate, undecane, 1-octen-3-ol and 2-butanone. Four sample concentrations have been exposed to each QCM sensor constructed. The detection system is based on the sample adsorption on the forty sensing films coated at the surfaces of forty AT-cut gold-coated quartz crystals. Each sensing film has been prepared with different solution concentrations of ten materials, usually used as chromatographic sta-tionary phases. Sensing film coating process shows excellent repeatability, with coefficient values less than 0.50%. The frequency shifts of the piezoelectric crystals due to the adsorption of the volatile compounds have been measured as sensor responses, using a static measurement system. The results show that only five QCM sensors, with high sensitivity values, are enough to the detection of the volatile compounds studied. Therefore, the developed detection system presented herein provides a rapid identification of organic volatile compounds with elevated olive oil sensory connotation and it could be a substitute technique to the analytical methods normally used for the analysis of the olive oil flavor.

Removal of Heteroaromatic Sulfur Compounds by a Non-noble Metal Fe Single-atom Adsorbent

Sulfur-containing compounds(SCCs)must be removed from fuels before use.In this study,a novel non-noble metal Fe single-atom adsorbent(SA-Fe/CN)was synthesized using a core-shell strategy and applied for the adsorptive removal of benzothiophene(BT)and dibenzothiophene(DBT).The adsorption isotherms,thermodynamics,kinetics,and adsorption-regeneration cycles of DBT and BT on SA-Fe/CN were studied.SA-Fe/CN exhibited a significant capacity to adsorb DBT,and the isothermal equilibrium was well described by the Langmuir isotherm.The Gibbs free energy values were negative(ΔG^(0)<0),indicating that the adsorption of DBT and BT was favored and spontaneous.The adsorption process conformed to the pseudo-second-order kinetic model with high R^(2) values(0.9994,0.9987).The adsorption capacity of SA-Fe/CN for DBT and BT reached 163.21 mg/g and 90.35 mg/g,respectively,due to the highly active sites of the single atom and electrostatic interaction with the sulfide.Therefore,SA-Fe/CN may be a promising adsorbent for SCC removal.

Theory of pleiotropic action of biologically active compounds and medicines—Basic principles and practical application

This article represents the main positions of the theory of pleiotropic action of biologically active compounds (BACs) and medicines, which has been designed by the author based on her own experimental researches. The term “pleiotropy” means the ability of the BACs and medicines to implement more than one mechanism of action resulting in the specific biological (pharmacological) effect. The interaction of these mechanisms forms a distinct pattern of biological response (pleiotropic pattern), which reflects the change in his character with the increased dose (concentration)-dependent efficacy of BACs and medicines. The article consists of description of different pleiotropic patterns established in experiments on the model of reactive oxygen species (ROS) generation by macrophages dependent on activity of specialized enzyme called Nox2-NAD(P)H oxidase (Nox2, EC 1.6.3.1). Moreover, it consists of explanation of pharmacodynamic nature of pleiotropic patterns by means of application Chou-Talalay median effect equalization and combination index (CI) theory. The novel theory explains unsolved until now universal aspects of activity BACs and medicines, such as slope angles of “dose-effect” dependences in the conditions relevant in vivo, and it is of fundamental interest. However, it has applications in experimental pharmacology, as it allows defining the choice of the individual compounds and combinations, modulating the trust effect selectively and efficiently. This knowledge opens up new approaches to medicines discovery and evaluation, their rational dosing and combining.

Preparation of Fe-Al Binary System Intermetallic Compounds by Multi-Layered Roll-Bonding

Iron aluminides exhibit good resistance to high-temperature sulfidizing and oxidizing environments and potential for structural applications at high temperatures under corrosive environments. In this study, Fe-Al intermetallic compound was prepared by multi-layered roll-bonding of elemental Fe and Al foils. The process consisted of the accumulative roll-bonding (ARE) for making a laminated Fe/Al sheet and the subsequent heat treatment promoting a solid phase reaction in the laminated Fe/Al sheet. The microstructures produced at each processing stage were characterized by optical microscopy and scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectroscopy (EDS). Vickers microhardness testing was used for hardness determination. A homogeneous intermetallic compound of Fe3Al or FeAl could be obtained after the subsequent heat treatment for 1.8 ks at 973 K and for 10.8 ks at 1123 or 1173 K.

A theoretical study on the molecular structure and chemical reactivity of traditional Chinese medicine extract isopimpinellin

Isopimpinellin(C13H10O5),alternative name 5,8-dimethoxypsoralen,is one of the furocoumarin compounds.This traditional Chinese medicine extract has attracted a great deal of attention in recent years due to its pharmacological properties,especially its antifungal effect.The main purpose of this study was to study the molecular structure and chemical reactivity of isopimpinellin using the density functional theory method.To understand and interpret the reactivity of isopimpinellin,various chemical reactivity descriptors such as chemical potential(μ),electronegativity(χ),chemical hardness(η)and electrophilicity(ω)and local reactivity index condensed Fukui function(fi(r))have been calculated with five hybrid functionals PBE1PBE,MPW1PW91,B3LYP,X3LYP and B3PW91.These chemical reactivity descriptors indicate that the isopimpinellin molecule has a good antioxidant activity,which could be one of the reasons for its action as an effective antifungal drug.The condensed Fukui functions of isopimpinellin molecule provide a complete scheme of chemical reactivity of one molecule.

ZSM-5分子筛对典型涂装VOCs的吸附性能及机理研究

通过水热法成功合成了一系列宽硅铝比(50、100、150、300、500、800、1500、3000)的ZSM-5分子筛,旨在研究其对涂装行业典型挥发性有机物(volatile organic compounds,VOCs)的吸附规律。同时,结合分子筛表面的酸性位点,以解析硅铝比对分子筛吸附性能的影响机制。实验结果表明,丙酮的吸附能力主要受自身极性、支链结构和分子筛表面酸位点的影响。而乙酸丁酯、苯乙烯、对二甲苯、苯、甲苯的吸附性能会同时受到自身的分子量、分子直径、极性、分子结构和官能团的影响,分子量和分子直径大、极性强且具有支链结构的VOCs更容易被ZSM-5分子筛吸附。这6种VOCs中,ZSM-5分子筛对丙酮的吸附效果最好,硅铝比对其吸附性能的影响也最大。这是因为丙酮比其他VOCs更容易吸附在Lewis酸位点上,硅铝比的改变会影响酸位点的数量。低硅铝比的分子筛由于具有较多的酸位点,更适用于丙酮的吸附。

构筑Ni/ZnCO_(2)O_(4)@ZnO复合金属氧化物脱硫剂及其反应吸附脱硫-再生性能研究

采用共沉淀法在ZnO中引入金属Co并使其形成复合金属氧化物,通过共沉淀-浸渍法构筑了不同Co含量的复合金属氧化物脱硫剂,考察其脱硫活性和再生性能。采用XRD、TEM、N_2低温吸附-脱附、XPS和H_(2)-TPR等对脱硫剂的结构和性质进行系统表征,证实得到了Ni/ZnCO_(2)O_(4)@ZnO结构的复合金属氧化物脱硫剂。复合金属氧化物脱硫剂中ZnCO_(2)O_(4)的形成有利于脱硫剂的颗粒尺寸减小、分散度提升、比表面积增大。反应后XRD显示,ZnCO_(2)O_(4)也可作为H_2S的吸附剂,从而提高了脱硫剂的硫吸附容量。所有的复合金属氧化物脱硫剂的脱硫性能显著优于Ni/ZnO,其中,Zn:Co物质的量比为1:1的脱硫剂NZCo-3具有最优的脱硫性能,该脱硫剂在反应温度300℃,氢压3 MPa,质量空速2.2 h^(-1),氢油体积比300的条件下脱硫率为100%,且经过六次循环后仍能够保持优异的脱硫性能。该研究结果为合理设计Ni/ZnO脱硫剂以提高其脱硫性能和再生性能提供新的思路。

生物质焦油模化物的热裂解ReaxFF模拟研究

实现热裂解过程中焦油的有效脱除是生物质热利用技术中亟待解决的问题。通过密度泛函理论研究生物质焦油3种典型模型化合物(甲苯、苯酚和萘)的分子结构性质,并基于ReaxFF反应力场对焦油模型化合物的热裂解过程进行分子动力学模拟研究,从分子层面对焦油热裂解的复杂反应过程进行深入研究。探索反应温度对热裂解特性的影响,详细研究甲苯、苯酚和萘的热裂解机理及中间自由基、气体产物的演化过程。结果表明:C—H键的Mayer键级小于C—C键,易于断裂,芳香环侧链结构中氢的Mulliken电荷数大,具有更强的活性;3种焦油模型化合物的热稳定性依次为:萘>苯酚>甲苯,其中苯酚具有高活性的含氧官能团,二次裂解易生成气体产物,而甲苯和萘二次裂解易生成稠环芳烃;甲苯、苯酚和萘的一级反应动力学热解表观活化能分别为314.03、362.39、396.74 kJ/mol。

乙烯利处理对去皮莲藕酚类和活性氧代谢的影响

目的探究乙烯利(ethephon,ET)处理对去皮莲藕(Nelumbo nucifera Gaertn)贮藏品质的影响及潜在作用机制。方法以鄂莲5号莲藕为实验材料,每12 h测定其在20℃贮藏期间的色泽、总酚含量、多酚氧化酶(polyphenol oxidase,PPO)、苯丙氨酸解氨酶(phenylalnine ammonialyase,PAL)、超氧阴离子(superoxide production,O_(2)^(-)·)的产生速率、过氧化氢(hydrogen peroxide,H2O_(2))含量、丙二醛(malondialdehyde,MDA)含量、羟基自由基(hydroxyl radical,·OH)生成速率、超氧化物歧化酶(superoxide dismutase,SOD)、过氧化氢酶(catalase,CAT)和过氧化物酶(peroxidase,POD)的变化规律。结果4.0 g/L ET溶液浸泡去皮莲藕5 min有效抑制了去皮莲藕的褐变,显著延缓了L^(*)的下降,在72 h贮藏后约为对照组的1.04倍(P<0.05)。在整个贮藏期间,与对照相比,ET处理提高了PAL和PPO的活性,诱导总酚物质含量的增加,ET处理组在60 h的总酚含量达到最高值,其含量为165.01 mg/kg,约为CK组的1.18倍。ET处理提高了去皮莲藕POD、SOD和CAT的活性,同时增强了1,1-二苯基-2-三硝基苯肼(1,1-diphenyl-2-picrylhydrazyl,DPPH)自由基清除率。ET抑制O_(2)^(-)·,降低·OH、MDA和H_(2)O_(2)含量。结论4.0 g/L ET处理可以通过诱导酚类物质的生成和提高自身的抗氧化能力来延缓去皮莲藕的品质劣变,可为维持果蔬品质方面的应用提供理论参考。

基于季节性污染特征的大气VOCs化学活性及源解析

挥发性有机物(VOCs)是对流层大气氧化性的重要影响因子,不同VOCs物种的化学反应活性与大气环境质量及污染过程关系密切。本文针对呼和浩特和包头采暖期长达半年的季节特征,选取冬夏季清洁天、污染天和沙尘天的不同时间窗口,识别并分析了两个城市大气中117种VOCs的体积浓度,计算了不同季节不同大气特征条件下不同VOCs物种的化学反应活性,并解析了两个城市大气VOCs的来源。结果表明,乙烯、乙醛、丙烷、丙烯、丙醛、正丁醛、异戊二烯、甲苯、间/对二甲苯等是两个城市大气的主要活性VOCs物种;不同大气特征条件下不同VOCs物种对OFP(臭氧生成潜势)和LOH(羟自由基反应速率)的影响差异较大,且影响大小并不单独依赖于各VOCs物种浓度;2个城市冬季大气中的O3对VOCs的浓度变化更敏感,夏季则对NOx的浓度变化更敏感,体现了这两个城市O3前体物的季节性差异;受季节特征及供暖方式的影响,2个城市冬季燃烧源排放约贡献大气VOCs的50%,机动车排放和LPG/NG源次之;与冬季相比,夏季机动车、生物源及LPG/NG、溶剂挥发等因子的重要性显著提升,而燃烧源因子的比重明显下降,意味着大气VOCs源具有显著的季节变化特征。本研究对准确辨析区域重污染天气特征与成因,实现“十四五”期间PM2.5与臭氧协同控制等意义重大.

复方黄柏液负压滴灌联合局部氧疗在3、4期压力性损伤患者中的应用

目的 探讨复方黄柏液负压滴灌联合局部氧疗在3、4期压力性损伤创面中的治疗效果。方法 将98例3、4期压力性损伤患者随机分为两组,每组49例。对照组给予生理盐水负压滴灌治疗,观察组给予复方黄柏液负压滴灌联合局部氧疗。治疗前,治疗2周、4周时评估两组压力性损伤愈合量表得分、治疗效果、住院时间及血清炎性因子水平。结果 治疗2周、4周,观察组压力性损伤愈合计分、C-反应蛋白、白细胞介素-6及住院时间显著低于对照组(均P<0.05),治疗4周观察组治疗效果显著优于对照组(P<0.05)。结论 复方黄柏液负压滴灌联合局部氧疗,可有效降低炎性因子水平,提高3、4期压力性损伤创面的治愈率,缩短住院时间。

湿摩擦牢度提升剂的复配与应用性能

使用自制的苯丙乳液与水性聚氨酯乳液作为织物的湿摩擦牢度提升剂,探究其在织物整理中的复配效果并优化整理工艺。结果表明:两种乳液以1∶2复配,总质量浓度为40 g/L,柔软剂的质量浓度为40 g/L,130℃焙烘3 min,黑色纯棉针织物的耐湿摩擦色牢度能提升2级。