高比活度碳-14标记氟噻草胺的合成与分析

为开展除草剂氟噻草胺在我国的登记代谢试验,本研究以4-氟[U-¹⁴C]苯胺为同位素原料,经还原胺化、缩合、取代、水解和醚化五步放化反应获得N-(4-氟[U-¹⁴C]苯基)-N-异丙基-2-((5-(三氟甲基)-1,3,4-噻二唑-2-基)氧基)乙酰胺(2,总活度201.65 MBq;比活度2 049.80 MBq·mmol^-1;化学纯度和放化纯度均大于98%,总放化收率39%);以[¹⁴C]硫氰酸钠为同位素原料,经加成、水解、环化、重氮化和醚化五步放化反应获得N-(4-氟苯基)-N-异丙基-2-((5-(三氟甲基)-1,3,4-[2-¹⁴C]噻二唑-2-基)氧基)乙酰胺(3,总活度287.86 MBq;比活度2 042.40 MBq·mmol^-1;化学纯度和放化纯度均大于98%,总放化收率14%)。两种标记物的结构经核磁共振氢谱(¹H NMR)和质谱(MS)分析确认,质量指标经高效液相色谱(HPLC-PDA)、放射性薄层成像分析(TLC-IIA)、在线放射性高效液相色谱(HPLC-FSA)和液体闪烁法(LSC)测定,均可作为放射性示踪剂。本研究结果为氟噻草胺的同位素示踪研究(包括该除草剂在我国的登记代谢试验)奠定了物质基础。     

土壤中红霉素结合残留在菜心中生物有效性研究

为探究土壤环境中红霉素污染的生物风险,本试验采用¹⁴C示踪技术,选取广东菜心为代表,研究红霉素结合残留的释放、转化及生物有效性,并探讨添加外源有机肥(如鸡粪、活性淤泥)对该过程的影响。结果表明,土壤中红霉素结合残留随着时间推移逐渐释放,在培养45 d时下降至引入量的59.83%,其中15.00%转化为可提态残留;植物根系的吸收和扰动能促进红霉素结合残留的释放和转化(P <0.05);土壤中的红霉素结合残留能够被广东菜心根部吸收并转运至可食部分,转运系数为0.34,表明红霉素结合残留在菜心体内不易向上运输;放射性自显影图片显示,被植物吸收的¹⁴C-红霉素及其放射性衍生物主要集中在叶片和根部;外源添加有机肥(鸡粪和活性淤泥)处理,一方面可抑制结合残留的释放,增加富啡酸中红霉素结合残留的含量(P<0.05),导致土壤中红霉素污染更持久,另一方面可促进植物对土壤中红霉素残留的吸收;腐殖质分级结果显示,红霉素结合残留主要集中在富啡酸中(87.92%~97.21%),并随着时间推移不断释放。本研究结果为科学评价红霉素的生态安全提供了理论支持。     

[噻唑基-2-14C]-毒氟磷在产蛋鸡体内的分布

为阐明毒氟磷在动物体内的分布代谢特征,并深入认识毒氟磷的安全性和膳食风险,本研究选择白羽产蛋鸡为试验对象,[噻唑基-2-¹⁴C]-毒氟磷为同位素示踪剂,研究了毒氟磷在产蛋鸡体内的排泄分布特征。结果表明,毒氟磷在产蛋鸡体内排泄水平高,首次给药24 h后即排泄出当日给药量的82.04%,连续给药7 d后的累计排泄率为82.24%。毒氟磷在组织中的总残留仅占引入量的3.81%,其中胃中残留量占比相对最高,占引入量的2.14%,而肺、肾、脂肪、胰腺中的放射性残留量均不超过引入量的0.01%,膳食评估结果表明在上述内脏组织中的毒氟磷残留无膳食风险。蛋、肌肉、心、脑、脾、卵巢等组织中未检测到放射性残留。本研究为科学评价毒氟磷在家禽中的安全性提供了试验依据。     

脉冲标记下甘蔗13C富集及氮磷钾含量变化

¹³C示踪是精准量化植物碳源贡献土壤碳的有效途径。为建立经济适用的甘蔗¹³C脉冲标记方法,同时获得¹³C富集蔗叶,本研究采用自制全密闭标记室进行标记试验,供试甘蔗品种为桂糖58号,设置0(CK)、0.32(T1)、0.64(T2)和1.28 g·m^-3(T3)4个Na₂¹³CO₃标记浓度,每隔7 d进行6 h的¹³CO₂脉冲标记,共标记6次。于第6次脉冲标记开始及结束后采集标记室内气体,测定CO₂浓度和δ¹³C-CO₂。并于第2、第4和第6次标记7 d后破坏性采集植株,测定蔗叶和根系δ¹³C值及全碳和N、P、K含量,计算蔗叶和根系¹³C标记效率。结果表明,在密闭标记时间内,外源释放的¹³CO₂ 95%以上被甘蔗光合作用利用。蔗叶δ^...     

Indirect effects of earthworms on microbial assimilation of labile carbon

Interactions between earthworms and microorganisms can be important in regulating the rate of soil carbon turnover and maintaining soil fertility in agroecosystems. Despite the significance of earthworms in nutrient cycling in agroecosystems, the indirect influence of earthworms on C assimilation by microorganisms has not been adequately quantified. We assessed microbial assimilation of ¹³C-labeled acetate in earthworm (Lumbricus terrestris) middens and surrounding soil collected from maize agroecosystems. Incorporation of ¹³C into microbial lipids was used as an indicator of microbial growth rates. Earthworm middens had significantly lower concentrations of microbial phospholipid phosphates and lower natural abundance δ¹³C than the surrounding soil. After incubation with ¹³C-labeled acetate, microbial communities in earthworm middens had greater ¹³C/¹²C ratios of microbial lipids than microbial communities from surrounding soil. The ¹³C enrichment per unit of microbial phospholipid was much greater in middens than in surrounding soil indicating that: (i) microbial lipid synthesis was significantly higher in the earthworm middens; (ii) microbial assimilation efficiency for ¹³C-labeled acetate was greater in midden soil; or (iii) assimilation of ¹³C-labeled acetate relative to other C sources was proportionately greater in middens than in the surrounding soil. Our results suggest that there were functional differences between microbial communities in earthworm middens and surrounding soil, probably due to a combination of physical, chemical, and biological changes in the midden microenvironment. The resulting differences in microbial communities or activity increased microbial growth rates and assimilation of readily available C substrates in middens relative to surrounding soil.     

Stability and mineralization of organic phosphorus incorporated into model humic polymers

The stability of the phosphate ester linkage in phosphoserine (PS) and phosphoethanolamine (PE) was evaluated after incorporation of these compounds into model humic polymers. Humic polymers prepared by oxidation of a mixture of substituted phenols in the presence of either PS or PE resulted in model humic materials containing from 0.25 to 0.94% P, values within the range found for organic P in natural soil humic materials. The organic P contained in model humic polymers was resistant to hydrolysis with 1 n HC1 and 1 n NaOH and resistance of the P ester to hydrolysis with 6 n HCl was increased through incorporation into model humic polymers. Organic P in model humic polymers was also stabilized towards hydrolysis with acid and alkaline phosphomonoesterases. Less than 11% of the organic P in polymers containing PS and PE was hydrolyzed by acid or alkaline phosphatase. The incorporation of PE into a model humic polymer markedly reduced the amount of P mineralized during incubation in soil when compared to P mineralized in soils treated with PE. For all environmental conditions imposed during soil incubations (i.e. pH, aeration, temperature), only 20% of the P in model humic polymer containing PE was released during a 16-week period. In contrast, > 60% of the P in either PS and PE added individually to soils or PS and PE intimately mixed with preformed model humic polymer and then added to soils was released during the initial 7 days of soil incubation. The results suggest that a portion of the unidentified organic P in soils may arise from the incorporation of organic compounds containing both amine and phosphate ester functional groups into humic materials and that the organic P thus formed is resistant to both chemical and enzymatic hydrolysis.     

C and N NMR spectroscopy as a tool in soil organic matter studies

Nuclear magnetic resonance (NMR) is a valuable tool for the characterization of soil organic matter and humification processes in soils. This review highlights soil organic matter studies based mainly on solid-state ¹³C and ¹⁵N NMR spectroscopy and some emerging applications, that may provide significant progress in our knowledge on soil organic matter. A major advantage of Nmr spectroscopy is that it can be used as a non-invasive method for solid soil samples or soil fractions. Although resolution is limited, one can obtain an overview on the organic matter structures present in the soil sample. Application of ¹³C and ¹⁵N NMR to soils has, for a long time, been confined to the study of bulk soils or humic extracts for structural characterization. The transformations of soil organic C and N are now being investigated after addition of ¹³C- and ¹⁵N-labelled parent materials to the soil and following their evolution in different C and N pools. With labelling techniques it is also possible to study the interaction of organic pollutants with soil organic matter. Contamination of a soil with man-made additives, such as soot or brown coal dust, can also be detected in soils or individual soil fractions.     

13C NMR of humic substances: pH and solvent effects

Since the concentration of free radicals in humic subtances increases at high pH the use of basic solutions for ¹³C NMR spectroscopy may cause broadening and loss of aromatic signals, with distortion of intensity distributions. No such effects were found in ¹³C spectra of soil humic and fulvic acid, an aquatic fulvic acid, and two phenolic polymers run in aqueous solutions at different pH values, and in dimethylsulphoxide. With increasing pH, the peak in the carboxyl region shifted in a manner consistent with greater dissociation of carboxyl and phenolic groups, and also certain features in the aliphatic and carboxyl regions were enhanced under some solution conditions. Elevated solution temperature (70°C) caused only slight improvement in the resolution of some lines. Chemical shifts were determined for some known phenolic and benzenecarboxylic acid compounds in DMSO and NaOD. The range for phenolic carbons extended to 173 ppm in NaOD, while some aromatic carbons occurred around 105 ppm, in the same region as anomeric carbons. Thus, even under quantitative acquisition conditions, relative areas may be used only to estimate proportions of different types of carbons and functional groups.     

氮肥种类和施用量对南洋杉苗期的影响

Nitrogenous fertilisers are under consideration for promoting the growth of nursery-reared hoop pine （Araucaria cunninghamii Alton ex A. Cunn） seedlings in the establishment phase of second rotation （2R） plantations. Using ^15N- labelled fertilisers, we investigated the effect of different forms （ammonium sulphate, ammonium nitrate, potassium nitrate and urea） and rates of application （0, 150 and 300 mg N kg^-1 dried soil） of fertilisers on the growth, ^15N recovery and carbon isotope composition （δ^13C） of hoop pine seedlings in a 12-month glasshouse trial in southeast Queensland, Australia. The ^15N-labelled fertilisers were applied to nursery-reared hoop pine seedlings, which were then grown in pots, containing ca. 1.2 kg dried soil, under well watered conditions for 12 months. Four seedlings from each treatment were harvested at 4-month intervals, divided into roots, stem and foliage, with a further subdivision for new and old foliage, and then analysed for ^15N, total N, δ^13C and total C. There was no significant response in the seedling growth to the form or rate of application of nitrogen （N） fertiliser within the 12-month period, indicating that the seedlings did not experience N deficiency when grown on second rotation hoop pine soils. While the combined ^15N recovery from soil and plant remained at around 70% throughout the experiment, the proportion of ^15N recovered from the plants increasing steadily over time. Nitrate containing fertilisers at 150 mg N kg^-1 soil gradually increased seedling foliage δ^13C over the 12-month period, indicating an increase in seedling water use efficiency.     

样本预处理方式对罗氏沼虾碳和氮稳定同位素比值检测的影响

为研究样本预处理方式对罗氏沼虾碳和氮稳定同位素比值检测的影响,分别选用3种保存温度(常温23℃/15 d、冷藏2℃/90 d、冷冻-18℃/360 d)、2种取样方式(虾仁取样、整虾取样),以新鲜沼虾样本为对照组,对比不同样本预处理方式对罗氏沼虾碳稳定同位素比值(δ¹³C)、氮稳定同位素比值(δ¹⁵N)、碳氮比(C/N)的影响。结果表明,不同保存温度和不同取样方式对罗氏沼虾δ¹³C、δ¹⁵N、C/N的影响明显。与对照组相比,常温保存条件下的δ¹⁵N偏移量最大(1.31‰~13.16‰,平均值为6.02‰),冷冻保存条件下的δ¹³C偏移量最大(2.34‰~2.84‰,平均值为2.57‰),室温保存条件下的C/N显著增加(P<0.05),冷藏和冷冻保存条件下的C/N显著减少(P<0.05)。不同取样方式对罗氏沼虾δ¹⁵N、δ¹³C的影响还取决于保存温度,在冷冻保存条件下,整虾取样的δ¹⁵N、δ¹³C显著高于虾仁取样,而在常温保存条件下,整虾取样的δ¹⁵N偏移量显著低于虾仁取样。因此,常温(23℃)和冷藏(2℃)条件不适合保存罗氏沼虾、冷冻(-18℃)保存罗氏沼虾的时间不宜超过60 d,建议新鲜沼虾采集后应立即干燥并开展碳和氮稳定同位素检测。本研究结果为水产品碳和氮稳定同位素比值检测的样本预处理方式提供了参考。     

Transformation of [14C] and [35S]labeled lignosulfonates during soil incubation

[¹⁴C] and [³⁵S]labeled lignosulfonates (LS) or [¹⁴C]labeled coniferyl alcohol dehydropolymer (DHP) were aerobically incubated in soil for 17 weeks. Respiratory ¹⁴CO₂ was compared with that from DHP or that from [U¹⁴C]cellulose. Less CO₂ was released from ring and side chain carbons of LS than from DHP, though similar amounts of CO₂ were released from the methoxyl groups of both compounds. After incubation, the soil samples were exhaustively extracted with water and then with a sodium pyrophosphate-NaOH solution. The water solubility of the originally completely-soluble LS carbons was greatly decreased by incubation, and a large portion of the extracted ³⁵S was detected as sulfate. The pyrophosphate extract was separated into humic and fulvie acids. The humic acid from soils incubated with LS contained low ³⁵S activity and a similar ¹⁴C activity to that from soils incubated with DHP. The fulvic acid from the soils incubated with LS contained higher amounts of ¹⁴C (and ³⁵S) than that of the soils incubated with DHP. More side chain ¹⁴C activity than other ¹⁴C activity was found in both, the water extract and the fulvic acid from soils incubated with LS. The high ³⁵S together with the high side chain ¹⁴C activity probably indicates an elimination of the side chain carbons together with sulfonic acid groups. Anaerobic incubation of soil with LS or DHP promoted breakdown and incorporation of LS and DHP into humus much less than aerobic incubation. The possible reduction in potential pollution from lignosulfonates due to the observed transformations in soil are discussed.     

鄱阳湖不同湿地植物群落光合碳储量及分配

稳定性碳同位素自然丰度(¹³C)表征生态系统碳循环关键过程,为了追踪陆地生态系统碳的动态及其分配,通过采用¹³C脉冲标记对不同植物光合碳分配及其向地下输入特征进行研究,探讨鄱阳湖不同湿地植物群落(藜蒿群落、水蓼群落、苔草群落和芦苇群落)连续4年(2015—2018年)光合碳储量及分配及其相关影响因素。结果表明:(1)2015—2018年土壤有机碳含量和有机碳储量平均值均呈一致的变化规律,其中以表层土壤最高,随土层深度的增加逐渐降低,20—40 cm以下土壤有机碳含量变化范围相对较小; 60—80 cm土壤有机碳含量最低; 土壤¹³C含量随土层深度的增加呈逐渐增加趋势,其中不同土层大致表现为藜蒿群落>水蓼群落>苔草群落>芦苇群落。(2)2015—2018年不同湿地植物群落土壤养分含量、地上和地下生物量平均值呈一致的变化趋势,均表现为藜蒿群落<水蓼群落<苔草群落<芦苇群落,不同植物群落差异均显著(p<0.05); 而全磷含量呈相反的变化趋势,不同植物群落差异均显著(p>0.05)。(3)脉冲标记当天不同植物¹³C值均表现为叶>茎>根>土壤,具体表现为藜蒿群落>水蓼群落>苔草群落>芦苇群落,这表明不同植物根部对光合固定新碳的富集程度较大。标记当天,不同植物地上¹³C固定百分比例较高,说明标记的效率较高且分配差异较大; 脉冲标记21 d后,¹³C值下降,固定的光合碳转移到土壤中的含量显著增加。(4)标记后植物-土壤系统各组分固定¹³C量占净光合¹³C总量分配比例呈现茎>叶>根>土壤的趋势,光合碳在不同植物各部分以及土体中都有所增加,主要集中在地上部分。(5)相关性分析结果表明,地上生物量与茎叶¹³C含量显著正相关(p<0.05),地下生物量与根和土壤¹³C含量显著正相关(p<0.05); 由此说明地上和地下生物量对光合碳的分配起着主导作用,有利于对地下碳平衡过程和固碳减排的理解。     

Effect of cover crop management on soil organic matter

Characterization of soil organic matter (SOM) is important for determining the overall quality of soils, and cover crop system may change SOM characteristics. The purpose of this study was to examine the effect of cover crops on the chemical and structural composition of SOM. We isolated humic substances (HS) from soils with the following cover crop treatments: (a) vetch (Vicia Villosa Roth.)/rye (Sesale cereale L.), (b) rye alone, and (c) check (no cover crops) that were treated with various nitrogen (N) fertilizer rates. CPMAS-TOSS (cross-polarization magic-angle-spinning and total sideband suppression) ¹³C NMR results indicated that humic acids (HA) from soils under rye only were more aromatic and less aliphatic in character than the other two cover crop systems without fertilizer N treatment. Based on the DRIFT (diffuse reflectance Fourier transform infrared) spectra peak O/R ratios, the intensities of oxygen-containing functional groups to aliphatic and aromatic (referred to as recalcitrant) groups, the highest ratio was found in the HA from the vetch/rye system with fertilizer N. The lowest ratio occurred at the vetch/rye system without fertilizer N treatment. The O/R ratio of fulvic acids (FA) can be ranked as: vetch/rye without fertilizer>vetch/rye with fertilizer>no cover crop without fertilizer>rye alone (with or without fertilizer) soils. Both organic carbon (OC) and light fraction (LF) contents were higher in soils under cover crop treatments with and without fertilizer N than soils with no cover crop. These chemical and spectroscopic data show that cover crops had a profound influence on the SOM and LF characteristics.     

Soil organic carbon and C abundance as related to tillage, crop residue, and nitrogen fertilization under continuous corn management in Minnesota

Long-term field experiments are among the best means to predict soil management impacts on soil carbon storage. Soil organic carbon (SOC) and natural abundance ¹³C (δ¹³C) were sensitive to tillage, stover harvest, and nitrogen (N) management during 13 years of continuous corn (Zea mays L.), grown on a Haplic Chernozem soil in Minnesota. Contents of SOC in the 0–15 cm layer in the annually-tilled [moldboard (MB) and chisel (CH)] plots decreased slightly with years of corn after a low input mixture of alfalfa (Medicago sativum L.) and oat (Avena sativa L.) for pasture; stover harvest had no effect. Storage of SOC in no-till (NT) plots with stover harvested remained nearly unchanged at 55 Mg ha⁻¹ with time, while that with stover returned increased about 14%. The measured δ¹³C increased steadily with years of corn cropping in all treatments; the NT with stover return had the highest increase. The N fertilization effects on SOC and δ¹³C were most evident when stover was returned to NT plots. In the 15–30 cm depth, SOC storage decreased and δ¹³C values increased with years of corn cropping under NT, especially when stover was harvested. There was no consistent temporal trend in SOC storage and δ¹³C values in the 15–30 cm depth when plots received annual MB or CH tillage. The amount of available corn residue that was retained in SOC storage was influenced by all three management factors. Corn-derived SOC in the 0–15 cm and the 15–30 cm layers of the NT system combined was largest with 200 kg N ha⁻¹ and no stover harvest. The MB and CH tillage systems did not influence soil storage of corn-derived SOC in either the 0–15 or 15–30 cm layers. The corn-derived SOC as a fraction of SOC after 13 years fell into three ranges: 0.05 for the NT with stover harvested, 0.15 for the NT with no stover harvest, and 0.09–0.10 for treatments with annual tillage; N rate had no effect on this fraction. Corn-derived SOC expressed as a fraction of C returned was positively biased when C returned in the roots was estimated from recovery of root biomass. The half-life for decomposition of the original or relic SOC was longer when stover was returned, shortened when stover was harvested and N applied, and sharply lengthened when stover was not harvested and N was partially mixed with the stover. Separating SOC storage into relic and current crop sources has significantly improved our understanding of the main and interacting effects of tillage, crop residue, and N fertilization for managing SOC accumulation in soil.     

Decomposition of algal cells and components and their stabilization through complexing with model humic acid-type phenolic polymers

Axenic cultures of Anacystis, Microcoleus, Plectonema and Synechococcus isolated from Greenfield sandy loam and of Anabaena flos-aquae, Nostoc muscorum and Chlorella pyrenoidosa from other sources were cultured under light and constant aeration and with [U-¹⁴C]-glucose in the nutrient medium. Whole cells, cell walls, cytoplasm and extracellular polysaccharides of selected species readily decomposed in the soil and after 22 weeks between 61 and 81% of the added C had evolved as CO₂. Complexing of cell wall and cytoplasmic preparations from A. flos-aquae and N. muscorum with model humic acid-type phenolic polymers reduced decomposition of the cell walls by 40% and of the cytoplasm by 70%. Over 50% of the residual 14C activity in the soil amended with whole algal cells remained in the 0.5% NaOH-extracted soil. With exception of Microcoleus sp. more of the residual ¹⁴C from cell walls, cytoplasm and polysaccharide fractions was present in the humic acid or fulvic acid fractions.     

茶叶与产地环境中稳定同位素和矿物元素特征及其相关性研究

为探究茶叶与茶园土壤、灌溉水源等产地环境中稳定同位素和矿物元素特征及其相关性,采用元素分析同位素质谱联用仪(EA-IRMS)和电感耦合等离子体质谱仪(ICP-MS)对山东日照和崂山的茶叶、栽培土壤及灌溉水源中4种稳定同位素比率(δ¹³C、δ¹⁵N、δD和δ¹⁸O)和23种矿物元素含量(Na、Mg、Al、K、Ca和Sr等)进行测定。结果显示,两地区中稳定同位素和矿物元素具有区域性特征,通过对茶叶中4种稳定同位素与栽培土壤(δ¹³C和δ¹⁵N)、灌溉水源(δD和δ¹⁸O)分别进行线性相关分析,结果表明,茶叶与栽培土壤中的δ¹⁵N相关性最大,R²为0.450 7,其次分别为栽培土壤中的δ¹³C(R²=0.289 5)、灌溉水源中的δ¹⁸O(R²=0.156 2)和δD(R²=0.021 4);同时,利用热图技术对茶叶与栽培土壤、灌溉水源中稳定同位素和矿物元素进行差异性及多重相关性分析,结果表明,茶叶与栽培土壤中δ¹³C呈较强负相关,而与灌溉水源中δ¹⁸O则无明显相关性。同时茶叶与栽培土壤中矿物元素也存在一定差异性,而茶叶中Cd、Li、Co、Sr、Mo与栽培土壤中相应矿物元素相关性较大。本研究初步揭示了稳定同位素在茶叶与栽培土壤、灌溉水源间的分馏情况以及与矿物元素的相关性,对研究农产品与环境因素间同位素分馏和元素累积规律具有一定的参考价值。     

穗肥施用时期对优质稻产量、氮素积累及品质的影响

为了探明优质晚籼稻(Oryza sativa L. subsp. xian)产量和品质协同提升的适宜的穗肥施用时期,采用大田微区¹⁵N示踪技术,以优质晚籼稻Y两优911和野香优莉丝为材料,设置3个穗肥施用时期(D₁：倒4叶期施肥;D₂：倒3叶期施肥;D₃：倒2叶期施肥),研究穗肥施用时期对优质稻产量、籽粒氮素积累及食味品质的影响。结果表明,随着穗肥施用时期的推迟,两个优质晚籼稻品种的产量先升高后降低,在D₂达到最高产量,较D₁、D₃显著增产4.30%～6.39%;籽粒总氮积累量、¹⁵N标记肥料氮素积累量及其占比、¹⁵N标记肥料氮素回收利用率、¹⁵N标记肥料氮素收获指数表现为增加趋势,D₂和D₃较D₁显著增加19.16%～21.26%、32.54%～50.75%、0.91～2.49、12.42～23.34和...     

初级芳香胺的高分辨质谱裂解规律研究

为探究初级芳香胺类化合物的质谱裂解规律,本研究采用超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法,在电喷雾正离子模式下采集数据,根据一、二级质谱离子的精确质荷比推导14种初级芳香胺类化合物可能的裂解途径。结果表明,由于分子结构中存在氨基基团,因此初级芳香胺类化合物极易被质子化,更易形成[M+H]⁺。断裂过程主要发生NH₃中性碎片的丢失,产生[M+H-NH₃]⁺特征碎片离子,在此基础上,氯代苯胺类化合物发生碳正离子重排后,丢失氯原子形成[·M+H-NH₃-Cl]⁺碎片离子。甲氧基取代苯胺类化合物可丢失CH₃O基团产生碎片离子[M+H-NH₃-CH₃O]⁺,或发生碳正离子转移重排至苯甲基,进一步丢失CH₃和CH₃O基团。甲基或甲氧基取代的联苯胺类化合物还会发生CN键断裂形成[M+H-NH]⁺,继而丢失NH₃中性碎片形成[M+H-NH-NH₃]⁺。偶氮苯类化合物中高键能的偶氮键不易断裂,碎片离子主要通过两侧的CN键断裂形成。本研究提出的最佳电离方式和质谱裂解规律为初级芳香胺类化合物的快速鉴定提供了重要依据。     

The sodium-amalgam reduction of soil and fungal humic substances

Two soil humic acids and a “humic acid” synthesized in the laboratory by Stachybotrys chartarum were reduced with Na-amalgam. The reduction products were methylated, separated by preparative gas chromatography and identified by matching their mass and micro-infrared spectra with those of authentic specimsens.Yields of reduction products identified ranged from 2.7 to 4.2% of the initial weights of the humic materials. Major products identified were N-methyl-benzylsulfonamide, methylated phenolic acids, aromatic aldehydes and C₆C₂ - and C₆C₃ - compounds with 0 in the side chains. Since the Na-amalgam reduction of both soil and fungal humic materials produces the same or similar compounds, the method provides little information on the origin of these compounds, that is, whether they are lignin- or flavonoid-derived or synthesized by microorganisms. Compared with oxidative degradation methods, Na-amalgam reduction appears to be inefficient and tells little about the chemical structure of humic acid polymers.     

不同发育期及授粉方式对设施甜瓜中稳定同位素比值变化的影响研究

为探究不同发育期及授粉方式对设施甜瓜稳定同位素比值变化的影响,本研究基于元素分析——稳定同位素比率质谱(EA-IRMS),测定在不同发育期和授粉方式中设施甜瓜的4种稳定同位素比值(δ¹³C、δ¹⁵N、δ¹⁸O和δ²H),采用单因素方差分析法解析激素授粉和中华蜜蜂授粉对甜瓜稳定同位素比值的差异性。结果表明,在相同的种植和环境条件下,自然分馏效应导致设施甜瓜在不同发育时期的同位素差异。在甜瓜发育期间,不同授粉方式设施甜瓜的δ¹³C、δ¹⁵N和δ¹⁸O值较稳定,无显著差异(P>0.05),而在发育30 d时激素授粉与蜜蜂授粉甜瓜的δ²H值分别为-43.63‰和-53.50‰,存在显著差异(P<0.05)。本研究初步揭示了稳定同位素在甜瓜发育过程中以及不同授粉方式下的分馏情况,其中δ²H值可作为甜瓜授粉方式的一项标识性指标,对丰富设施甜瓜溯源体系具有重要意义。