Добірка наукової літератури з теми "Alkali-reactivity of CDW component"

Оформте джерело за APA, MLA, Chicago, Harvard та іншими стилями

Оберіть тип джерела:

Ознайомтеся зі списками актуальних статей, книг, дисертацій, тез та інших наукових джерел на тему "Alkali-reactivity of CDW component".

Біля кожної праці в переліку літератури доступна кнопка «Додати до бібліографії». Скористайтеся нею – і ми автоматично оформимо бібліографічне посилання на обрану працю в потрібному вам стилі цитування: APA, MLA, «Гарвард», «Чикаго», «Ванкувер» тощо.

Також ви можете завантажити повний текст наукової публікації у форматі «.pdf» та прочитати онлайн анотацію до роботи, якщо відповідні параметри наявні в метаданих.

Статті в журналах з теми "Alkali-reactivity of CDW component"

1

Yu, Esther Dawen, Alba Grifoni, Aaron Sutherland, Hannah Voic, Eric Wang, April Frazier, Natalia Jimenez-Truque, et al. "Balanced Cellular and Humoral Immune Responses Targeting Multiple Antigens in Adults Receiving a Quadrivalent Inactivated Influenza Vaccine." Vaccines 9, no. 5 (April 23, 2021): 426. http://dx.doi.org/10.3390/vaccines9050426.

Повний текст джерела
Анотація:
The role of T cell immunity has been acknowledged in recent vaccine development and evaluation. We tested the humoral and cellular immune responses to Flucelvax®, a quadrivalent inactivated seasonal influenza vaccine containing two influenza A (H1N1 Singapore/GP1908/2015 IVR-180 and H3N2 North Carolina/04/2016) and two influenza B (Iowa/06/2017 and Singapore/INFTT-16-0610/2016) virus strains, using peripheral blood mononuclear cells stimulated by pools of peptides overlapping all the individual influenza viral protein components. Baseline reactivity was detected against all four strains both at the level of CD4 and CD8 responses and targeting different proteins. CD4 T cell reactivity was mostly directed to HA/NA proteins in influenza B strains, and NP/M1/M2/NS1/NEP proteins in the case of the Influenza A strains. CD8 responses to both influenza A and B viruses preferentially targeted the more conserved core viral proteins. Following vaccination, both CD4 and CD8 responses against the various influenza antigens were increased in day 15 to day 91 post vaccination period, and maintained a Th1 polarized profile. Importantly, no vaccine interference was detected, with the increased responses balanced across all four included viral strains for both CD4 and CD8 T cells, and targeting HA and multiple additional viral antigens.
Стилі APA, Harvard, Vancouver, ISO та ін.
2

Murphy, Juneann W., Fredda Schafer, Arturo Casadevall, and Adekunle Adesina. "Antigen-Induced Protective and Nonprotective Cell-Mediated Immune Components against Cryptococcus neoformans." Infection and Immunity 66, no. 6 (June 1, 1998): 2632–39. http://dx.doi.org/10.1128/iai.66.6.2632-2639.1998.

Повний текст джерела
Анотація:
ABSTRACT Mice immunized with two different cryptococcal antigen preparations, one a soluble culture filtrate antigen (CneF) in complete Freund’s adjuvant (CFA) and the other heat-killed Cryptococcus neoformans cells (HKC), develop two different profiles of activated T cells. CneF-CFA induces CD4+ T cells responsible for delayed-type hypersensitivity (DTH) reactivity and for amplification of the anticryptococcal DTH response, whereas HKC induce CD4+ and CD8+ T cells involved in anticryptococcal DTH reactivity and activated T cells which directly kill C. neoformans cells. The main purpose of this study was to assess the level of protection afforded by each of the two different T-cell profiles against challenge with viable C. neoformans cells, thereby identifying which activated T-cell profile provides better protection. CBA/J mice immunized with CneF-CFA had significantly better protective responses, based on better clearance of C. neoformans from tissues, on longer survival times, and on fewer and smaller lesions in the brain, than HKC-immunized mice or control mice similarly infected with C. neoformans. Both immunization protocols induced an anticryptococcal DTH response, but neither induced serum antibodies to glucuronoxylmannan, so the protection observed in the CneF-CFA immunized mice was due to the activated T-cell profile induced by that protocol. HKC-immunized mice, which displayed no greater protection than controls, did not have the amplifier cells. Based on our findings, we propose that the protective anticryptococcal T cells are the CD4+ T cells which have been shown to be responsible for DTH reactivity and/or the CD4+ T cells which amplify the DTH response and which have been previously shown to produce high levels of gamma interferon and interleukin 2. Our results imply that there are protective and nonprotective cell-mediated immune responses and highlight the complexity of the immune response to C. neoformans antigens.
Стилі APA, Harvard, Vancouver, ISO та ін.
3

Bottino, C., G. Tambussi, S. Ferrini, E. Ciccone, P. Varese, M. C. Mingari, L. Moretta, and A. Moretta. "Two subsets of human T lymphocytes expressing gamma/delta antigen receptor are identifiable by monoclonal antibodies directed to two distinct molecular forms of the receptor." Journal of Experimental Medicine 168, no. 2 (August 1, 1988): 491–505. http://dx.doi.org/10.1084/jem.168.2.491.

Повний текст джерела
Анотація:
Two mAbs directed to the TCR-gamma/delta were analyzed for their pattern of reactivity with CD3+WT31- cell populations or clones. In normal individuals, the BB3 mAb reacted with approximately 2/3 of peripheral blood CD3+WT31- lymphocytes, whereas delta-TCS-1 stained approximately 1/3 of such cells. In addition, the sum of the percentages of BB3+ and delta-TCS-1+ cells approximated the percentages of peripheral blood CD3+WT31- lymphocytes in seven normal donors tested. Also, in peripheral blood-derived polyclonal CD3+WT31- populations, cultured in IL-2, cells reacting with one or another mAb accounted for the whole cell population. On the other hand, only delta-TCS-1-reactive cells, but not BB3+ cells, could be detected in unfractionated as well as in CD4-8-thymocyte populations. Analysis of peripheral blood-derived CD3+WT31- clones showed that 70% of 72 clones analyzed reacted with BB3 mAb, but not with delta-TCS-1 mAb. On the other hand, delta-TCS-1 mAb stained the remaining BB3- clones. Five clones expressing medium-low amounts of CD8 antigen were BB3- delta-TCS-1+. Both types of clones lysed the Fc gamma receptor-bearing P815 target cell in the presence of anti-CD3 mAb (but not of mAb directed against HLA-DR, CD7 molecules, or TCR-alpha/beta). In this cytolytic assay, BB3 mAb induced target cell lysis only by BB3+ clones, whereas delta-TCS-1 mAb was effective only with delta-TCS-1+ clones. The CD3-associated surface molecules expressed by BB3+ or delta-TCS-1+ clones were analyzed after cell surface iodination and immunoprecipitation with the corresponding anti-TCR mAb or with anti-CD3 mAb (in digitonin-containing buffer). In SDS-PAGE, molecules immunoprecipitated from 13 BB3+ clones displayed, under nonreducing conditions, a molecular weight of 80 kD (in some cases, a minor 38-kD band could be detected). Under reducing conditions, two major components of 44 and 41 kD (and a minor component of 38 kD) were detected. On the other hand, TCR molecules immunoprecipitated from 11 different delta-TCS-1+ clones appeared as a diffuse band of 41-44 kD, both under reducing and nonreducing conditions (under non-reducing condition, an additional 38-kD band was present). Therefore, BB3+ cells express a disulphide-linked form of TCR-gamma/delta whereas delta-TCS-1+ cells express a non-disulphide-linked form.(ABSTRACT TRUNCATED AT 400 WORDS)
Стилі APA, Harvard, Vancouver, ISO та ін.
4

Garssen, J., H. Van Loveren, K. Kato, and P. W. Askenase. "Antigen receptors on Thy-1+ CD3- CS-initiating cell. In vitro desensitization with hapten-amino acid or hapten-Ficoll conjugates, versus hapten-protein conjugates, suggests different antigen receptors on the immune cells that mediate the early and late components of murine contact sensitivity." Journal of Immunology 153, no. 1 (July 1, 1994): 32–44. http://dx.doi.org/10.4049/jimmunol.153.1.32.

Повний текст джерела
Анотація:
Abstract In murine contact sensitivity (CS) models, cutaneous immune responses are caused by the activity of two different Ag-specific Thy-1+ CD5+ cells. These two different cell subsets act in an obligate sequence to mediate separate early and late components of CS that are accompanied respectively by skin swelling responses at 2 and 24 h after local challenge with the hapten. The early-acting CS-initiating cells are not conventional T cells inasmuch as they are surface negative for CD4, CD8, and CD3. In contrast to this non-MHC-restricted, CS-initiating cell, the classical late-acting CS effector T cell that is recruited locally is CD3+, CD4+, CD8-, and is MHC-restricted. In our study, we have conducted experiments in which a mixture of immune CS-initiating and CS-effector cells were desensitized by incubation in vitro at 37 degrees C with various hapten-amino acid and hapten-carrier conjugates, before i.v. transfer and subsequent ear challenge of normal recipient mice. Desensitization was achieved with multivalent complexes of the relevant hapten conjugated to a variety of unrelated nonmurine carrier proteins, and, in some instances, with monovalent hapten conjugated to amino acid. Because the CS-mediating cells were desensitized in a hapten-specific manner, but these same cells transferred CS reactivity that was hapten/MHC-class II specific, it was suggested previously that these results argued in favor of a two-receptor model for T cell recognition of Ag, one receptor for hapten and the other for MHC. Our study suggests that these findings need to be reinterpreted because CS reactions are mediated by two different, Thy-1+ Ag-specific cells that act in an obligate sequence. Our data suggest that the late-acting Ag/MHC-specific CS-effector T cells are not hapten-specific. In fact, desensitization with hapten alone has a locus of action solely on the Ag receptor of the first-acting Thy-1+ CS-initiating cells--which are therefore truly hapten-specific and which are required for local recruitment of the Ag/MHC-specific late CS-effector T cells.
Стилі APA, Harvard, Vancouver, ISO та ін.
5

Rosat, Jean-Pierre, Ethan P. Grant, Evan M. Beckman, Christopher C. Dascher, Peter A. Sieling, Daphney Frederique, Robert L. Modlin, Steven A. Porcelli, Stephen T. Furlong та Michael B. Brenner. "CD1-Restricted Microbial Lipid Antigen-Specific Recognition Found in the CD8+ αβ T Cell Pool". Journal of Immunology 162, № 1 (1 січня 1999): 366–71. http://dx.doi.org/10.4049/jimmunol.162.1.366.

Повний текст джерела
Анотація:
Abstract It is generally accepted that TCR αβ+ CD8+ T cells recognize immunogenic peptides bound to MHC-encoded class I molecules. This recognition is a major component of the cellular response mediating immune protection and recovery from viral infections and from certain intracellular bacterial infections. Here, we report two human CD8+ TCR αβ+ T cell lines specific for Mycobacterium tuberculosis Ags presented in the context of CD1a or CD1c Ag-presenting molecules. These T cells recognize lipid Ags and display cytotoxicity as well as strong Th cell type I cytokine responses. By extending presentation by the CD1 system to the major TCR αβ+ CD8+ T cell pool, this system gains wider applicability beyond the double negative subset of T cells previously shown to have this reactivity. This implies that previous assumptions about the role of CD8+ T cells in microbial immunity may require revision as the relative proportions of CD1-restricted and MHC class I-restricted CD8+ T cells are further defined.
Стилі APA, Harvard, Vancouver, ISO та ін.
6

Su, Charles, Shoichi Iida, Toyofumi Abe, and Robert Fairchild. "Endogenous memory CD8 T cells exhibit increased early proliferation in cardiac allografts subjected to prolonged ischemia (TRAN3P.880)." Journal of Immunology 192, no. 1_Supplement (May 1, 2014): 202.19. http://dx.doi.org/10.4049/jimmunol.192.supp.202.19.

Повний текст джерела
Анотація:
Abstract Memory T cells induced to microbial infections provide protection to subsequent exposures but can have cross-reactivity with allogeneic MHC molecules. High numbers of memory T cells with donor reactivity in human and non-human primate recipients prior to transplant are associated with poorer allograft survival and resistance to costimulatory blockade strategies given to induce long-term graft survival. Rodent transplant models have failed to replicate the detrimental impact of endogenous memory T cells on allograft survival and tolerance induction, raising questions about the sufficiency of these models to study this component of alloimmunity. We have recently shown a direct association between increasing duration of cold ischemic storage and numbers of early graft infiltrating memory CD8 T cells that markedly up-regulate effector functions and directly mediate costimulatory blockade resistant rejection of cardiac allografts in a mouse model. Here we show that endogenous memory CD8 T cells exhibit increased early proliferation in grafts subjected to prolonged ischemia that is supported by memory CD4 T cells. Recipient depletion of CD4 T cells or treatment with MR1 (anti-CD40L) at transplant significantly decreased early memory CD8 T cell proliferation and extended survival of grafts subjected to prolonged cold ischemia. These studies provide novel insights into endogenous memory CD8 T cell mediated graft injury and the poor outcomes associated with cadaver donor grafts.
Стилі APA, Harvard, Vancouver, ISO та ін.
7

Kim, Seon-Hee, Chungyong Han, Byoung S. Kwon та Beom K. Choi. "CD4 depletion potentiates anti-tumor immunity in adoptive immunotherapy by increasing IL-18Rαhi endogenous CD8+ T cells". Journal of Immunology 204, № 1_Supplement (1 травня 2020): 170.7. http://dx.doi.org/10.4049/jimmunol.204.supp.170.7.

Повний текст джерела
Анотація:
Abstract Adoptive T cell therapy (ACT) requires lympho-depletion pre-conditioning to eliminate immune-suppressive elements to allow for the efficient engraftment of adoptively transferred tumor-reactive T cells. Because anti-CD4 monoclonal antibody depletes CD4+ immune-suppressive cells to enhance anti-tumor immunity, combinations of anti-CD4 treatment and ACT have synergistic potential in cancer therapy. We designed a post-ACT conditioning regimen that involves weekly treatment with anti-CD4 (CD4post). Using murine melanoma, cyclophosphamide and tumor-reactive CD8+ T cell infusion were included to represent an ACT model. We evaluated anti-tumor effects and immunologic changes of T cells. CD4post in ACT markedly increased tumor suppression and survival. Remarkably, CD4post worked differently on ex vivo primed CD8+ T cells versus endogenous CD8+ T cells. CD4post substantially increased the proliferation of ex vivo primed CD8+ T cells, while increasing endogenous CD8+ T cell differentiation and effector function. Endogenous CD8+ T cells upregulated activation/exhaustion markers and exhibited a skewed TCR repertoire, implying that CD4post boosted tumor-reactivity. Accordingly, CD4post-experienced endogenous CD8+ T cells showed enhanced intra-tumoral infiltration and exhibited greater anti-tumor activity against melanoma in vitro. Importantly, enrichment of the IL-18Rαhi subset was critical for boosting anti-tumor responses, as IL-18Rα+ cell-depletion CD8+ T cells resulted in diminished anti-tumor activity. This study highlights the clinical relevance of CD4post to ACT and gives insights into the characteristics of the immunological components that drive the augmented cancer–immunity cycle in ACT.
Стилі APA, Harvard, Vancouver, ISO та ін.
8

Kazemi, Pezhman, Mohammad Reza Nikudel, Mashalah Khamehchiyan, Paritosh Giri, Shima Taheri, and Simon Martin Clark. "Assessment of Alkali–Silica Reaction Potential in Aggregates from Iran and Australia Using Thin-Section Petrography and Expansion Testing." Materials 15, no. 12 (June 17, 2022): 4289. http://dx.doi.org/10.3390/ma15124289.

Повний текст джерела
Анотація:
The alkali–silica reaction can shorten concrete life due to expansive pressure build-up caused by reaction by-products, resulting in cracking. Understanding the role of the aggregate, as the main reactive component, is essential for understanding the underlying mechanisms of the alkali–silica reaction and thereby reducing, or even preventing, any potential damage. The present study aims to investigate the role of petrographic studies along with accelerated tests in predicting and determining the potential reactivity of aggregates, including granite, rhyodacite, limestone, and dolomite, with different geological characteristics in concrete. This study was performed under accelerated conditions in accordance with the ASTM C1260 and ASTM C1293 test methods. The extent of the alkali–silica reaction was assessed using a range of microanalysis techniques including optical microscopy, scanning electron microscopy, energy-dispersive X-ray analysis, and X-ray powder diffraction. The results showed that a calcium-rich aggregate with only a small quantity of siliceous component but with a higher porosity and water adsorption rate can lead to degradation due to the alkali–silica reaction, while dolomite aggregate, which is commonly considered a reactive aggregate, showed no considerable expansion during the conducted tests. The results also showed that rhyodacite samples, due to their glassy texture, the existence of strained quartz and quartz with undulatory extinction, as well as the presence of weathering minerals, have a higher alkali-reactivity potential than granite samples.
Стилі APA, Harvard, Vancouver, ISO та ін.
9

Clutton, Genevieve Tyndale, Sallay Kallon, Ann Weideman, Yinyan Xu, Joanna Warren, Olivia Council, Damir Alzhanov, et al. "CD3 and CD8 coreceptor down-modulation are inversely associated with CD8 T cell functional avidity in humans." Journal of Immunology 204, no. 1_Supplement (May 1, 2020): 94.2. http://dx.doi.org/10.4049/jimmunol.204.supp.94.2.

Повний текст джерела
Анотація:
Abstract This study investigated the function of memory CD8 T cells in HIV-infected people durably suppressed on antiretroviral therapy (HIV+ cART). We assessed bulk and virus-specific memory CD8 T cells in HIV+ cART and HIV-seronegative individuals (HIV−) by flow cytometry. We observed a population of CD3+ CD8dim CD14− CD16− (CD8dim) T cells that was expanded as a percentage of total CD8 T cells in both HIV− and CMV-seropositive individuals. Bulk memory CD8dim T cells expressed significantly higher CD69 and less MHC Class I and CD127 ex vivo than CD8bright T cells, suggesting recent activation. CD8dim T cells expressed less GLUT1 and PGC-1α and took up less glucose (2-NBDG) and lipid (Bodipy) than CD8bright T cells, indicating relatively lower metabolic activity. Multimer reactivity was used to examine CMV-, EBV- and HIV-specific CD8 T cells ex vivo. Virus-specific populations were consistently CD8high. However, after peptide stimulation, antigen-specific CD8 T cells down-regulated CD3 and CD8. CMV-specific CD8 T cells down-regulated CD3 and CD8 more than HIV-specific cells. CD3 and CD8 downregulation were strongly correlated with the functional avidity of the response. A strong correlation between GLUT1 down-regulation and CD8 down-regulation was also observed, suggesting an association between CD8 expression and metabolic activity. These results suggest that the expanded CD8dim population in HIV+ cART individuals, who are >90% CMV-seropositive, may be driven by ongoing activation of high-avidity CMV-specific CD8 T cells. They also suggest that different virus-specific CD8 T cell populations differentially downregulate components of the TCR complex and metabolism after antigen stimulation, possibly to avoid excessive activation.
Стилі APA, Harvard, Vancouver, ISO та ін.
10

Picker, Louis J., Andrew W. Sylwester, Bridget L. Mitchell, Cara Taormina, Christian Pelte, John Edgar, Florian Kern, et al. "T Cell Recognition of HCMV: Pan-Genome Analysis of Immunogenic Open-Reading Frames." Blood 104, no. 11 (November 16, 2004): 606. http://dx.doi.org/10.1182/blood.v104.11.606.606.

Повний текст джерела
Анотація:
Abstract Human Cytomegalovirus (HCMV) is among the largest and most complex of known viruses with 150–200nm virions enclosing a double stranded 230kb DNA genome capable of coding for >200 proteins. HCMV infection is life-long, and for the vast majority of immune competent individuals clinically benign. Disease occurs almost exclusively in the setting of immune deficiency, suggesting that the stable host-parasite relationship that characterizes these infections is the result of an evolutionarily “negotiated” balance between viral mechanisms of pathogenesis and the host immune response. In keeping with, and perhaps because of this balance, the human CD4+ T cell response to whole HCMV viral lysates is enormous, with median peripheral blood frequencies of HCMV-specific cells ~5–10 fold higher than for analogous preparations of other common viruses. Although certain HCMV ORFs have been identified as targets of either the CD4+ or CD8+ T cell response, the specificities comprising the CD4+ T cell response, and both the total frequencies and component parts of the CD8+ T cell response are unknown. Here, we used cytokine flow cytometry and ~14,000 overlapping 15mer peptides comprising all 213 HCMV ORFs encoding proteins >100 amino acids in length to precisely define the total CD4+ and CD8+ HCMV-specific T cell responses and the HCMV ORFs responsible for these responses in 33 HCMV-seropositive, HLA-disparate donors. An additional 9 HCMV seronegative donors were similarly examined to define the extent to which non-HCMV responses cross-react with HCMV-encoded epitopes. We found that when totaled, the median frequencies of HCMV-specific CD4+ and CD8+ T cells in the peripheral blood of the seropositive subjects were 4.0% and 4.5% for the total CD4+ or CD8+ T cell populations, respectively (which corresponds to 9.1% and 10.5% of the memory populations, respectively). The HCMV-specific CD4+ and CD8+ T cell responses included a median 12 and 7 different ORFs, respectively, and all told, 73 HCMV ORFs were identified as targets for both CD4+ and CD8+ T cells, 26 ORFs as targets for CD8+ T cells alone, and 43 ORFS as targets for CD4+ T cells alone. UL55, UL83, UL86, UL99, and UL122 were the HCMV ORFs most commonly recognized by CD4+ T cells; UL123, UL83, UL48, UL122 and UL28 were the HCMV ORFs most commonly recognized by CD8+ T cells. The relationship between immunogenicity and 1) HLA haplotype and 2) ORF expression and function will be discussed. HCMV-seronegative individuals were non-reactive with the vast majority of HCMV peptides. Only 7 potentially cross-reactive responses were identified (all by CD8+ T cells) to 3 ORFs (US32, US29 and UL116) out of a total of almost 4,000 potential responses, suggesting fortuitous cross-reactivity with HCMV epitopes is uncommon. These data provide the first glimpse of the total human T cell response to a complex infectious agent, and will provide insight into the rules governing immunodominance and cross-reactivity in complex viral infections of humans.
Стилі APA, Harvard, Vancouver, ISO та ін.

Частини книг з теми "Alkali-reactivity of CDW component"

1

Hendry, Robin Findlay. "Natural Kinds in Chemistry." In Essays in the Philosophy of Chemistry. Oxford University Press, 2016. http://dx.doi.org/10.1093/oso/9780190494599.003.0019.

Повний текст джерела
Анотація:
Chemical substances such as gold and water provide paradigm examples of natural kinds: They are so central to philosophical discussions on the topic that they often provide the grounds for quite general philosophical claims—in particular that natural kinds must be hierarchical, discrete, and independent of interests. In this chapter I will argue that chemistry in fact undermines such claims. In what follows I will (i) introduce the main kinds of chemical kinds, namely chemical substances and microstructural species; (ii) critically examine some general criteria for being a natural kind in the light of how they apply to chemical kinds; and finally (iii) present two broad theories of how chemical substances are individuated. The primary purpose of this article is to bring scientific detail and sophistication to a topic—natural kinds—which has a long but not always honorable history in philosophy, but chemists can also learn something from these discussions. Chemistry is in the business of making general claims about substances, a fact which is embodied in the periodic table, as well as in the systems of nomenclature and classification published by the International Union of Pure and Applied Chemistry (IUPAC). At several points in the history of their subject, chemists appear to have faced choices about which general categories should appear in these systems. Understanding why these choices were made, and the alternatives rejected, gives us an insight into whether chemistry might have developed differently. This is central to understanding why chemistry looks the way it does today. So, what are the chemical kinds? Chemists study the structure and behavior of substances such as gold, water and benzene, and also of microscopic species such as gold atoms, and water and benzene molecules. They group together higher kinds of substances: groups of elements such as the halogens and alkali metals, broader groups of elements such as the metals, and classes of compounds that share either an elemental component (e.g., chlorides), a microstructural feature (e.g., carboxylic acids), or merely a pattern of chemical reactivity (e.g., acids).
Стилі APA, Harvard, Vancouver, ISO та ін.

Тези доповідей конференцій з теми "Alkali-reactivity of CDW component"

1

"Assessment of Formula-Based Structural Annotation of Humic Substances by Mild Chemical Derivatization and Mass Spectrometry." In Sixth International Conference on Humic Innovative Technologies "Humic Substances and Eco-Adaptive Technologies ”(HIT – 2021). Non-Commercial Partnership "Center for Biogenic Resources "Humus Sapiens" (NP CBR "Humus Sapiens"), 2021. http://dx.doi.org/10.36291/hit.2021.mikhnevich.002.

Повний текст джерела
Анотація:
Natural organic matter (NOM) plays an important role in the environment and its chemical properties and molecular composition reflect balance between mineralization and sequestration of organic carbon. Ultrahigh resolution mass spectrometry (e.g., FTICR MS) provides essential molecular information about NOM. However, NOM molecular heterogeneity prevents application of tandem MS experiments and direct structural information is ultimately missing leaving opportunities to only ambiguous formula-based annotation. The main aim of this work was to develop a chemical workflow to reliably examine the accuracy of several FTICR MS-derived structural indices with the focus on aromaticity and O-functional groups, which greatly impact compound properties. Four NOM samples of different origin (coal, oxidized lignin, river, and permafrost thaw) were brominated by NBS in acetonitrile for 24 hrs at RT. Carboxylic groups in all samples were determined by selective deuteromethylation using CD 3OD/SOCl2 reaction and by HATU amidation with 15N labeled glycine. Carbonyl groups were reduced by NaBD4. All parent and labeled mixtures were analyzed by ESI FTCR MS. Custom python scripts were developed to treat spectra and enumerate specific structural moieties in individual components. Obtained data was used to assess reliability of exact aromaticity indices (AI)1 and aromaticity equivalents (Xc) 2. Lignin- and coal-derived samples turned out to be the most sensitive to bromination which corroborated with the model phenolic structures. On contrary, permafrost thaw, which is enriched with labile species, was mostly resistant to bromination - 22% of molecular ions were brominated. Moreover, unlike oxidized riverine sample, coal NOM included polybrominated species, which implies that reaction efficiency depends on reactivity (i.e. substituents) of aromatic fragments. Samples were characterized by drastically different bromine distributions on van Krevelen diagrams, which correlated with the distribution of non-carboxylic oxygen atoms. Further, we compared AI and Xc aromaticity indices in terms of the proportion of correctly assigned aromatics. The data on brominated molecules were in good agreement with the AI values; however, apparently AI tends to overestimate the number of non-aromatics in the sample since it describe averaged aromaticity rather than the factual presence of aromatic ring. On the other hand, Xc perfectly recognized non-aromatics. In general, a higher proportion of correctly attributed aromatics was observed for the aromaticity equivalent Xc (up to 68%), which tends to find aromatic moieties in non-aromatic molecules assigned by AI. Still, we observed a number of aromatic- and condensed aromatic-assigned compounds, which were resistant to bromination or included lesser Br-atoms than the evaluated number of aromatic rings. Reaction with NaBD4 and enumeration of labeling series revealed the presence of carbonyl groups in these species, which in case of multiple reducing could be reliably assigned to quinone – condensed non-aromatic compounds. The approach may be of great importance in biogeochemical and medicinal studies of NOM. Acknowledgements. This work was supported by the Russian Science Foundation gran No 21-47-04405. References 1. Zherebker, A., Lechtenfeld, O. J., Sarycheva, A., Kostyukevich, Y., Kharybin, O., Fedoros, E. I. and Nikolaev, E. N. Anal. Chem., 2020, 92 (13), 9032-9038; 2. Yassine, M.M., Harir, M., Dabek-Zlotorzynska, E. and Schmitt-Kopplin, P. Rapid Commun. Mass Spectrom., 2014, 28, 2445-2454.
Стилі APA, Harvard, Vancouver, ISO та ін.
Ми пропонуємо знижки на всі преміум-плани для авторів, чиї праці увійшли до тематичних добірок літератури. Зв'яжіться з нами, щоб отримати унікальний промокод!

До бібліографії