scholarly journals Analysis of the Structural Aspects of Tannin-Based Adhesives by 2D-NMR

Materials ◽  
2021 ◽  
Vol 14 (19) ◽  
pp. 5479
Author(s):  
Sachikazu Omura ◽  
Yoshinori Kawazoe ◽  
Daisuke Uemura
Keyword(s):  
Benzene Ring ◽  
Water Resistance ◽  
Multiple Bond ◽  
2D Nmr ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Chemical Structures ◽  
Correlation Spectrum ◽  
The Difference ◽  
Structural Aspects

We developed non-toxic, harmless adhesives composed of all-natural and renewable resources, of which one was composed of tannin and gelatin, which unfortunately was lacking water resistance, and the other of tannin and ε-poly-l-lysine. In this study, we analyzed the chemical structures of these adhesives by two-dimensional nuclear magnetic resonance (2D-NMR) to explain the difference in water-resistance of the two glues. The results showed that only one proton was left in the benzene ring of tannin after mixing. This suggests that the amino group of the protein was directly attached to the benzene ring by a Michael addition-type reaction, and not to the hydroxyl group. In addition, the heteronuclear multiple bond correlation spectrum of the tannin-poly-l-lysine compound indicated that the hydroxyl groups of the tannin oxidized, suggesting the improvement of its water resistance.

STUDIES ON LIGNIN AND RELATED COMPOUNDS: XVI. PHENOL LIGNIN FROM SPRUCE WOOD, FROM FREUDENBERG SPRUCE LIGNIN AND WILLSTÄTTER SPRUCE LIGNIN

1935 ◽  
Vol 13b (2) ◽  
pp. 61-77 ◽  
Author(s):  
Irene Koerber Buckland ◽  
Fritz Brauns ◽  
Harold Hibbert
Keyword(s):  
Condensation Product ◽  
Analytical Data ◽  
Insoluble Fraction ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Condensation Products ◽  
Building Unit ◽  
Spruce Wood ◽  
Analytical Results ◽  
The Difference

The condensation of lignin with phenol by treatment of spruce wood meal with this solvent, using hydrogen chloride as catalyst, yields two chemically different phenol lignins, namely, an ether-insoluble and an ether-dioxane–soluble phenol lignin, in a ratio of approximately 3 to 1. Duplicate preparations gave the same yields of these two fractions, analyses of which gave concordant results, indicating homogeneity and constancy of composition.The analytical results of the ether-insoluble phenol lignin, and of its methylated and acetylated derivatives, can be interpreted on the basis of the Brauns–Hibbert formula for the "native" lignin unit. It is found, in this way, that the ether-insoluble phenol lignin contains three new free phenolic hydroxyl groups capable of methylation with diazomethane, while one phenol group has reacted with one hydroxyl group in the lignin unit with formation of a phenyl-oxygen ether linkage.The analytical results of the ether-dioxane–soluble phenol lignin indicate that a much larger quantity of phenol has condensed with the "native" lignin building unit than in the case of the ether-insoluble fraction. The exact number of phenol molecules reacting to form this condensation product has not been determined experimentally although calculations based on analytical data point to a number as large as 15 or 21.The phenol condensation products were obtained from Freudenberg and Willstätter lignins in nearly quantitative yield and found to differ from the directly extracted phenol lignin in that neither of them could be resolved into two fractions, thus indicating that some change had taken place in the native lignin during the isolation process. The Brauns-Hibbert formula can also be applied to interpret the experimental data in both cases. These lignins appear to contain the same fundamental building unit as the ether-insoluble phenol lignin fraction isolated directly from spruce wood, with the difference that the former probably have one additional hydroxyl group capable of acetylation and diazomethane-methylation.The correlation found to exist in the present investigation between the phenol condensation products from native spruce lignin, isolated Freudenberg lignin and Willstätter lignin is regarded as providing definite experimental evidence indicating the presence of a chemical unit common to various lignins. The phenol condensation products, it is considered, may serve as valuable reference compounds for proving the identity of lignins obtained from different sources and by use of different chemical reagents.

The hydroxyl stretching frequencies and conformations of Flavan-4-ols and Thiaflavan-4-ols

1969 ◽  
Vol 22 (11) ◽  
pp. 2337 ◽  
Author(s):  
GF Katekar ◽  
AG Moritz
Keyword(s):  
Carbon Tetrachloride ◽  
Benzene Ring ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Frequency Shifts ◽  
Characteristic Frequencies ◽  
Carbon Tetrachloride Solution ◽  
Free Hydroxyl ◽  
Related Compounds

The hydroxyl stretching frequencies of some 2,4-cis and 2,4-trans flavan-4-ols, thiaflavan-4-ols, and related compounds have been measured in dilute carbon tetrachloride solution. Characteristic frequencies are observed at 3626�2 cm-1 (free hydroxyl), 3616�1, and 3597�2 cm-1. The 3616 and 3597 cm-1 bands are assigned to pseudo-axial and pseudo-equatorial hydroxyl groups respectively. Evidence is presented to show that the frequency shifts arise from differences in the interaction of the hydroxyl group with the π-electrons of the fused benzene ring, and that these flavans and thiaflavans exist in half- chair, rather than sofa conformations.

Determination of Phenolic Hydroxyl Groups in Lignin by Combined Use of 1H NMR and UV Spectroscopy

Holzforschung ◽  
1999 ◽  
Vol 53 (5) ◽  
pp. 529-533 ◽  
Author(s):  
Eija Tiainen ◽  
Torbjörn Drakenberg ◽  
Tarja Tamminen ◽  
Kirsi Kataja ◽  
Anneli Hase
Keyword(s):  
Uv Spectroscopy ◽  
Spectroscopic Properties ◽  
Phenolic Hydroxyl ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Model Compounds ◽  
H Nmr ◽  
Combined Use ◽  
Phenolic Hydroxyl Groups ◽  
The Difference

Summary Two independent spectroscopic methods are presented and compared for the quantitation of the phenolic hydroxyl groups in lignins. The combined information is used to further elucidate the character of the lignin samples examined. The UV method is based on the difference of the spectroscopic properties of the ionised and the nonionised phenol. The method using 1H NMR spectroscopy is based on the exchange of phenolic protons in D2O. The difference in integrated proton intensities in the sample dissolved in DMSO and the sample with additional 20% D2O is proportional to the phenolic protons. The method based on UV spectroscopy uses differences in the maxima close to 300 nm and 350 nm of the sample dissolved in alkali and the neutral sample. The results using the two independent methods are in agreement for milled wood lignin, for kraft lignin and for model compounds carrying one aromatic hydroxyl group. For modified lignins and for model compounds with more than one aromatic hydroxyl group, the UV method gives too low values for phenolic hydroxyl groups. The combined results obtained by the two methods however provide information of the total amount of the phenolic groups and of the nature of the phenolic structure formed by the lignin refining.

Proton magnetic resonance spectra and conformation of mevalonolactone and 3,3-dimethylvalerolactone

1971 ◽  
Vol 24 (8) ◽  
pp. 1659 ◽  
Author(s):  
RN Johnson ◽  
NV Riggs
Keyword(s):  
Energy Difference ◽  
Equilibrium Mixture ◽  
Hydroxyl Group ◽  
Proton Spectrum ◽  
Hydroxyl Groups ◽  
Methylene Proton ◽  
Ring Proton ◽  
Starting Point ◽  
Methylene Groups ◽  
The Difference

The ring-proton spectrum at 60 MHz of mevalonolactone (3-hydroxy-3- methylvalerolactone) has been examined in a range of solvents and that of 3,3- dimethylvalerolactone in deuterochloroform a t 30°. All the spectra are complicated by long-range coupling between the 2- and 4-methylene protons, but a complete set of magnetic parameters, for the MM'XX' spectrum of the 4- and 5-methylene groups of 3,3-dimethylvalerolactone may be extracted from the spectrum of the 5-methylene (XX') protons alone. Such parameters as can be extracted for mevalonolactone suggest there is little dependence of conformation on solvent. At 100 MHz in hexa- deuteroacetone alone, or in mixtures with benzene, the 2-methylene protons show only a small internal chemical shift and are readily completely decoupled; the residual 4,5-methylene-proton four-spin spectrum gave a set of parameters used as the starting point for iterative analysis of the complete six-spin ring-proton spectrum. I t is proposed that mevalonolactone in solution is a rapidly inverting equilibrium mixture of half-chair conformers in which the conformer having the hydroxyl group axial is favoured c. 4.5 : 1 at 30°. The corresponding free-energy difference (c. 750 cal mol-1) is close to the difference of conformational free-energies of methyl and hydroxyl groups in cyclohexane systems, which suggests that no special polar factor is operating in the mevalonolactone equilibrium.

Unusual pyranosyl cembranoid diterpene from Sarcophyton trocheliophorum

2016 ◽  
Vol 71 (12) ◽  
pp. 1211-1217 ◽  
Author(s):  
Mohamed Shaaban ◽  
Mohamed A. Ghani ◽  
Khaled A. Shaaban
Keyword(s):  
Quantum Coherence ◽  
Soft Coral ◽  
High Resolution Mass Spectrometry ◽  
Nuclear Overhauser Effect ◽  
Multiple Bond ◽  
2D Nmr ◽  
Correlation Spectroscopy ◽  
Multiple Quantum ◽  
Chemical Structures ◽  
Sarcophyton Trocheliophorum

Abstract9-Hydroxy-10,11-dehydro-sarcotrocheliol (1), a new pyrane-based cembranoid diterpene, has been isolated along with three other known compounds, namely, sarcotrocheliol acetate (2), (+)-sarcophytol A (3), and (−)-sarcophytonin A (4), from the organic extract of the soft coral Sarcophyton trocheliophorum. The chemical structures of compounds 1–4 were determined on the basis of their 1D and 2D NMR [1H, 13C, 1H–1H correlation spectroscopy, heteronuclear multiple-quantum coherence, heteronuclear multiple-bond correlation, and nuclear Overhauser effect (NOE)] and mass spectra [electron ionization (EI), electrospray ionization, and high resolution mass spectrometry (HRMS)], and by comparison with related structures. The compounds 1–4 showed neither antimicrobial activity against 11 diverse tested microorganisms, nor cytotoxicity against brine shrimp, whereas the soft coral extract showed low cytotoxicity with a mortality rate of 1.7%.

scholarly journals Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2131
Author(s):  
Leonardo Dalseno Antonino ◽  
Júlia Rocha Gouveia ◽  
Rogério Ramos de Sousa Júnior ◽  
Guilherme Elias Saltarelli Garcia ◽  
Luara Carneiro Gobbo ◽  
...  
Keyword(s):  
Experimental Work ◽  
Chemical Structure ◽  
31P Nmr ◽  
Kraft Lignin ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Diphenylmethane Diisocyanate ◽  
Complex Chemical ◽  
Heterogeneous Reactivity ◽  
Phenolic Hydroxyl Groups

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. 31P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.

scholarly journals Enhancement of Antioxidant and Hydrophobic Properties of Alginate via Aromatic Derivatization: Preparation, Characterization, and Evaluation

Polymers ◽  
2021 ◽  
Vol 13 (15) ◽  
pp. 2575
Author(s):  
Smaher M. Elbayomi ◽  
Haili Wang ◽  
Tamer M. Tamer ◽  
Yezi You
Keyword(s):  
Radical Scavenging Activity ◽  
Radical Scavenging ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Gravimetric Analysis ◽  
Scanning Calorimetry ◽  
Benzoyl Group ◽  
Antioxidant Evaluation ◽  
Thermo Stability

The preparation of bioactive polymeric molecules requires the attention of scientists as it has a potential function in biomedical applications. In the current study, functional substitution of alginate with a benzoyl group was prepared via coupling its hydroxyl group with benzoyl chloride. Fourier transform infrared spectroscopy indicated the characteristic peaks of aromatic C=C in alginate derivative at 1431 cm−1. HNMR analysis demonstrated the aromatic protons at 7.5 ppm assigned to benzoyl groups attached to alginate hydroxyl groups. Wetting analysis showed a decrease in hydrophilicity in the new alginate derivative. Differential scanning calorimetry and thermal gravimetric analysis showed that the designed aromatic alginate derivative demonstrated higher thermo-stability than alginates. The aromatic alginate derivative displayed high anti-inflammatory properties compared to alginate. Finally, the in vitro antioxidant evaluation of the aromatic alginate derivative showed a significant increase in free radical scavenging activity compared to neat alginate against DPPH (2,2-diphenyll-picrylhydrazyl) and ABTS free radicals. The obtained results proposed that the new alginate derivative could be employed for gene and drug delivery applications.

Two-dimensional NMR studies of acrylate copolymers

2009 ◽  
Vol 81 (3) ◽  
pp. 389-415 ◽  
Author(s):  
A. S. Brar ◽  
Ashok Kumar Goyal ◽  
Sunita Hooda
Keyword(s):  
Methyl Methacrylate ◽  
Methyl Acrylate ◽  
Quantum Coherence ◽  
Multiple Bond ◽  
Microstructural Analysis ◽  
2D Nmr ◽  
Correlation Spectroscopy ◽  
Nmr Studies ◽  
Poly Methyl Methacrylate ◽  
Nmr Study

High-resolution NMR spectroscopy is the most versatile, reliable, and generally acceptable technique for the determination of the microstructure of polymers. 2D NMR techniques, along with 1D NMR, have more potential to study absolute configurational assignments and sequence distribution of copolymers. Physical and chemical properties of polymers are influenced fundamentally by their microstructure. We discuss the detailed microstructure analysis of a large number of homopolymers, copolymers, and terpolymers. 2D NMR study of poly(methyl methacrylate) (PMMA), poly(methyl acrylate) (PMA), and poly(methacrylonitrile) (PMAN) is discussed in this article. In addition to homopolymers, 2D heteronuclear single-quantum coherence (HSQC), total correlation spectroscopy (TOCSY), and heteronuclear multiple-bond correlation (HMBC) study of different copolymers such as poly(methyl methacrylate-co-methyl acrylate), poly(styrene-co-methyl methacrylate), and poly(methyl methacrylate-co-methacrylonitrile) have also been reported here. This in turn helps in microstructural analysis of terpolymers such as poly(methacrylonitrile-co-styrene-co-methyl methacrylate), poly(acrylonitrile-co-methyl methacrylate-co-methyl acrylate), and poly(ethylene-co-vinyl acetate-co-carbon monoxide).

Bisquaternary ammonium salts derived from 3α,12α-Diamino-5β-cholane and 3α,12α-Diamino-24-nor-5β-cholane

1971 ◽  
Vol 24 (3) ◽  
pp. 521 ◽  
Author(s):  
S Ahmed ◽  
M Alauddin ◽  
B Caddy ◽  
M Martin-Smith ◽  
WTL Sidwell ◽  
...  
Keyword(s):  
Deoxycholic Acid ◽  
Ammonium Salts ◽  
Hydroxyl Group ◽  
Amino Compound ◽  
Hydroxyl Groups ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Polyhydric Alcohols ◽  
Methane Sulphonate ◽  
Methylene Group

The preparation of 3α,12α-bisdimethylamino-5β-cholane dimethiodide, 3α,12α-bisdimethylamino-5β-cholane dimethiodide, 3α,12α- bisdimethylamino-24-nor-5β-cholanedimethiodide, and 3α,12α- bisdimethylamino-24-nor-5β-cholanediethiodide, from deoxycholic acid are described. During this work it was found that attempted copper- quinoline decarboxylation of dehydrocholic acid gives rise to lactol formation, and that what had previously been considered to be 3α,12α- dihydroxy-5β-cholane is a mixture of this compound and 12α,24- dihydroxy-5β-cholane. Comparable selectivity of attack by methanesulphonyl chloride and toluene-p-sulphonyl chloride occurs with various polyhydric alcohols derived from bile acids, as evidenced from the products of reduction of the sulphonates with lithium aluminium hydride. With both 5α- and 5β-cholane derivatives, a C 3 equatorial hydroxyl group exhibits comparable reactivity to the terminal primary hydroxyl group, generated from the bile acid carboxylic group, towards both sulphonyl chlorides. With axial hydroxyl groups at C 7 and C 12, toluene-p-sulphonate formation is much more difficult than methane- sulphonate formation. Reduction by means of lithium aluminium hydride of equatorial sulphonate esters at C 7 and C 12 gives rise to a methylene group, but the axial sulphonates under the same conditions give the axial alcohol. The same clear distinction between equatorial and axial sulphonate esters is not observed at C 3 and C 6, but 17α- methanesulphonyloxy-5α-androstane gives 5α-androstane and the 17β- ester gives 17β-hydroxy-5α-androstane. Reduction of 12-oximino groups in both 5α- and 5β-cholanes with sodium and ethanol, hydrogen in the presence of a catalyst, or lithium aluminium hydride gives solely the 12α-amino compound.

Resistance Tests of an Articulated Pusher Barge System in Deep and Shallow Water

2021 ◽  
Author(s):  
Li Zhang ◽  
Lei Xing ◽  
Mingyu Dong ◽  
Weimin Chen
Keyword(s):  
Shallow Water ◽  
Water Depth ◽  
Deep Water ◽  
Water Resistance ◽  
Model Tests ◽  
System 2 ◽  
Changing Trend ◽  
The Difference ◽  
Transport Vessel ◽  
Resistance Performance

Abstract Articulated pusher barge vessel is a short-distance transport vessel with good economic performance and practicability, which is widely used in the Yangtze River of China. In this present work, the resistance performance of articulated pusher barge vessel in deep water and shallow water was studied by model tests in the towing tank and basin of Shanghai Ship and Shipping Research Institute. During the experimental investigation, the articulated pusher barge vessel was divided into three parts: the pusher, the barge and the articulated pusher barge system. Firstly, the deep water resistance performance of the articulated pusher barge system, barge and the pusher at design draught T was studied, then the water depth h was adjusted, and the shallow water resistance at h/T = 2.0, 1.5 and 1.2 was tested and studied respectively, and the difference between deep water resistance and shallow water resistance at design draught were compared. The results of model tests and analysis show that: 1) in the study of deep water resistance, the total resistance of the barge was larger than that of the articulated pusher barge system. 2) for the barge, the shallow water resistance increases about 0.4–0.7 times at h/T = 2.0, 0.5–1.1 times at h/T = 1.5, and 0.7–2.3 times at h/T = 1.2. 3) for the pusher, the shallow water resistance increases about 1.0–0.4 times at h/T = 2.7, 1.2–0.9 times at h/T = 2.0, and 1.7–2.4 times at h/T = 1.6. 4) for the articulated pusher barge system, the shallow water resistance increases about 0.2–0.3 times at h/T = 2.0, 0.5–1.3 times at h/T = 1.5, and 1.0–3.5 times at h/T = 1.2. Furthermore, the water depth Froude number Frh in shallow water was compared with the changing trend of resistance in shallow water.

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