Manifestation of anomeric form, ring structure, and linkage in the 13c-n.m.r. spectra of oligomers and polymers containing D-fructose: maltulose, isomaltulose, sucrose, leucrose, 1-kestose, nystose, inulin, and grass levan

doi:10.1016/0008-6215(79)80005-1

Carbohydrate Research

Volume 76, Issue 1, November 1979, Pages 45-57

https://doi.org/10.1016/0008-6215(79)80005-1 Get rights and content

Abstract

¹³C-N.m.r. spectroscopy has been used to determine the equilibrium composition of solutions of maltulose and isomaltulose in deuterium oxide. Resonance assignments have been made for maltulose, isomaltulose, sucrose, leucrose, 1-kestose, nystose, inulin, and grass levan. Some earlier assignments for sucrose and grass levan are corrected. The resonances of the D-glucopyranosyl group in maltulose and isomaltulose have been observed to be sensitive to the ring and anomeric forms of the adjacent D-fructose residue. Spin-lattice relaxation-times (T1) and nuclear Overhauser enhancement factors (n.O.e.f.) for the carbon atoms of the D-fructofuranosyl residues of inulin have been measured, and used in conjunction with deuteration, to aid in resonance and linkage assignments.

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Further evidence later demonstrated the non-cariogenic potential of isomaltulose, as it is not metabolized by Streptococcus mutans, the etiological agent of dental caries (Hamada, Koga, & Ooshima, 1984; Maki et al., 1983; Topitsoglou, Sasaki, Takazoe, & Frostell, 1984). The authors highlighted that this potential can be associated with the isomaltulose structure previously elucidated by Jarell, Conway, Moyna, & Smith (1979) through 13C NMR spectroscopy. They showed that isomaltulose is composed of D-glucose and D-fructose joined by an α-1,6-glycosidic linkage (Fig. 1); a structure that makes it more stable than sucrose at adverse pH and temperature conditions.
Consumers are concerned with the amount of sucrose added to foods and its effects on human health. One way to reduce this concern is through the consumption of sucrose substitutes, such as isomaltulose. Isomaltulose is an alternative sugar that should be regarded by the food industry as much healthier than sucrose, due to its beneficial properties; these include, low glycemic index and slow hydrolysis, prebiotic potential, and low cariogenic potential. In this work, a bibliometric analysis associated with a review of literature was conducted as a rigorous method for exploring and analyzing large volumes of scientific data, to understand the global scenario and identify the trends regarding isomaltulose. Important facts from its history and origin were discussed, as well the main research and countries that have contributed to its growing interest in the food industry. Over the years, from the discovery of new beneficial properties, more studies have been conducted, demonstrating that the interest in isomaltulose has been increasing. Finally, we concluded that isomaltulose is a promising sucrose substitute that could change the scenario of the sugar-rich foods market; and its use for the development of new products is highly encouraged.
Synthesis of highly stable bacterial cellulosic pocket for drug storage
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Citation Excerpt :
As the steric interactions of inulin side group correspond to R1 = R2 = C4O4H8, it was realized that this ring replacement tilted (φ,Ψ) to rather unexpected values when compared with the crystalline state conformation of substituted polyoxyethylenes (Mensink et al., 2015a). It should be noted that the regular (2→l)-β-D linkage in inulin results in an "isotactic" structure for the pocket (Jarrell, Conway, Moyna, & Smith, 1979). It is to be known that the ω values for crystalline poly(alky1eneoxides) was defined to be either 180° or near to 60°, with two crystalline polymorphs.
Inulin was introduced to the fructose permeates of Gluconacetobacter xylinus (ATCC 10,245) bacterial strain to successfully synthesize empty cellulosic pockets for possible drug storage. FTIR Spectroscopy analysis confirmed a slight variation in the hydrogen bonds at 2893 cm⁻¹ due to CH and CH₂ stretching whiles Conformational analysis revealed that inulobiose extending all-trans conformation corresponded to φ = Ψ = ω = 180°. Fructofuranose moiety, the anomeric carbon was defined as C2. The definition of torsional angles φ = ϴ(C1-C2-0-CI'), Ψ = ϴ (C2-0-C 1′-C2′), and ω = ϴ(0-C1′-C2′-0′) followed the proposed convention. Glycosidic angle C1′0 l'C2′ was taken to be 114.0° and both O6 hydroxyl groups in inulobiose were fixed in a trans position, compelling the hydroxyl group to sterically favor comparison with the gauche orientation of sucrose structure. XRD analysis results indicated a typical cellulose type I. DSC and TGA analysis revealed a highly stable pocket until about 260°C.
Bioinspired Production of Antibacterial Sucrose Isomerase-Sponge for the Synthesis of Isomaltulose
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Isomaltulose is a new functional sweetener that possesses biological characteristics and can be obtained by enzymatic synthesis using sucrose as substrate. In this study, the sucrose isomerase (SIase) was successfully immobilized on the sponge synthesized with ϵ‐poly‐l‐lysine and gelatin. The inhibition zones proved that the sponge possessed a significant bacteriostatic function, which can effectively prevent the collapse of the scaffolds of the immobilized enzymes. The immobilized SIase activity reached up to 71.58 U g⁻¹ (the SIase loading was about 153.43 mg g⁻¹), and the activity recovery was approximately 84.50%. After immobilization, the optimum pH of SIase decreased from 6.0 to 5.5 and the optimum temperature increased from 30 °C to 40 °C. The affinity of SIase to substrate was basically unchanged. Immobilized SIase still exhibited more than 90% sucrose conversion after 13 consecutive cycles, which indicated that it had a good operational stability. Furthermore, the immobilized SIase has the potential for isomaltulose production, with 200 g L⁻¹ sucrose solution as its substrate in the food industry. Isomaltulose was isolated in 83.58% yield and high purity (97.3%).
Fructooligosaccharides and fructans analysis in plants and food crops
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Citation Excerpt :
However there is limited use of these methods because of technical, practical or even economical reasons, such as the cost of the equipment. Nuclear magnetic resonance (NMR) was first developed by some researchers to investigate the anomeric form, ring structure, and linkage of oligomers and polymers containing d-fructose and β-d-fructofuranosyl groups or residues [60–62]. Based on these applications and during the 1990s, Shiomi and Yamada [63] and Carpita et al. [64] identified different anomer configurations of some FOS using 1H NMR and 13C NMR.
Because fructooligosaccharides (FOS) and fructans are increasingly important in food and nutrition sciences, separation and analysis tools, in particular with the development of analytical chemistry, are slowly but rationally being developed for their separation and identification in plants, crops, and food products. Several chromatographic and other methods have been described to assess FOS and fructans, however, most of these methods are technically complicated, time-consuming and expensive. Although modern techniques have evolved tremendously, FOS and fructans analyses involve multiple and/or sequential extractions, chemical or biochemical polymers hydrolysis, and multiple chromatographic and/or other analytical runs to quantify these polymers. This paper aims to review and describe the different chromatographic techniques and other methods that are used to separate, analyze and quantify FOS and fructans
Bioassay-guided isolation of urease and α-chymotrypsin inhibitory constituents from the stems of Lawsonia alba Lam. (Henna)
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Citation Excerpt :
The specific rotation of compound 2 was − 38.0. Analysis of the NMR, DEPT, HMQC and HMBC (Table 2) revealed a fructose [39] moiety [δHa 3.70 (1H, d, J = 12.0 Hz), δHb 3.63 (1H, d, J = 12.0 Hz), δC 61.6, CH2-1, δH 4.03 (1H, d, J = 5.0 Hz), δC 83.2, CH-3, δH 3.88 (1H, dd, J = 6.5, 5.0 Hz), δC 78.4, CH-4, δH 3.83 (1H, ddd, J = 6.5, 2.5, 2.0 Hz), δC 83.8, CH-5, δHa 3.74 (1H, dd, J = 12.0, 2.5 Hz), δHb 3.60 (1H, dd, J = 12.0, 5.0 Hz), δC 62.6, CH2-6] substituted with a n-butyl chain [δH 3.61, (2H, t, J = 7.0 Hz), δC 61.9, CH2-1′, δH 1.53, (2H, m), δC 33.4, CH2-2′, δH 1.39, (2H, m), δC 20.4, CH2-3′, δH 0.92, (3H, t, J = 7.5 Hz), δC 14.2, CH3-4′] at one of the oxygen. In the 13C-NMR (Broad Band decoupled) spectrum a quaternary carbon present at δC 108.7 was attributed to C-2.
Seven constituents were isolated from the stems of Lawsonia alba Lam., following an activity-guided isolation, which include two new constituents, namely lawsorosemarinol (1) and lawsofructose (2), one known compound 2-(β-d-glucopyranosyloxy)-1, 4-naphthoquinone (3) and four compounds, 4-hydroxy coumarine (4), 3-(4-hyroxyphenyl)-triacontyl-(Z)-propenoate (5), 3-(4-hydroxy-3-methoxyphenyl)-triacontyl-(Z)-propenoate (6) and 7-hydroxy-4-methyl coumarin (7) first time isolated from Lawsonia alba. Their structure elucidation was based on spectroscopic data analyses. Compounds 3 and 7 showed a moderate inhibition of urease activity, while rest of them showed less than 50% inhibition. These compounds did not show any significant inhibition against α-chymotrypsin.
Fructans
2012, The Biochemistry of Plants: A Comprehensive Treatise

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^☆: Issued as NRCC Publication No. 17607

¹: Visiting Research Officer under the Exchange Programme of the Canadian international Development Agency; present address, Universidad de la Republica, Facultad de Quimica, Montevideo, Uruguay.

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Manifestation of anomeric form, ring structure, and linkage in the 13c-n.m.r. spectra of oligomers and polymers containing D-fructose: maltulose, isomaltulose, sucrose, leucrose, 1-kestose, nystose, inulin, and grass levan☆

Abstract

Methods Enzymol., Part C

Carbohydr. Res.

Carbohydr. Res.

Carbohydr. Res.

Biochem. Biophys. Res. Commun.

Carbohydr. Res.

Carbohydr. Res.

J. Am. Chem. Soc.

Carbohydr. Res.

Aust. J. Chem.

Can. J. Chem.

Can. J. Chem.

Manifestation of anomeric form, ring structure, and linkage in the ¹³c-n.m.r. spectra of oligomers and polymers containing D-fructose: maltulose, isomaltulose, sucrose, leucrose, 1-kestose, nystose, inulin, and grass levan☆