Comparison of Open Digestion Methods for the Determination of Rare Earth Elements in Plant Samples by ICP-MS

An analytical procedure for the reliable determination of rare earth elements (REEs) in plant samples by inductively coupled plasma-mass spectrometry (ICP-MS) was developed. The influence of the main matrix elements was investigated first. It was established that moderate amounts (0.1–1.0%) of dissolved solids decreased the REEs signals significantly. Internal standardization with indium proved to be useful for obtaining correct results. Various digestion procedures were next applied to converting various solid plant samples to aqueous solution, namely dry-ashing, dry-ashing including a hydrofluoric acid (HF) step, and wet digestion using hydrogen peroxide (H₂O₂) and nitric acid (HNO₃). Obtained results showed that the simple dry-ashing procedure was sufficient for plants. A certified reference material (BCR-670, aquatic plant) was used to validate the accuracy of the method. Relative standard deviations varied from 1% (holmium, gadolinium) to 4% (europium). Detection limits between 13 (lanthanum) and 0.02 ng L^?1 (lutetium) were achieved.     

Boron fertilization and liming for Eucalyptus urograndis cropped on sandy arenosol of Brazilian pampa

Boron (B) requirement and its interaction with liming for eucalyptus plantations in sandy soils of Brazilian Pampa are poorly understood. Aiming to diminish this gap, seedlings of Eucalyptus urograndis were grown in pots with Arenosol fertilized with B at rates 0.0, 1.0, 2.5, 5.0 and 10.0 mg B dm^?3, with and without liming. Results of shoot and root dry matter and stem diameter did not evidence the necessity of B fertilization. With the exception of the 1.0 mg B dm^?3+lime, all other B-fertilized treatments promoted visual symptoms of toxicity, which were partially mitigated by liming. Liming exacerbated the B loss by leaching, but after five months, limed soils had higher content of available B and their plants had higher B concentration in shoots and roots. For our conditions, application of ≥2.5 mg B dm^?3 can cause serious toxic injuries to plants and enlarge dramatically the B losses leaching.     

城市污泥生物干化过程的有机质转化与产水规律

城市污泥生物干化期间,微生物降解有机质产生水分,影响最终的干化效率。该研究采用自动控制技术进行城市污泥生物干化,测定了干化过程不同阶段的有机质组分转化,并通过水分平衡方程计算了污泥干化过程中堆体的产水量,研究了干化过程的产水规律。结果表明,第1次高温期是有机质降解最快的时期,日均降幅达6.68 kg/(t·d);生物干化完成时,有机质中的易降解有机质(易水解物和脂类)比例由49.91%降至37.94%,腐殖酸的比例由39.34%升至54.14%;堆体总产水量为61.80 kg/t,产水速率排序为:第1次高温期升温期第2次高温期降温期,其中第1次高温期日均产水速率达6.51 kg/(t·d),该时期也是有机质降解速率最大的时期。整个生物干化过程中,堆体产水量与蒸发量的比值为1:6.7,产水量远低于蒸发量,各阶段的产水量变化可为优化生物干化工艺提供参考。     

基于量子化学的木质素热裂解中环类化合物形成的理论及实验研究

利用傅里叶变换红外光谱仪分析木质素微观结构,应用裂解气相色谱-质谱联用技术(Py-GC/MS)进行木质素的热裂解产物分析。研究结果表明:300和400℃时没有检测到多环芳烃等复杂结构,可见在该温度下,裂解产物并未发生二次缩合作用;在800℃下,苯和甲苯的GC含量增加,苯酚基本保持不变,并开始出现多环芳烃化合物。以密度泛函理论B3LYP/6-31G(d,p)为基础对木质素的裂解反应过程进行了分子动力学模拟研究,对比分析实验数据和模拟数据,推断出木质素热裂解中环类化合物的形成演化机理:300~400℃主要发生CC键的断裂和羟基脱落(路径R5-1)以及C1—Cα键的断裂(路径R5-2);400~800℃发生的C1—Cα键断裂反应(路径R4-1),苯环上甲氧基官能团脱去反应(路径R4-4)和苯环上甲氧基均裂(路径R5-3);与苯环上甲氧基官能团均裂反应(路径R4-3)相比,苯环C1—Cα断裂反应(路径R4-2)发生的可能性更大;路径2、路径3和路径5的产物量均在800℃左右达到最大,其产物分别为联苯、菲以及芘。     

杭菊栽培品种小黄菊鲜花和制成品香气组成分析

以SDE法提取小黄菊鲜花和制成品的香精油,用GC MS进行定性定量分析,发现: (1)从鲜花和制成品中分别检出76和88种化合物,主要成分是单萜、倍半萜及含氧衍生物;(2)鲜花和制成品中共有成分62种,其中含量较高的有桉叶醇、樟脑、马鞭草烯醇乙酸酯、六甲基苯等;(3)在鲜花中的含量至少十倍于制成品的组分有莰烯、β 水芹烯、α 水芹烯、(E) 罗勒烯、(Z) 罗勒烯、二环［222］辛 5 烯 2 酮、别罗勒烯、D 马鞭草烯酮、藏花醛、六甲基苯;(4)鲜花精油中有14种组分是制成品精油中没有的,有α 宁烯醛、α 小茴香烯、古巴烯等;(5)制成品精油中的含量远高于鲜花中含量的组分有6 甲基 5 庚烯 2 酮、α 姜烯、β 倍半水芹烯、α 柠檬醛、棕榈酸、α 姜黄烯、反 柠檬烯氧化物、α 没药醇等;(6)制成品中特有组分有26种,有麝香草酚、苯乙醛、α 萜品醇、γ 毕澄茄烯等。研究结果揭示了小黄菊香气特征,可供栽培、加工和品审时参考。     

Vitamin C,B5, and B6 contents of segregating potato populations detected by GC‐MS: a method facilitating breeding potatoes with improved vitamin content

Vitamin C, B5, and B6 contents of potato tubers were measured by gas chromatography‐mass spectrometry (GC‐MS). Two diploid potato populations derived from two different crosses were analyzed. Plants were grown at two locations under different environmental conditions. Measurements of vitamin content of tubers showed high variation in both populations. A weak correlation was found between the vitamin concentrations of tubers harvested at the two locations. Correlations between the mean values of vitamins in field‐grown tubers and in different tissues derived from in vitro or greenhouse‐grown potato plants were also determined. A very high correlation between the vitamin content of field‐ and greenhouse‐grown tubers, and between field‐grown tubers and sink leaves of greenhouse‐grown plants was detected. This finding can facilitate breeding by preselection of individuals with improved vitamin content under greenhouse conditions at their early developmental stage.     

超高效液相色谱-串联质谱法测定猪肉中非甾体抗炎药残留量

研究建立了猪肉中美洛昔康、氟尼辛、卡洛芬和托芬那酸四种非甾体抗炎药残留量的超高效液相色谱-串联质谱（UPLC-MS/MS）检测方法。样品中残留的药物经乙腈提取,提取液浓缩后用乙腈-0.1%甲酸水溶液溶解,正己烷液-液分配净化,最后采用电喷雾串联质谱仪在正离子多反应监测扫描（MRM）模式下进行测定,基质外标法定量。四种药物在各自的线性范围内,线性关系良好,相关系数均为0.999。对猪肉中美洛昔康、氟尼辛、卡洛芬和托芬那酸在定量限（LOQ）、2.5 倍定量限（2.5 LOQ）和5 倍定量限（5 LOQ）三个添加浓度水平下的回收率进行测定,其平均回收率在在72.1%和87.3% 之间,相对标准偏差在2.8%和6.7%之间。美洛昔康、氟尼辛、卡洛芬和托芬那酸的定量限(S/N≥10)分别为1.6、1.6、80 和8.0 μg/kg。该方法不使用固相萃取柱,简化了操作步骤,节约了检测成本,灵敏度、准确度和精密度均符合多残留检测技术的要求,可为猪肉中非甾体抗炎药残留量的测定提供技术支持。     

奶牛临床和亚临床酮病的血浆代谢组学研究

【目的】基于代谢组学的气相色谱(GC)/质谱(MS)联用技术分析临床酮病、亚临床酮病和健康的奶牛血浆代谢谱,观察奶牛体内代谢产物的变化,寻找内源性代谢分子标记物,用于发现奶牛临床和亚临床酮病的早期诊断及病情进展的特征生物标志物,并阐明该病发病机制。【方法】收集临床酮病奶牛血样24例,亚临床酮病奶牛33例,健康对照组奶牛23例,静脉采集试验奶牛血液,分离血浆,检测其β-羟丁酸、血糖等生化指标。将血浆样品预处理后,运用GC/MS联用技术检测各组奶牛血浆代谢产物,利用质谱数据库对其进行鉴定。采用主成分分析（principal component analysis, PCA）和偏最小二乘判别分析法（partial least squares discriminant analysis, PLS-DA）等多元统计方法对临床酮病组、亚临床酮病组和健康对照组奶牛检测数据进行模式识别分析。通过PLS-DA方法建立疾病诊断模型后,筛选潜在的疾病生物标记物。【结果】 以80例奶牛血浆样品为分析对象,研究建立了内源性代谢物谱的GC/MS分析方法,并利用NIST（2008）商业质谱数据库对检测到的代谢物进行快速鉴定,共检测出267个变量。将代谢组数据导入SIMCA-P软件进行主成分分析和偏最小二乘法判别分析,代谢组数据可将患病组与健康组分别聚类区分,并且寻找到组间种类无差别代谢物为40种。结果显示与对照组相比,临床和亚临床酮病的差异代谢物均为32个,临床酮病与亚临床酮病组相比有13个差异代谢物。通过查找KEGG数据库,对代谢物进行分析,这些代谢物主要与氨基酸代谢、脂肪代谢和碳水化合物代谢等能量代谢途径相关。【结论】基于代谢组学的GC/MS技术对酮病奶牛血浆进行检测,并结合多元统计分析,共在临床、亚临床酮病和健康组之间发现40种代谢物（主要为脂肪酸,氨基酸和碳水化合物等物质）。证明奶牛血浆样品的GC/MS代谢谱可以有效地对临床酮病组、亚临床酮病组与健康对照组进行区分。该结果也进一步证明了利用代谢组学技术,在一定程度上可以揭示奶牛临床和亚临床酮病的发生和发展变化,而这些对组间分类有贡献的差异代谢物可能是奶牛酮病诊断的潜在代谢标记物和客观指标。通过研究可以发现奶牛临床和亚临床酮病的发生和发展过程中,其血浆内的部分代谢物的代谢模式和代谢途径发生了改变。此外,新的潜在的代谢物也为奶牛酮病的诊断和预防提供了一定的新思路。     

三角帆蚌内脏团不同部位插核育珠对珍珠囊形成的影响

对三角帆蚌(Hyriopsis comingii)内脏团不同部位进行插核, 研究各组珍珠囊形成、结构以及珍珠质沉积的差异, 从而确定出有利于珍珠形成的插核核位。实验选取内脏团5个部位(I: 斧足内脏团前端; II: 斧足内脏团中部; III: 近生殖腺部; IV: 近胃部; V: 近肾部)进行插核, 并分别在插核后第20、50、90、150 天(thd)采集内脏团插核部位进行组织固定, 利用石蜡切片、HE染色研究不同插核部位珍珠囊结构及珍珠质沉积情况。结果表明: (1) 插核施术后20 d, II组插核位点最早形成单层低柱状上皮细胞, 为次生珍珠囊; (2) 插核施术后50 d, I、II、III组均形成了珍珠囊上皮细胞, 而IV、V组插核位点未出现类似的柱状细胞。其中II、III组珍珠囊上皮细胞前端含有大量体积较大的颗粒物; (3) 插核施术后90 d, I、III组珍珠囊细胞间出现大量细胞间隙, I、II组珍珠囊表皮细胞具有多核现象的细胞数量增多, 且II、III组上皮细胞中颗粒物数量增多, 而IV、V组插核位点形成了复层扁平上皮细胞; (4) 插核施术后150 d, I、III组珍珠囊内表皮细胞间隙变少。II组珍珠囊上皮细胞游离端存在大量的微绒毛, 其与III组相似, 珍珠囊上皮细胞细胞核明显增多, 颗粒物减少。该时期, IV组在插核位点上形成了不连续的低柱细胞、V组插核位点仍未出现珍珠囊细胞。(5) 三角帆蚌在插核术后养殖150 d后, I、II、III组珠核表面出现明显的珍珠质沉积, II、III组珍珠质沉积均匀, I组不均匀, 并且II组沉积的珍珠层厚度(0.85 mm±0.06 mm)显著大于I、III组(P<0.05; 0.62 mm±0.07 mm, 0.56 mm±0.03 mm), 而IV、V组珠核表面没有珍珠质沉积。研究结果表明, 三角帆蚌内脏团不同插核部位珍珠囊上皮细胞的形成存在明显差异, 斧足–内脏团前端、斧足–内脏团中部以及近生殖腺部插核能形成完整的珍珠囊结构并沉积珍珠质, 其中斧足–内脏团中部插核更有利于珍珠的生长。本研究旨为淡水珍珠贝的内脏团育珠研究工作提供实践基础和理论依据。