David M. Jaramillo, Lisa M. Bauman, Carlos Henrique Paiva Camisa Nova, Lais Lima, Edzard van Santen
Rationale
Stable isotopes can be useful for tracking diet composition and other physiological processes in ruminants. These techniques rely on the fact that tissues directly reflect the animal's diet. Blood is a dynamic tissue that can be separated into serum, plasma, and red blood cell (RBC) components. Numerous collection tubes for blood are commercially available. No studies have compared the isotopic composition from cattle blood as affected by collection tube. This study compared commercially available serum and plasma tubes and evaluated how they may affect δ13C, δ15N, and C and N concentrations from blood in lactating dairy cattle.
Methods
For plasma and RBC, treatments were five collection tubes containing different anticoagulants: dipotassium ethylenediaminetetraacetic acid (K2EDTA), tripotassium EDTA (K3EDTA), NaF/K oxalate, Li heparin (LiHep), and Na heparin (NaHep). For serum analysis, the three collection tubes were a RedTop (contained no coagulating agent) and TigerTop and Red+CAT, which both contained clot activator and serum separator gel, each made by two different manufacturers. All samples were collected via tail venipuncture in cows. All samples were processed, freeze dried, and analyzed in triplicate for δ13C, δ15N, and C and N.
Conclusions
While mean differences exist on the δ13C and δ15N from plasma and red blood cells, differences were minimal. Clot activator gels in serum tubes did not affect the δ13C and δ15N composition. This study showed that, while isotopic values may differ slightly from different blood collection tubes, these differences were often small, which may have little impact on the interpretation of research results when serum or RBC are analyzed. The isotopic composition of C and N concentrations of serum was not affected by the three tubes used within this study. Researchers will have to understand these differences and decide whether or not these may impact the objectives and the results of a given study.
{"title":"Blood Collection Tube has Minimal Interference on the Carbon and Nitrogen Isotope Composition of Plasma, Red Blood Cells, and Serum in Cow Blood","authors":"David M. Jaramillo, Lisa M. Bauman, Carlos Henrique Paiva Camisa Nova, Lais Lima, Edzard van Santen","doi":"10.1002/rcm.10109","DOIUrl":"10.1002/rcm.10109","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Stable isotopes can be useful for tracking diet composition and other physiological processes in ruminants. These techniques rely on the fact that tissues directly reflect the animal's diet. Blood is a dynamic tissue that can be separated into serum, plasma, and red blood cell (RBC) components. Numerous collection tubes for blood are commercially available. No studies have compared the isotopic composition from cattle blood as affected by collection tube. This study compared commercially available serum and plasma tubes and evaluated how they may affect δ<sup>13</sup>C, δ<sup>15</sup>N, and C and N concentrations from blood in lactating dairy cattle.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>For plasma and RBC, treatments were five collection tubes containing different anticoagulants: dipotassium ethylenediaminetetraacetic acid (K2EDTA), tripotassium EDTA (K3EDTA), NaF/K oxalate, Li heparin (LiHep), and Na heparin (NaHep). For serum analysis, the three collection tubes were a RedTop (contained no coagulating agent) and TigerTop and Red+CAT, which both contained clot activator and serum separator gel, each made by two different manufacturers. All samples were collected via tail venipuncture in cows. All samples were processed, freeze dried, and analyzed in triplicate for δ<sup>13</sup>C, δ<sup>15</sup>N, and C and N.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>While mean differences exist on the δ<sup>13</sup>C and δ<sup>15</sup>N from plasma and red blood cells, differences were minimal. Clot activator gels in serum tubes did not affect the δ<sup>13</sup>C and δ<sup>15</sup>N composition. This study showed that, while isotopic values may differ slightly from different blood collection tubes, these differences were often small, which may have little impact on the interpretation of research results when serum or RBC are analyzed. The isotopic composition of C and N concentrations of serum was not affected by the three tubes used within this study. Researchers will have to understand these differences and decide whether or not these may impact the objectives and the results of a given study.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"39 21","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144688143","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The conventional method for measuring carbon and oxygen isotopes in carbonates involves the reaction of carbonate minerals with phosphoric acid (PPA) to generate CO2, followed by purification and isotopic analysis. During this reaction, a temperature-dependent oxygen isotope acid fractionation factor (AFF) is introduced, as not all oxygen is released in CO2. Although the temperature dependence of AFF has been extensively studied in pure carbonate minerals, little research has been conducted on AFF variations in mixed carbonate minerals with diverse chemical and mineralogical compositions. This study aims to investigate the range of AFF variations in carbonates containing multiple mineral phases.
Methods
Oxygen isotope compositions of CO2 produced from CaCO3-MgCO3 mixed minerals reacting with PPA at 25°C, 50°C, 70°C, and 90°C were analyzed using a GasBench II system coupled with a Thermo Finnigan Delta V Plus isotope ratio mass spectrometer.
Results
The AFF values for CaCO3-MgCO3 mixed minerals fall between those of pure calcite and dolomite, generally aligning with theoretical predictions. Additionally, the fractionation gradient (dδ18O/dT−1) increases with rising mole Mg and dolomite content, indicating a systematic trend in fractionation behavior.
Conclusions
These findings provide a framework for AFF correction based on mole Mg or dolomite content, enhancing the reliability and precision of oxygen isotope measurements in natural impure carbonates.
测量碳酸盐中碳氧同位素的传统方法包括碳酸盐矿物与磷酸（PPA）反应产生二氧化碳，然后进行纯化和同位素分析。在这个反应中，引入了一个温度依赖的氧同位素酸分馏因子（AFF），因为不是所有的氧都以CO2的形式释放。虽然人们对纯碳酸盐矿物中AFF的温度依赖性进行了广泛的研究，但对具有不同化学和矿物组成的混合碳酸盐矿物中AFF变化的研究却很少。本研究旨在探讨含多矿物相碳酸盐中AFF的变化范围。方法采用GasBench II系统和Thermo Finnigan Delta V Plus同位素比值质谱仪，分析CaCO3-MgCO3混合矿物与PPA在25°C、50°C、70°C和90°C反应产生的CO2的氧同位素组成。结果CaCO3-MgCO3混合矿物的AFF值介于纯方解石和白云石之间，与理论预测基本一致。分馏梯度（dδ18O/dT−1）随Mg摩尔数和白云石含量的增加而增大，表明分馏行为有系统的趋势。结论这些发现为基于摩尔Mg或白云石含量的AFF校正提供了框架，提高了天然不纯碳酸盐中氧同位素测量的可靠性和精度。
{"title":"Acid Fractionation Factor of Oxygen Isotopes in Mixed Calcite–Dolomite Samples: Implications for Data Correction","authors":"Linlin Cui, Xu Wang, Lianjun Feng, Xiaomei Zhang","doi":"10.1002/rcm.10108","DOIUrl":"10.1002/rcm.10108","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>The conventional method for measuring carbon and oxygen isotopes in carbonates involves the reaction of carbonate minerals with phosphoric acid (PPA) to generate CO<sub>2</sub>, followed by purification and isotopic analysis. During this reaction, a temperature-dependent oxygen isotope acid fractionation factor (AFF) is introduced, as not all oxygen is released in CO<sub>2</sub>. Although the temperature dependence of AFF has been extensively studied in pure carbonate minerals, little research has been conducted on AFF variations in mixed carbonate minerals with diverse chemical and mineralogical compositions. This study aims to investigate the range of AFF variations in carbonates containing multiple mineral phases.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>Oxygen isotope compositions of CO<sub>2</sub> produced from CaCO<sub>3</sub>-MgCO<sub>3</sub> mixed minerals reacting with PPA at 25°C, 50°C, 70°C, and 90°C were analyzed using a GasBench II system coupled with a Thermo Finnigan Delta V Plus isotope ratio mass spectrometer.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>The AFF values for CaCO<sub>3</sub>-MgCO<sub>3</sub> mixed minerals fall between those of pure calcite and dolomite, generally aligning with theoretical predictions. Additionally, the fractionation gradient (dδ<sup>18</sup>O/dT<sup>−1</sup>) increases with rising mole Mg and dolomite content, indicating a systematic trend in fractionation behavior.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>These findings provide a framework for AFF correction based on mole Mg or dolomite content, enhancing the reliability and precision of oxygen isotope measurements in natural impure carbonates.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"39 21","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144672714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alpha-hemoglobin stabilizing protein (AHSP) is an erythroid-specific protein forming a stable complex with free α-hemoglobin, but not with β-hemoglobin or hemoglobin A (α2β2), thus preventing harmful aggregation of α-hemoglobin during normal erythroid cell development and avoiding its pro-oxidant activity. Although its function has been extensively studied in erythroid cells, its presence in preterm newborns' oral fluid remains unexplored. Given the high susceptibility of preterm infants to hematological disorders, characterizing AHSP in their oral fluid could provide valuable insights into fetal erythropoiesis and its potential role as a biomarker for neonatal anemia and transfusion needs.
Methods
The primary structure of AHSP was determined by high-resolution top-down proteomic analysis using a nano-HPLC–ESI–MS/MS approach on oral fluid samples from preterm newborns. Specimens were collected non-invasively from infants, promptly treated with formic acid, and analyzed with an Orbitrap-based mass spectrometry platform. The intact protein's molecular mass and fragmentation pattern were assessed to determine its primary structure and post-translational modifications. Statistical analysis was performed to explore correlations between AHSP presence and neonatal clinical parameters, including anemia and transfusion needs.
Results
The experimental monoisotopic molecular mass value [M + H+]1+ at m/z 11744.958 ± 0.3 was inconsistent with the protein sequence reported in the literature, and the MS/MS fragmentation pattern was in agreement with the loss of the N-terminal methionine residue followed by Nα-terminal acetylation, a very common post-translational modification, now recognized as having an important role in modulating protein function, localization and protein stability and turnover. The sporadic samples having detectable amounts of AHSP resulted from preterm newborns with severe anemic status, while all were submitted to iron supplementation.
Conclusions
Although the data obtained so far cannot be used for quantitative analysis or statistical evaluation, AHSP appears to stand out as a potential early biomarker of neonatal hematological disorders, highlighting a new perspective for future investigations.
α-血红蛋白稳定蛋白（AHSP）是一种红细胞特异性蛋白，与游离α-血红蛋白形成稳定的复合物，而不与β-血红蛋白或血红蛋白a （α2β2）形成稳定的复合物，从而阻止α-血红蛋白在正常红细胞发育过程中的有害聚集，避免其促氧化活性。尽管其在红系细胞中的功能已被广泛研究，但其在早产儿口腔液中的存在仍未被探索。鉴于早产儿对血液系统疾病的高度易感性，表征其口液中的AHSP可以为胎儿红细胞生成及其作为新生儿贫血和输血需求的生物标志物的潜在作用提供有价值的见解。方法采用纳米高效液相色谱- esi -质谱联用技术对早产儿口腔液进行高分辨率自上而下蛋白质组学分析，确定AHSP的一级结构。从婴儿身上无创采集标本，立即用甲酸处理，并使用基于orbitrap的质谱分析平台进行分析。评估完整蛋白的分子质量和片段模式，以确定其初级结构和翻译后修饰。统计分析探讨AHSP存在与新生儿临床参数（包括贫血和输血需求）之间的相关性。结果实验单同位素分子质量值[M + H+]1+在M /z 11744.958±0.3处与文献报道的蛋白质序列不一致，MS/MS片段模式与n端甲硫氨酸残基缺失和n α端乙酰化一致，这是一种非常常见的翻译后修饰，目前被认为在调节蛋白质功能中起重要作用。定位和蛋白质的稳定性和周转。具有可检测量的AHSP的零星样本来自严重贫血状态的早产新生儿，而所有人都补充了铁。尽管目前获得的数据不能用于定量分析或统计评估，但AHSP作为新生儿血液病的潜在早期生物标志物显得尤为突出，为未来的研究提供了新的视角。
{"title":"Characterization of N-Terminal Acetylated α-Hemoglobin Stabilizing Protein (AHSP) by Top-Down High-Resolution Mass Spectrometry From Human Preterm Newborns Oral Fluid","authors":"Federica Iavarone, Chiara Tirone, Simona Fattore, Davide De Tomaso, Nicoletta Menzella, Giovanni Vento, Alessandra Olianas, Barbara Manconi, Tiziana Cabras, Giulia Guadalupi, Cristina Contini, Mozhgan Boroumand, Claudia Desiderio, Alexandra Muntiu, Antonella Fiorita, Matteo Fraschini, Vassilios Fanos, Gavino Faa, Irene Messana, Massimo Castagnola","doi":"10.1002/rcm.10107","DOIUrl":"10.1002/rcm.10107","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Alpha-hemoglobin stabilizing protein (AHSP) is an erythroid-specific protein forming a stable complex with free α-hemoglobin, but not with β-hemoglobin or hemoglobin A (α<sub>2</sub>β<sub>2</sub>), thus preventing harmful aggregation of α-hemoglobin during normal erythroid cell development and avoiding its pro-oxidant activity. Although its function has been extensively studied in erythroid cells, its presence in preterm newborns' oral fluid remains unexplored. Given the high susceptibility of preterm infants to hematological disorders, characterizing AHSP in their oral fluid could provide valuable insights into fetal erythropoiesis and its potential role as a biomarker for neonatal anemia and transfusion needs.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>The primary structure of AHSP was determined by high-resolution top-down proteomic analysis using a nano-HPLC–ESI–MS/MS approach on oral fluid samples from preterm newborns. Specimens were collected non-invasively from infants, promptly treated with formic acid, and analyzed with an Orbitrap-based mass spectrometry platform. The intact protein's molecular mass and fragmentation pattern were assessed to determine its primary structure and post-translational modifications. Statistical analysis was performed to explore correlations between AHSP presence and neonatal clinical parameters, including anemia and transfusion needs.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>The experimental monoisotopic molecular mass value [M + H<sup>+</sup>]<sup>1+</sup> at <i>m/z</i> 11744.958 ± 0.3 was inconsistent with the protein sequence reported in the literature, and the MS/MS fragmentation pattern was in agreement with the loss of the N-terminal methionine residue followed by Nα-terminal acetylation, a very common post-translational modification, now recognized as having an important role in modulating protein function, localization and protein stability and turnover. The sporadic samples having detectable amounts of AHSP resulted from preterm newborns with severe anemic status, while all were submitted to iron supplementation.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>Although the data obtained so far cannot be used for quantitative analysis or statistical evaluation, AHSP appears to stand out as a potential early biomarker of neonatal hematological disorders, highlighting a new perspective for future investigations.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"39 21","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/rcm.10107","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rania Benazza, Mathieu Fanuel, Hélène Rogniaux, David Ropartz
Rationale: Hemicelluloses are abundant carbohydrate components in plant cell walls. They play a crucial structural role in binding cellulose microfibrils, in addition to other biological functions. Their high structural variability directly influences their biological properties, making it important to establish a structure-function relationship. In the case of galactomannans, this complexity lies in branching, large size, in addition to isomerism, which makes their characterization challenging. In this context, we have demonstrated that cyclic ion mobility spectrometry (IMS), combined with porous graphitic carbon (PGC) chromatography, mass spectrometry (MS), and multistage MS/MS fragmentation (IMSn), is a powerful tool for the detailed elucidation of galactomannan structures.
Methods: In this study, we show that our multistage IMSn sequencing approach, previously validated for homo-linear oligosaccharides (OS), can be successfully applied to hetero-branched hemicelluloses with careful adjustments. Our approach consists of building a database (DB) library of high-resolution IMS (HR-IMS) profiles of disaccharidic and trisaccharidic fragments. Then, the sequence of the oligosaccharide of interest is retrieved by comparing the HR-IMS profile of its disaccharidic and trisaccharide fragments with the profiles from the DB library.
Results: In fact, our IMSn experiments on galactomannan reveal arrival time distribution (ATD) profiles matching with known reference structures, confirming the co-existence of multiple isomers. In addition, we proved that this approach could be improved by incorporating trisaccharidic fragments to our DB library, serving in the characterization of higher degree of polymerization (DP) structures (DP4 in this case).
Conclusions: Overall, this work paves the way for the characterization of even more complex oligosaccharides, which can be potentially used for bio-based material conception.
{"title":"Deciphering Branched Galactomannan Structures via Multistage Ion Mobility MS and MS<sup>n</sup> Fragmentation (Multistage IMS<sup>n</sup>).","authors":"Rania Benazza, Mathieu Fanuel, Hélène Rogniaux, David Ropartz","doi":"10.1002/rcm.10100","DOIUrl":"https://doi.org/10.1002/rcm.10100","url":null,"abstract":"<p><strong>Rationale: </strong>Hemicelluloses are abundant carbohydrate components in plant cell walls. They play a crucial structural role in binding cellulose microfibrils, in addition to other biological functions. Their high structural variability directly influences their biological properties, making it important to establish a structure-function relationship. In the case of galactomannans, this complexity lies in branching, large size, in addition to isomerism, which makes their characterization challenging. In this context, we have demonstrated that cyclic ion mobility spectrometry (IMS), combined with porous graphitic carbon (PGC) chromatography, mass spectrometry (MS), and multistage MS/MS fragmentation (IMS<sup>n</sup>), is a powerful tool for the detailed elucidation of galactomannan structures.</p><p><strong>Methods: </strong>In this study, we show that our multistage IMS<sup>n</sup> sequencing approach, previously validated for homo-linear oligosaccharides (OS), can be successfully applied to hetero-branched hemicelluloses with careful adjustments. Our approach consists of building a database (DB) library of high-resolution IMS (HR-IMS) profiles of disaccharidic and trisaccharidic fragments. Then, the sequence of the oligosaccharide of interest is retrieved by comparing the HR-IMS profile of its disaccharidic and trisaccharide fragments with the profiles from the DB library.</p><p><strong>Results: </strong>In fact, our IMS<sup>n</sup> experiments on galactomannan reveal arrival time distribution (ATD) profiles matching with known reference structures, confirming the co-existence of multiple isomers. In addition, we proved that this approach could be improved by incorporating trisaccharidic fragments to our DB library, serving in the characterization of higher degree of polymerization (DP) structures (DP4 in this case).</p><p><strong>Conclusions: </strong>Overall, this work paves the way for the characterization of even more complex oligosaccharides, which can be potentially used for bio-based material conception.</p>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":" ","pages":"e10100"},"PeriodicalIF":1.8,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144625139","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Brittany D. M. Hodges, JungSoo Kim, Giel Berden, Jonathan Martens, Christopher A. Zarzana
The infrared multiphoton dissociation spectrum of the gas-phase uranyl perchlorate anion ([UO2(ClO4)3]−) was measured. The asymmetric uranyl stretch lies somewhere between 930 and 1030 cm−1, though it could not be deconvoluted from a closely located perchlorate stretching mode. The experimentally measured spectrum was in good agreement with spectra calculated using density functional theory with the B3LYP and TPSSh functionals and Grimme's D3 dispersion corrections with Becke–Johnson damping. The calculations suggest that the asymmetric uranyl stretch lies in the range of 970–980 cm−1, about 20–30 cm−1 higher than for the analogous uranyl trinitrato complex and consistent with perchlorate as a weaker ligand than nitrate. Like the uranyl trinitrato anion, fragmentation of [UO2(ClO4)3]− by collision-induced dissociation resulted in loss of a ClO3• radical to form [UO3(ClO4)2]−. Infrared multiphoton dissociation measurements of [UO3(ClO4)2]− indicate that the structure of the product ion has an O− ligand bound to the uranyl in a T-arrangement and two perchlorate ligands, matching the findings from uranyl nitrato complexes. The uranyl stretch in this complex was slightly separated from the perchlorate modes and was measured at 906 cm−1, slightly higher than for the analogous nitrate complex, again consistent with perchlorate as a weaker ligand than nitrate in the gas phase.
{"title":"Investigation of Uranyl Perchlorate Anion Complexes in the Gas Phase via Infrared Multiphoton Dissociation and Collision-Induced Dissociation","authors":"Brittany D. M. Hodges, JungSoo Kim, Giel Berden, Jonathan Martens, Christopher A. Zarzana","doi":"10.1002/rcm.10106","DOIUrl":"10.1002/rcm.10106","url":null,"abstract":"<div>\u0000 \u0000 <p>The infrared multiphoton dissociation spectrum of the gas-phase uranyl perchlorate anion ([UO<sub>2</sub>(ClO<sub>4</sub>)<sub>3</sub>]<sup>−</sup>) was measured. The asymmetric uranyl stretch lies somewhere between 930 and 1030 cm<sup>−1</sup>, though it could not be deconvoluted from a closely located perchlorate stretching mode. The experimentally measured spectrum was in good agreement with spectra calculated using density functional theory with the B3LYP and TPSSh functionals and Grimme's D3 dispersion corrections with Becke–Johnson damping. The calculations suggest that the asymmetric uranyl stretch lies in the range of 970–980 cm<sup>−1</sup>, about 20–30 cm<sup>−1</sup> higher than for the analogous uranyl trinitrato complex and consistent with perchlorate as a weaker ligand than nitrate. Like the uranyl trinitrato anion, fragmentation of [UO<sub>2</sub>(ClO<sub>4</sub>)<sub>3</sub>]<sup>−</sup> by collision-induced dissociation resulted in loss of a ClO<sub>3</sub><sup>•</sup> radical to form [UO<sub>3</sub>(ClO<sub>4</sub>)<sub>2</sub>]<sup>−</sup>. Infrared multiphoton dissociation measurements of [UO<sub>3</sub>(ClO<sub>4</sub>)<sub>2</sub>]<sup>−</sup> indicate that the structure of the product ion has an O<sup>−</sup> ligand bound to the uranyl in a T-arrangement and two perchlorate ligands, matching the findings from uranyl nitrato complexes. The uranyl stretch in this complex was slightly separated from the perchlorate modes and was measured at 906 cm<sup>−1</sup>, slightly higher than for the analogous nitrate complex, again consistent with perchlorate as a weaker ligand than nitrate in the gas phase.</p>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"39 20","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144615198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This paper presents an in-depth evaluation of the laser diode thermal desorption (LDTD) device interfaced to a mass spectrometer and identifies the critical method parameters to evaluate when developing a new procedure.
Methods
Samples were solvent extracted and spotted in a 96-well plate. In the case of biological fluids, hydrolysis followed by solid phase extraction is required. The solvent in the 96-well plate is evaporated, followed by mass spectrometric analysis (MS) with atmospheric pressure chemical ionization (APCI). Where applicable, the instrument is operated in a data-dependent mode, with a full-scan mass spectrum followed by MS/MS spectra with a total runtime of 18 s per well.
Results
Five key experiments (sample dilution, gas flow, laser ramp, ion saturation/ion suppression, and signal enhancement) were evaluated as critical parameters that could potentially be encountered in method development, and practical solutions are proposed.
Conclusions
Interfacing LDTD with a mass spectrometer allows for rapid screening for many analytes in a wide range of samples, with either minimal or complex sample preparation. Addressing all critical method parameters can aid in creating a sensitive and robust procedure.
{"title":"Critical Method Parameters to Evaluate When Developing a Method Using a Laser Diode Thermal Desorption (LDTD) Coupled to a Mass Spectrometer","authors":"Jonathan Rochon, Serge Auger, Eshwar Jagerdeo","doi":"10.1002/rcm.10104","DOIUrl":"10.1002/rcm.10104","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>This paper presents an in-depth evaluation of the laser diode thermal desorption (LDTD) device interfaced to a mass spectrometer and identifies the critical method parameters to evaluate when developing a new procedure.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>Samples were solvent extracted and spotted in a 96-well plate. In the case of biological fluids, hydrolysis followed by solid phase extraction is required. The solvent in the 96-well plate is evaporated, followed by mass spectrometric analysis (MS) with atmospheric pressure chemical ionization (APCI). Where applicable, the instrument is operated in a data-dependent mode, with a full-scan mass spectrum followed by MS/MS spectra with a total runtime of 18 s per well.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>Five key experiments (sample dilution, gas flow, laser ramp, ion saturation/ion suppression, and signal enhancement) were evaluated as critical parameters that could potentially be encountered in method development, and practical solutions are proposed.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>Interfacing LDTD with a mass spectrometer allows for rapid screening for many analytes in a wide range of samples, with either minimal or complex sample preparation. Addressing all critical method parameters can aid in creating a sensitive and robust procedure.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"39 20","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144589952","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In electrospray ionization mass spectrometry (ESI-MS) systems, two critical challenges persist: (1) under-expanded supersonic jets at the atmospheric pressure interface (API) cause ion losses and reduced transmission efficiency; (2) residual solvents and charged droplets entering vacuum stages lead to contamination and elevated chemical noise, degrading analysis accuracy.
Methods
A dual-channel off-axis ion funnel with a deflection electrode (DC-OFIDE) was developed to address these challenges. This device integrates three core components: an ion drift channel (IDC), an ion funnel channel (IFC), and a deflection electrode. The IDC and IFC are separated by conjoined gaps. Ions within the gas stream emanating from the API are extracted from the IDC via a deflection field, while a retarding axial field prolongs ions' residence time, ensuring efficient transfer to the IFC. This DC-OFIDE features an enlarged entrance aperture (Φ18 mm) to accommodate a multi-capillary interface, enhancing compatibility with high-conductance sample introduction systems.
Results
Compared with the original conventional ion funnel (CIF), the DC-OFIDE achieved a threefold enhancement in caffeine ion intensity and a broader m/z transmission window. It demonstrated robust neutral and droplet suppression, maintaining 80% ion intensity even under tripled serum volume infused. In drug screening of hair samples, baseline noises in drug ion peaks were reduced by 36%–82%, with a quadrupled signal-to-noise ratio improvement observed for 6-monoacetylmorphine.
Conclusions
This DC-OFIDE significantly enhances ion transmission efficiency and chemical noise suppression in ESI-MS, establishing its potential for high-fidelity analysis of complex samples.
{"title":"Dual-Channel Off-Axis Ion Funnel With a Deflection Electrode","authors":"Mengfei Shan, La Chen, Jun Wang, Luhong Wen","doi":"10.1002/rcm.10103","DOIUrl":"10.1002/rcm.10103","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>In electrospray ionization mass spectrometry (ESI-MS) systems, two critical challenges persist: (1) under-expanded supersonic jets at the atmospheric pressure interface (API) cause ion losses and reduced transmission efficiency; (2) residual solvents and charged droplets entering vacuum stages lead to contamination and elevated chemical noise, degrading analysis accuracy.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>A dual-channel off-axis ion funnel with a deflection electrode (DC-OFIDE) was developed to address these challenges. This device integrates three core components: an ion drift channel (IDC), an ion funnel channel (IFC), and a deflection electrode. The IDC and IFC are separated by conjoined gaps. Ions within the gas stream emanating from the API are extracted from the IDC via a deflection field, while a retarding axial field prolongs ions' residence time, ensuring efficient transfer to the IFC. This DC-OFIDE features an enlarged entrance aperture (Φ18 mm) to accommodate a multi-capillary interface, enhancing compatibility with high-conductance sample introduction systems.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>Compared with the original conventional ion funnel (CIF), the DC-OFIDE achieved a threefold enhancement in caffeine ion intensity and a broader <i>m/z</i> transmission window. It demonstrated robust neutral and droplet suppression, maintaining 80% ion intensity even under tripled serum volume infused. In drug screening of hair samples, baseline noises in drug ion peaks were reduced by 36%–82%, with a quadrupled signal-to-noise ratio improvement observed for 6-monoacetylmorphine.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>This DC-OFIDE significantly enhances ion transmission efficiency and chemical noise suppression in ESI-MS, establishing its potential for high-fidelity analysis of complex samples.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"39 20","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144519733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Min Li, Zhuo-chun Wei, Feng-xiang Zhang, Hai-jun Li
Rationale
Semen Hoveniae (SH), known as Zhijuzi in Chinese, is extensively utilized in China for the management of alcoholic liver disease (ALD) due to its recognized detoxification properties. Despite its extensive historical use, the detailed chemical profile and anti-ALD mechanisms of SH remain inadequately understood, significantly restricting its further therapeutic development.
Methods
The chemical constituents of SH were systematically profiled using ultra high-performance liquid chromatography coupled with time-of-flight mass spectrometry (UHPLC-Q-TOF MS). Potential molecular targets of identified compounds were predicted using the SwissTargetPrediction platform. Common targets were subsequently analyzed via Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analysis using the DAVID database. Network pharmacology results were validated by molecular docking.
Results
Seventy-six compounds were identified or tentatively characterized in SH, including 50 flavonoids, 15 saponins, 5 terpenes, 3 alkaloids, 2 phenylpropanoids, and 1 other type, among which seven were unambiguously identified using reference standards. Furthermore, seven potentially novel components were identified. Network pharmacology and molecular docking analyses elucidated the molecular mechanisms underlying SH's therapeutic effects on ALD. Three core molecular targets—AKT1, SRC, and EGFR—were identified. Key pathways closely related to ALD, such as glutathione metabolism and arachidonic acid metabolism, were notably enriched, suggesting their crucial roles in SH's hepatoprotective mechanisms. Molecular docking studies confirmed strong binding affinities (binding energies lower than −5.0 kcal/mol) between six active compounds (laricetrin, apigenin, quercetin, kaempferol, myricetin, and syringetin) and the three core targets (AKT1, SRC, and EGFR).
Conclusions
This study comprehensively characterizes the chemical compositions of SH and elucidates its potential mechanisms against ALD. These findings substantiate the hepatoprotective potential of SH, providing a solid scientific foundation for its traditional use and promoting the development of novel therapeutic approaches for ALD.
{"title":"Phytochemical Analysis of Semen Hoveniae and Its Potential Mechanism Against Alcoholic Liver Disease via an Integrated Approach Combining UHPLC-Q-TOF MS, Network Pharmacology, and Molecular Docking","authors":"Min Li, Zhuo-chun Wei, Feng-xiang Zhang, Hai-jun Li","doi":"10.1002/rcm.10097","DOIUrl":"10.1002/rcm.10097","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Semen Hoveniae (SH), known as Zhijuzi in Chinese, is extensively utilized in China for the management of alcoholic liver disease (ALD) due to its recognized detoxification properties. Despite its extensive historical use, the detailed chemical profile and anti-ALD mechanisms of SH remain inadequately understood, significantly restricting its further therapeutic development.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>The chemical constituents of SH were systematically profiled using ultra high-performance liquid chromatography coupled with time-of-flight mass spectrometry (UHPLC-Q-TOF MS). Potential molecular targets of identified compounds were predicted using the SwissTargetPrediction platform. Common targets were subsequently analyzed via Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analysis using the DAVID database. Network pharmacology results were validated by molecular docking.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>Seventy-six compounds were identified or tentatively characterized in SH, including 50 flavonoids, 15 saponins, 5 terpenes, 3 alkaloids, 2 phenylpropanoids, and 1 other type, among which seven were unambiguously identified using reference standards. Furthermore, seven potentially novel components were identified. Network pharmacology and molecular docking analyses elucidated the molecular mechanisms underlying SH's therapeutic effects on ALD. Three core molecular targets—AKT1, SRC, and EGFR—were identified. Key pathways closely related to ALD, such as glutathione metabolism and arachidonic acid metabolism, were notably enriched, suggesting their crucial roles in SH's hepatoprotective mechanisms. Molecular docking studies confirmed strong binding affinities (binding energies lower than −5.0 kcal/mol) between six active compounds (laricetrin, apigenin, quercetin, kaempferol, myricetin, and syringetin) and the three core targets (AKT1, SRC, and EGFR).</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>This study comprehensively characterizes the chemical compositions of SH and elucidates its potential mechanisms against ALD. These findings substantiate the hepatoprotective potential of SH, providing a solid scientific foundation for its traditional use and promoting the development of novel therapeutic approaches for ALD.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"39 20","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144519938","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Quercetin is an example of a pentahydroxylated flavonol compound studied extensively due to its excellent biological activity (e.g., antioxidant, antiviral, and antimicrobial). The antioxidant properties of flavonoids are influenced by the arrangement of the substituents around the molecule, a phenomenon known as the structure–activity relationship (SAR). SAR studies the relationship between compounds' structural characteristics and their biological activity in drug design.
Methods
Quercetin was silylated with MTBSTFA using a semiautomated flow system, and the order in which hydroxyl groups were silylated was used to derive the sequential reactivity of quercetin.
Results
The collision-induced dissociation MS/MS fragmentation of the precursor ion of quercetin is influenced by the electrospray ionization (+ and − modes) and an increase in collision energy (CE). Structure elucidation with in-depth high-resolution tandem mass spectrometric analysis revealed that silylation primarily occurs at A7 and is sequentially followed by B3′, B4′, C3, and A5.
Conclusions
Retro-Dials Alder cleavage of the C-ring plays a significant role in the MS/MS fragmentations of silylated quercetin, maintaining the integrity of the fragment ions and subsequently allowing tracking of the position of the silyl group.
{"title":"Unveiling Flavonoid Reactivity: A High-Resolution Mass Spectrometry Journey Through the Silylation of Quercetin","authors":"Thabang Bernette Ncongwane, Ntakadzeni Edwin Madala, Derek Tantoh Ndinteh, Elize Smit","doi":"10.1002/rcm.10101","DOIUrl":"10.1002/rcm.10101","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Quercetin is an example of a pentahydroxylated flavonol compound studied extensively due to its excellent biological activity (e.g., antioxidant, antiviral, and antimicrobial). The antioxidant properties of flavonoids are influenced by the arrangement of the substituents around the molecule, a phenomenon known as the structure–activity relationship (SAR). SAR studies the relationship between compounds' structural characteristics and their biological activity in drug design.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>Quercetin was silylated with MTBSTFA using a semiautomated flow system, and the order in which hydroxyl groups were silylated was used to derive the sequential reactivity of quercetin.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>The collision-induced dissociation MS/MS fragmentation of the precursor ion of quercetin is influenced by the electrospray ionization (+ and − modes) and an increase in collision energy (<span>CE</span>). Structure elucidation with in-depth high-resolution tandem mass spectrometric analysis revealed that silylation primarily occurs at A7 and is sequentially followed by B3′, B4′, C3, and A5.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>Retro-Dials Alder cleavage of the C-ring plays a significant role in the MS/MS fragmentations of silylated quercetin, maintaining the integrity of the fragment ions and subsequently allowing tracking of the position of the silyl group.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"39 20","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/rcm.10101","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144519732","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tetrandrine is a bisbenzylisoquinoline alkaloid with diverse pharmacological activities and faces critical pharmaceutical challenges due to its inherent photolability under environmental stressors. Despite its therapeutic potential, systematic investigations into its photodegradation mechanisms and impurity profiling remain conspicuously absent, posing risks to drug quality control and regulatory compliance.
Methods
Structural elucidation of degradation products (DPs) was achieved through advanced analytical techniques, including high-resolution mass spectrometry (HRMS), 1D/2D nuclear magnetic resonance (NMR) spectroscopy, and comparative fragmentation analysis. Key degradation drivers—including light intensity, atmospheric composition, aqueous content, and pH extremes—were quantitatively assessed through designed single-variable experiments.
Results
Seven photodegradants (DP-1 to DP-7) were structurally characterized, including two quaternary ammonium enantiomers (DP-2 and DP-3) from N-oxidation, a benzophenone derivative (DP-4) via benzylic C–H oxidation, and macrocyclic cleavage products (DP-1 and DP-7) through oxidative C–C bond scission. Degradation exhibited irradiance threshold behavior (> 10 mW cm−2 for 80% conversion) and oxygen dependency (R2 = 0.98). Alkaline conditions (0.1 M NaOH) induced complete degradation within 0.5 h through ·OH-mediated radical chain reactions, while aqueous media (40% H2O) accelerated hydrolysis.
Conclusions
This study provides the first mechanistic atlas of tetrandrine's photodegradation, identifying three dominant pathways: oxidative skeletal modification, oxidative ring-opening, and radical-mediated C–N cleavage. This study establishes a robust framework for the impurity analysis of natural product-derived drugs and provides actionable guidelines for stabilizing tetrandrine during manufacturing and storage.
{"title":"Impurity Profiling and Mechanistic Investigation of the Photochemical Degradation of Tetrandrine","authors":"Jinmei Tan, Feng Wang, Ruihan Zheng, Weiran Yang, Jinlong Chen","doi":"10.1002/rcm.10102","DOIUrl":"10.1002/rcm.10102","url":null,"abstract":"<div>\u0000 \u0000 \u0000 <section>\u0000 \u0000 <h3> Rationale</h3>\u0000 \u0000 <p>Tetrandrine is a bisbenzylisoquinoline alkaloid with diverse pharmacological activities and faces critical pharmaceutical challenges due to its inherent photolability under environmental stressors. Despite its therapeutic potential, systematic investigations into its photodegradation mechanisms and impurity profiling remain conspicuously absent, posing risks to drug quality control and regulatory compliance.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Methods</h3>\u0000 \u0000 <p>Structural elucidation of degradation products (DPs) was achieved through advanced analytical techniques, including high-resolution mass spectrometry (HRMS), 1D/2D nuclear magnetic resonance (NMR) spectroscopy, and comparative fragmentation analysis. Key degradation drivers—including light intensity, atmospheric composition, aqueous content, and pH extremes—were quantitatively assessed through designed single-variable experiments.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Results</h3>\u0000 \u0000 <p>Seven photodegradants (DP-1 to DP-7) were structurally characterized, including two quaternary ammonium enantiomers (DP-2 and DP-3) from N-oxidation, a benzophenone derivative (DP-4) via benzylic C–H oxidation, and macrocyclic cleavage products (DP-1 and DP-7) through oxidative C–C bond scission. Degradation exhibited irradiance threshold behavior (> 10 mW cm<sup>−2</sup> for 80% conversion) and oxygen dependency (<i>R</i><sup>2</sup> = 0.98). Alkaline conditions (0.1 M NaOH) induced complete degradation within 0.5 h through ·OH-mediated radical chain reactions, while aqueous media (40% H<sub>2</sub>O) accelerated hydrolysis.</p>\u0000 </section>\u0000 \u0000 <section>\u0000 \u0000 <h3> Conclusions</h3>\u0000 \u0000 <p>This study provides the first mechanistic atlas of tetrandrine's photodegradation, identifying three dominant pathways: oxidative skeletal modification, oxidative ring-opening, and radical-mediated C–N cleavage. This study establishes a robust framework for the impurity analysis of natural product-derived drugs and provides actionable guidelines for stabilizing tetrandrine during manufacturing and storage.</p>\u0000 </section>\u0000 </div>","PeriodicalId":225,"journal":{"name":"Rapid Communications in Mass Spectrometry","volume":"39 20","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144519741","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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