SYNTHESIS AND OPTICAL PROPERTIES OF CAMPHOR-SABSTITUTED TETRAPYRAZINOPORPHYRAZINES

The synthesis of the complexes of Cu, Ni, Co, Pd, Sn, Hg of 1',7',7'-trimethylbicyclo[2.2.1]heptano-[2',3'-b]-2,3-pyrazinoporphyrazine for new materials for variety of potential applications is described. Metallic complexes were synthesized by the template cyclotetramerization of dicarbonitrile with metal chlorides at temperature 140-150 ºС for 20 min. Ammonium molybdate tetrahydrate was used as a catalyst. The products were purificated by chromatography on silica gel (eluent -chloroform). Complexes of Pd, Sn and Hg were synthesized for the first time. The metallocomplexes of camphor-substituted tetrapyrazinoporphyrazine are crystalline substances of dark blue color, not fusible up to 300 ° C, which have good solubility in chloroform, toluene, ethanol, acetone, DMF, acetic and trifluoroacetic acids. The chemical structures of the complexes of Cu, Ni, Co, Pd, Sn, Hg of 1',7',7'-trimethylbicyclo[2.2.1]heptano-[2’,3’-b]-2,3-pyrazinoporphyrazine obtained in this study were characterized by proton nuclear magnetic resonance and mass spectrometry. The absence of impurity signals in the 1H NMR spectra indicates a high degree of purity of the compounds obtained. For copper, nickel and cobalt complexes, a good correlation was found between the experimental and literature data on the chemical shifts of protons in 1H NMR spectra. Optical properties of the synthesized complexes were studied. The electronic absorption spectra of the complexes in their chloroform, DMF, acetic acid and sulfuric acid solutions were obtained. In organic solvents the typical B band (Soret band, around 400 nm) and Q band (in 600-700 nm region) of phthalocyanines were identified in this study. Complexes of Pd, Sn and Hg in their sulfuric acid solutions are non-stable. The influence of the chemical structure of metalic complexes and solvents on the optical properties was studied. Emission properties of the synthesized complexes of Pd and Hg in their chloroform and DMF solutions were analyzed. Hg-porphyrazine has very intensive fluorescence. The solution has blue color and red fluorescence at common condition.Forcitation:Kuvshinov G.V., Ziyadova T.M., Kuvshinova S.A., Koifman O.I. Synthesis and optical properties of camphor-sabstituted tetrapyrazinoporphyrazines. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2017. V. 60. N 4. P. 60-67.

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Large-Scale Evaluation of Major Soluble Macromolecular Components of Fish Muscle from a Conventional 1H-NMR Spectral Database

Molecules ◽

10.3390/molecules25081966 ◽

2020 ◽

Vol 25 (8) ◽

pp. 1966 ◽

Cited By ~ 1

Author(s):

Feifei Wei ◽

Minoru Fukuchi ◽

Kengo Ito ◽

Kenji Sakata ◽

Taiga Asakura ◽

...

Keyword(s):

1H Nmr ◽

Nmr Spectra ◽

Large Scale ◽

Fish Muscle ◽

1H Nmr Spectra ◽

Proton Nuclear Magnetic Resonance ◽

Training Dataset ◽

Small Scale ◽

Additional Measurement ◽

Molecular Components

Conventional proton nuclear magnetic resonance (1H-NMR) has been widely used for identification and quantification of small molecular components in food. However, identification of major soluble macromolecular components from conventional 1H-NMR spectra is difficult. This is because the baseline appearance is masked by the dense and high-intensity signals from small molecular components present in the sample mixtures. In this study, we introduced an integrated analytical strategy based on the combination of additional measurement using a diffusion filter, covariation peak separation, and matrix decomposition in a small-scale training dataset. This strategy is aimed to extract signal profiles of soluble macromolecular components from conventional 1H-NMR spectral data in a large-scale dataset without the requirement of re-measurement. We applied this method to the conventional 1H-NMR spectra of water-soluble fish muscle extracts and investigated the distribution characteristics of fish diversity and muscle soluble macromolecular components, such as lipids and collagens. We identified a cluster of fish species with low content of lipids and high content of collagens in muscle, which showed great potential for the development of functional foods. Because this mechanical data processing method requires additional measurement of only a small-scale training dataset without special sample pretreatment, it should be immediately applicable to extract macromolecular signals from accumulated conventional 1H-NMR databases of other complex gelatinous mixtures in foods.

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Data mining and knowledge discovery in proton nuclear magnetic resonance (1H-NMR) spectra using frequency to information transformation (FIT)

Knowledge-Based Systems ◽

10.1016/s0950-7051(01)00147-2 ◽

2002 ◽

Vol 15 (4) ◽

pp. 251-259 ◽

Cited By ~ 5

Author(s):

H. Valafar ◽

F. Valafar

Keyword(s):

Data Mining ◽

Nuclear Magnetic Resonance ◽

Magnetic Resonance ◽

Knowledge Discovery ◽

1H Nmr ◽

Nmr Spectra ◽

1H Nmr Spectra ◽

Proton Nuclear Magnetic Resonance ◽

Information Transformation ◽

Nuclear Magnetic

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Chemical composition, optical properties, and oxidative potential of water- and methanol-soluble organic compounds emitted from the combustion of biomass materials and coal

10.5194/acp-2021-159 ◽

2021 ◽

Author(s):

Tao Cao ◽

Meiju Li ◽

Chunlin Zou ◽

Xingjun Fan ◽

Jianzhong Song ◽

...

Keyword(s):

Optical Properties ◽

Organic Compounds ◽

1H Nmr ◽

Water Soluble ◽

Proton Nuclear Magnetic Resonance ◽

Resonance Spectroscopy ◽

Oxidative Potential ◽

Strong Light ◽

Chemical Structures ◽

Biomass Materials

Abstract. Biomass burning (BB) and coal combustion (CC) are important sources of brown carbon (BrC) in ambient aerosols. In this study, six biomass materials and five types of coal were combusted to generate fine smoke particles. The BrC fractions, including water-soluble organic compounds (WSOC), humic-like substances (HULIS), and methanol-soluble organic compounds (MSOC), were subsequently fractionated and their optical properties and chemical structures were then comprehensively investigated using UV-visible spectroscopy, proton nuclear magnetic resonance spectroscopy (1H-NMR), and fluorescence extraction-emission matrix spectroscopy (EEM) combined with parallel factor analysis (PARAFAC). In addition, the oxidative potential (OP) of BB and CC BrC was measured with the dithiothreitol (DTT) method. The results showed that WSOC, HULIS, and MSOC accounted for 2.3 %–22 %, 0.5 %–10 %, and 6.4 %–73 % of the total mass of combustion-derived PM2.5, respectively, with MSOC extracting the highest concentrations of organic compounds. The MSOC fractions had the highest light absorption capacity (mass absorption efficiency at 365 nm (MAE365): 1.0–2.7 m2/gC) for both BB and CC smoke, indicating that MSOC contained more of the strong light-absorbing components. Therefore, MSOC may better represent the total BrC than the water-soluble fractions. Some significant differences were observed between the BrC fractions emitted from BB and CC, with more water-soluble BrC fractions with higher MAE365 and lower absorption Ångström exponent values detected in smoke emitted from BB than from CC. The EEM-PARAFAC analysis identified four fluorophores: two protein-like, one humic-like, and one polyphenol-like. The protein-like substance was the dominant component of WSOC (47 %–80 %), HULIS (44 %–87 %), and MSOC (42 %–70 %). The 1H-NMR results suggested that BB BrC contained more oxygenated aliphatic functional groups (H-C-O), whereas CC BrC contained more unsaturated fractions (H-C-C = and Ar-H). The DTT assays indicated that BB BrC generally had a stronger OP (DTTmass, 2.6–85 pmol/min/μg) than CC BrC (DTTmass, 0.4–11 pmol/min/μg), with MSOC having a stronger OP than WSOC and HULIS. Therefore, the BrC fractions from BB had higher OP values than those from CC.

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Molecular characterization of dissolved organic matter from subtropical wetlands: a comparative study through the analysis of optical properties, NMR and FTICR/MS

Biogeosciences Discussions ◽

10.5194/bgd-12-13711-2015 ◽

2015 ◽

Vol 12 (16) ◽

pp. 13711-13765 ◽

Cited By ~ 5

Author(s):

N. Hertkorn ◽

M. Harir ◽

K. M. Cawley ◽

P. Schmitt-Kopplin ◽

R. Jaffé

Keyword(s):

Organic Matter ◽

Optical Properties ◽

Dissolved Organic Matter ◽

Molecular Characterization ◽

1H Nmr ◽

High Field ◽

Nmr Spectra ◽

Chemical Diversity ◽

1H Nmr Spectra

Abstract. Wetlands provide quintessential ecosystem services such as maintenance of water quality, water supply and biodiversity, among others; however, wetlands are also among the most threatened ecosystems worldwide. They are usually characterized by high levels of natural dissolved organic matter (DOM), representing a critical component in wetland biogeochemistry. This study describes the first detailed, comparative, molecular characterization of DOM in sub-tropical, pulsed, wetlands, namely the Everglades (USA), the Pantanal (Brazil) and the Okavango Delta (Botswana), using optical properties, high field nuclear magnetic resonance (NMR) and ultrahigh resolution mass spectrometry (FT-ICRMS), and compares compositional features to variations in organic matter sources and flooding characteristics (i.e. differences in hydroperiod). While optical properties showed both similarities and differences between these ecosystems, these differences were mainly based on the degree of aromaticity of the DOM. Analogies were such that an established excitation emission matrix fluorescence parallel factor analysis (EEM-PARAFAC) model for the Everglades was perfectly applicable to the other two wetlands. High-field (500 and 800 MHz) NMR spectra with cryogenic detection provided exceptional coverage and chemical description of wetland solid phase extracted (SPE) DOM. Area-normalized 1H NMR spectra of selected samples revealed clear distinctions of samples along with pronounced congruence within the three pairs of wetland DOM. Within sample pairs (long vs. short hydroperiod sites), internal differences mainly referred to intensity variations (denoting variable abundance) rather than to alterations of NMR resonances positioning (denoting diversity of molecules). The relative disparity was largest between the Everglades long and short hydroperiod samples, whereas Pantanal and Okavango samples were more alike among themselves. Otherwise, molecular divergence was most obvious in the case of unsaturated protons (δH > 5 ppm). The larger discrimination observed between 1H NMR spectra of DOM from different wetlands in comparison with the intrinsic variance among DOM within each wetland readily suggests the presence of an individual molecular signature, characteristic of each particular wetland. 2-D NMR spectroscopy for a particular sample revealed a large richness of aliphatic and unsaturated substructures, likely derived from microbial sources such as periphyton in the Everglades. In contrast, the chemical diversity of aromatic wetland DOM likely originates from a combination of higher plant sources, progressive microbial and photochemical oxidation, and contributions from combustion-derived products (e.g. black carbon). In addition, FT-ICRMS spectra allowed far-reaching classifications of wetland DOM. While DOM of both Okavango and Pantanal showed near 57 ± 2 % CHO, 8 ± 2 % CHOS, 33 ± 2 CHNO, and < 1 % CHNOS molecules, the mass spectra of Everglades samples were fundamentally different compared to those as well as among long and short hydroperiod samples, as they were markedly enriched in CHOS and CHNOS at the expense of CHO and CHNO compounds. Here, four groups of CHOS molecules were differentiated as (a) saturated sulfolipids, (b) unsaturated sulfolipids, (c) molecularly diverse DOM-type CHOS molecules, (d) and particularly enriched in the Everglades short hydroperiod site, a large set of aromatic and oxygen-deficient "black sulphur" compounds. The significantly higher proportion of CHOS compounds in general for the Everglades samples is likely the result of higher inputs of agriculture-derived and sea spray derived sulphate to this wetland compared to the others. Although wetland DOM samples were found to share many molecular features, each sample was unique in its composition, which reflected specific environmental drivers and/or specific biogeochemical processes.

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1H-NMR metabolic profiling of wines from three cultivans, three soil types and two contrasting vintages

OENO One ◽

10.20870/oeno-one.2007.41.2.850 ◽

2007 ◽

Vol 41 (2) ◽

pp. 103

Author(s):

Giuliano Elias Pereira ◽

Jean-Pierre Gaudillère ◽

Cornelis Van Leeuwen ◽

Ghislaine Hilbert ◽

Mickaël Maucourt ◽

...

Keyword(s):

1H Nmr ◽

Metabolic Profiling ◽

Nmr Spectra ◽

Partial Least Square ◽

1H Nmr Spectra ◽

Proton Nuclear Magnetic Resonance ◽

Soil Types ◽

Quality Traits ◽

Grape Quality ◽

Nmr Signals

Aims: Differences in wine flavour proceed primarily from grape quality. Environmental factors (climate, soil), cultivars and training systems modify many grape and wine quality traits. Metabolic profiling based on proton nuclear magnetic resonance (1H-NMR) spectra has been proved to be useful to study multifactorial effects of the vine environment on intricate grape quality traits. The capacity of this method to discriminate the environmental effects on wine has to be demonstrated.Methods and results: : 1H-NMR spectra were made from wines produced with grapes harvested at maturity of three cultivars (Cabernet-Sauvignon, Cabernet franc and Merlot) and three soil types (gravely, sandy and clayey) during two vintages (2002 and 2003). Data were analysed by multivariate statistical methods. Principal component analysis applied on the NMR spectra data were not always able to separate satisfactorily wines from the 3 soil types. Conversely, partial least square analysis separated clearly the 3 soil types independently of the vintage and cultivar.Conclusion: By comparing the NMR signals that contribute to the two first axes of the PCA and PLS analyses, a significant soil effect on NMR signals in wines is reported. However, the effect of the vintage on wine composition was greater then the effect of the soil type.Significance and impact of study: After validation on a larger number of wine samples this chemical profiling will be a useful new method to the qualify wines in relation to climate, soil, and cultivar effects which contribute to the terroir.

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Univariate Statistical Analysis as a Guide to 1H-NMR Spectra Signal Assignment by Visual Inspection

Metabolites ◽

10.3390/metabo9010015 ◽

2019 ◽

Vol 9 (1) ◽

pp. 15 ◽

Cited By ~ 3

Author(s):

Chenglin Zhu ◽

Beatrice Vitali ◽

Gilbert Donders ◽

Carola Parolin ◽

Yan Li ◽

...

Keyword(s):

Statistical Analysis ◽

1H Nmr ◽

Nmr Spectra ◽

Visual Inspection ◽

Signal To Noise Ratio ◽

1H Nmr Spectra ◽

Proton Nuclear Magnetic Resonance ◽

Signal Assignment ◽

Hands On ◽

Interested User

In Proton Nuclear Magnetic Resonance (1H-NMR) spectroscopy, the signals assignment procedure is normally conducted by visual inspection of the spectra, by taking advantage of the innate predisposition of human eye for pattern recognition. In the case of untargeted metabolomics investigations on food and body fluids, the complexity of the spectra may lead the user to overlook signals, independently from their biological relevance. Here, we describe a four steps procedure that is designed to guide signals assignment task by visual inspection. The procedure can be employed whenever an experimental plan allows for the application of a univariate statistical analysis on a point-by-point basis, which is commonly the case. By comparing, as a proof of concept, 1H-NMR spectra of vaginal fluids of healthy and bacterial vaginosis (BV) affected women, we show that the procedure is also readily usable by non-experts in three particularly challenging cases: overlapping multiplets, poorly aligned signals, and signals with very poor signal-to-noise ratio. The paper is accompanied by the necessary codes and examples written in R computational language to allow the interested user gaining a hands-on impression of the procedure’s strengths and weaknesses.

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