Intra- and Intermolecular H-Bonds of Alcohols in DMSO, 1H-NMR Analysis of Inter-Residue H-Bonds in Selected Oligosaccharides: Cellobiose, Lactose, N,N′-Diacetylchitobiose, Maltose, Sucrose, Agarose, and Hyaluronates

Bernet, Bruno; Vasella, Andrea

doi:10.1002/1522-2675(20000906)83:9<2055::aid-hlca2055>3.0.co;2-c

Cited by 43 publications

(16 citation statements)

References 31 publications

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“…The precise assignments of cellobiose in DMSO‐ d 6 /TEACl are shown in Table . The 1 H‐NMR spectrum exhibits sufficient resolution to separate the distinct proton signals of cellobiose which were consistent with the detailed assignments of the cellobiose peaks reported in Zhang's work . The signals of methenyl protons of C(1) and C(1′) of cellobiose merge into one peat at 4.3 ppm, whereas strong peaks at 1.1 and 3.2 ppm corresponded to the methyl (Ta) and methenyl (Tb) protons on TEA + , respectively.…”

Section: Resultssupporting

confidence: 87%

Effects of salt on homogeneous succinoylation of lignocellulosic fibers in dimethyl sulfoxide/tetraethylammonium chloride under mild condition

Chen

et al. 2015

J of Applied Polymer Sci

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Effects of salt in the homogeneous succinoylation of ball milled mulberry wood in dimethyl sulfoxide (DMSO)/tetraethylammonium chloride (TEACl) was investigated using viscometry and two-dimensional nuclear overhauser effect NMR spectroscopy (2D NOESY). The intrinsic viscosity of mulberry wood solution strongly depends on the TEACl dosage indicating that the change in hydrodynamic size of polymers caused by the interactions between salt and polymers in solution. 2D NOESY spectra reveal that TEA 1 cations bind to the cellobiose in DMSO by the interactions between methenyl of TEA 1 and C(1)/C(1 0 ) group of cellobiose and the intensities of the crosspeaks increased with an increase in TEACl dosage. Taking cellobiose as a model compound for cellulose, it can be expected that TEA 1 cations and cellulose forms a polyelectrolyte-like complex. The yields of homogeneous succinoylation of mulberry wood in DMSO/TEACl benefits from the interactions between TEA 1 cations and cellulose evidenced by weight percent gain, Fourier transform infrared spectra as well as CP/MAS 13 C-NMR spectra. V C VC 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41912.

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Section: Resultssupporting

confidence: 87%

Effects of salt on homogeneous succinoylation of lignocellulosic fibers in dimethyl sulfoxide/tetraethylammonium chloride under mild condition

Chen

et al. 2015

J of Applied Polymer Sci

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“…The former hydrophobic attraction does not seem to happen in DMSO solvents, whereas the effect of the latter is conceivable since the thixotropy and aggregation during the GPC measurements disappeared after blocking the hydroxyl groups of DNFB-PR2000 by phenylcarbamoylation. Some studies suggested the formation of hydrogen bonding in DMSO [32][33][34], while most of them have investigated intramolecular hydrogen bonding. As one of the studies suggested [34], upfield and downfield shifts should be observed for the resonances of H-donor and H-acceptor protons incorporated in hydrogen bonding, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…Some studies suggested the formation of hydrogen bonding in DMSO [32][33][34], while most of them have investigated intramolecular hydrogen bonding. As one of the studies suggested [34], upfield and downfield shifts should be observed for the resonances of H-donor and H-acceptor protons incorporated in hydrogen bonding, respectively. However, changes in the chemical shift values of OH groups were observed with all polyrotaxanes as compared to those of free CDs (see Experimental section and ref.…”

Section: Resultsmentioning

confidence: 99%

Strongly thixotropic viscosity behavior of dimethylsulfoxide solution of polyrotaxane comprising α-cyclodextrin and low molecular weight poly(ethylene glycol)

Araki

Ito

2007

Polymer

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A strong thixotropic viscosity behavior was observed when polyrotaxane prepared from α-cyclodextrins (CDs) and poly(ethylene glycol) (PEG) with a molecular weight of 2000 was dissolved in dimethylsulfoxide (DMSO). A 10 wt% solution liquefied by vigorous shaking was rapidly gelated by standing --this sol-gel transition was reversible. The time for recovering the viscosity was dependent on the polyrotaxane concentration, i.e., a 10wt% solution regelated within 30 s, whereas several hours were required for the gelation of a 2.5wt% solution. The thixotropic nature of the solution was also confirmed by the clockwise hysteresis curve of the viscosity when the shear rate was increased and decreased. The gel permeation chromatography (GPC) measurement of the polyrotaxane in DMSO exhibited peaks in the high molecular weight region. The peak disappeared after the phenylcarbamoylation of polyrotaxane, suggesting that the peak was due to loose aggregations of polyrotaxane in DMSO. On the other hand, the DMSO solution of polyrotaxane prepared from CD and PEG with a molecular weight of 3350-whose inclusion ratio (51%) is slightly lower than that of PEG2000 polyrotaxane (72%)-neither demonstrated the abovementioned thixotropic viscosity nor the peak corresponding to the aggregations occurring during the GPC measurement. The thixotropic behavior was speculated to be caused by the combined contribution of intermolecular attractive hydrogen bonding and higher rigidity of polyrotaxane prepared from PEG 2000 than that of polyrotaxane prepared from PEG3350, presumably due to the higher inclusion ratio of the former than that of the latter. Key Word: Polyrotaxane, Thixotropy, intermolecular hydrogen bonding 2 INTRODUCTIONPolyrotaxane is a typical supramolecular material that possesses linear molecule threading through many cyclic molecules, which can freely slide or rotate over the linear molecule [1][2][3][4]. Great advances have been made in the investigation of polyrotaxane since the discovery of the formation of pseudopolyrotaxane by the spontaneous inclusion complexation of cyclodextrins (CDs) and linear polymers by Harada et al. [5][6][7][8][9]. The formation of the inclusion complex with CDs and various linear polymers via spontaneous self-assembly was thoroughly investigated by Harada et al. [1,5,6], who successfully prepared polyrotaxane by binding bulky end groups (such as dinitrophenyl moieties) to the ends of pseudopolyrotaxane, i.e., the inclusion complex of CDs and PEG [7][8][9]. A wide variety of attractive concepts have been reported to date after the first finding by Harada, such as the preparation of a "molecular tube" by cross-linking adjacent CDs in single polyrotaxane followed by the dissociation of the included PEG [10], an insulated molecular wire comprising a conducting polymer and a molecular tube [11,12], a drug delivery system using polyrotaxane carrying drugs on the CD moiety [13], multivalent ligand system [14], the construction of an energy transfer system using polyrotaxane with photoluminescent...

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“…Cellobiose and methyl cellobioside in aqueous solutions have been studied extensively by NMR spectroscopy where various measures of coupling constants[14]–[19] have been determined. More recent studies have sought to quantify the populations of hydrogen bonds across the β-(1→4) linkages in solutions of disaccharides [18]–[21]. Cellobiose has also been investigated extensively by computation, from early stereochemical approaches[22] and molecular dynamics (MD) simulations[23]–[25] to modern quantum mechanical methods [26], [27].…”

Section: Introductionmentioning

confidence: 99%

Structural Evidence for Inter-Residue Hydrogen Bonding Observed for Cellobiose in Aqueous Solution

2012

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The structure of the disaccharide cellulose subunit cellobiose (4-O-β-D-glucopyranosyl-D-glucose) in solution has been determined via neutron diffraction with isotopic substitution (NDIS), computer modeling and nuclear magnetic resonance (NMR) spectroscopic studies. This study shows direct evidence for an intramolecular hydrogen bond between the reducing ring HO3 hydroxyl group and the non-reducing ring oxygen (O5′) that has been previously predicted by computation and NMR analysis. Moreover, this work shows that hydrogen bonding to the non-reducing ring O5′ oxygen is shared between water and the HO3 hydroxyl group with an average of 50% occupancy by each hydrogen-bond donor. The glycosidic torsion angles φH and ψH from the neutron diffraction-based model show a fairly tight distribution of angles around approximately 22° and −40°, respectively, in solution, consistent with the NMR measurements. Similarly, the hydroxymethyl torsional angles for both reducing and non-reducing rings are broadly consistent with the NMR measurements in this study, as well as with those from previous measurements for cellobiose in solution.

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Intra- and Intermolecular H-Bonds of Alcohols in DMSO, 1H-NMR Analysis of Inter-Residue H-Bonds in Selected Oligosaccharides: Cellobiose, Lactose, N,N′-Diacetylchitobiose, Maltose, Sucrose, Agarose, and Hyaluronates

Cited by 43 publications

References 31 publications

Effects of salt on homogeneous succinoylation of lignocellulosic fibers in dimethyl sulfoxide/tetraethylammonium chloride under mild condition

Effects of salt on homogeneous succinoylation of lignocellulosic fibers in dimethyl sulfoxide/tetraethylammonium chloride under mild condition

Strongly thixotropic viscosity behavior of dimethylsulfoxide solution of polyrotaxane comprising α-cyclodextrin and low molecular weight poly(ethylene glycol)

Structural Evidence for Inter-Residue Hydrogen Bonding Observed for Cellobiose in Aqueous Solution

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