scholarly journals Tuning the Properties of High Molecular Weight Chitosans to Develop Full Water Solubility Within a Wide pH Range

2020 ◽  
Author(s):  
Anderson Fiamingo ◽  
Sergio Paulo Campana Filho ◽  
Osvaldo Novais Oliveira Junior
Keyword(s):  
Molecular Weight ◽  
Biomedical Applications ◽  
Random Distribution ◽  
Water Solubility ◽  
Aqueous Media ◽  
Degree Of Polymerization ◽  
Molecular Weights ◽  
H Nmr ◽  
Wide Ph Range ◽  
Ph Range

<p>The preparation of chitosans soluble in physiological conditions has been sought for years, but so far solubility in non-acidic aqueous media has only been achieved at the expense of lowering chitosan molecular weight. In this work, we applied the multistep ultrasound-assisted deacetylation process (USAD process) to β-chitin and obtained extensively deacetylated chitosans with high molecular weights (Mw ≥ 1,000,000 g mol<sup>-1</sup>). The homogeneous <i>N</i>-acetylation of a chitosan sample resulting from three consecutive USAD procedures allowed us to produce chitosans with a high weight average degree of polymerization (DPw ≈ 6,000) and tunable degrees of acetylation (DA from 5 to 80%). <i>N</i>-acetylation was carried out under mild conditions to minimize depolymerization, while preserving a predominantly random distribution of 2-amino-2-deoxy-D-glucopyanose (<i>GlcN</i>) and 2-acetamido-2-deoxy-D-glucopyanose (<i>GlcNAc</i>) units. This close to random distribution, inferred with deconvolution of nuclear magnetic resonance (<sup>1</sup>H NMR) spectra, is considered as responsible for the solubility within a wide pH range. Two of the highly <i>N</i>-acetylated chitosans (DA ≈ 60 % and ≈ 70 %) exhibited full water solubility even at neutral pH, which can expand the biomedical applications of chitosans. </p>

scholarly journals Tuning the Properties of High Molecular Weight Chitosans to Develop Full Water Solubility Within a Wide pH Range

2020 ◽  
Author(s):  
Anderson Fiamingo ◽  
Sergio Paulo Campana Filho ◽  
Osvaldo Novais Oliveira Junior
Keyword(s):  
Molecular Weight ◽  
Biomedical Applications ◽  
Random Distribution ◽  
Water Solubility ◽  
Aqueous Media ◽  
Degree Of Polymerization ◽  
Molecular Weights ◽  
H Nmr ◽  
Wide Ph Range ◽  
Ph Range

<p>The preparation of chitosans soluble in physiological conditions has been sought for years, but so far solubility in non-acidic aqueous media has only been achieved at the expense of lowering chitosan molecular weight. In this work, we applied the multistep ultrasound-assisted deacetylation process (USAD process) to β-chitin and obtained extensively deacetylated chitosans with high molecular weights (Mw ≥ 1,000,000 g mol<sup>-1</sup>). The homogeneous <i>N</i>-acetylation of a chitosan sample resulting from three consecutive USAD procedures allowed us to produce chitosans with a high weight average degree of polymerization (DPw ≈ 6,000) and tunable degrees of acetylation (DA from 5 to 80%). <i>N</i>-acetylation was carried out under mild conditions to minimize depolymerization, while preserving a predominantly random distribution of 2-amino-2-deoxy-D-glucopyanose (<i>GlcN</i>) and 2-acetamido-2-deoxy-D-glucopyanose (<i>GlcNAc</i>) units. This close to random distribution, inferred with deconvolution of nuclear magnetic resonance (<sup>1</sup>H NMR) spectra, is considered as responsible for the solubility within a wide pH range. Two of the highly <i>N</i>-acetylated chitosans (DA ≈ 60 % and ≈ 70 %) exhibited full water solubility even at neutral pH, which can expand the biomedical applications of chitosans. </p>

scholarly journals Synthesis of water-soluble chitosan for biomedical applications

2015 ◽  
Vol 18 (3) ◽  
pp. 170-180
Author(s):  
Anh Thi Tram Tu ◽  
Huy Thuc Ha
Keyword(s):  
Drug Delivery ◽  
Molecular Weight ◽  
Iron Oxide ◽  
Biomedical Applications ◽  
Drug Delivery Systems ◽  
Water Soluble ◽  
Oxide Nanoparticles ◽  
Wide Ph Range ◽  
Ft Ir ◽  
Ph Range

Highly deacetylated chitosan (CS) reacted with anhydride acetic (Ac2O) to produce chitosan with various degree of deacetylation (DDA) depending on the CS/Ac2O ratios. The structure of products was characterized by FT-IR, 1H NMR, 13C NMR, and the molecular weight was identified by GPC. The DDA of products decreases as the CS/Ac2O ratio increases. The products with less than 80 % DDA were soluble in water with a wide pH range. The water-soluble chitosan can be used in many biomedical applications such as manufacturing drug delivery systems or functionalized iron oxide nanoparticles.

scholarly journals Oligomeric alkylpyridinium surfactants prepared via ATRP

e-Polymers ◽  
2011 ◽  
Vol 11 (1) ◽  
Author(s):  
Xin Su ◽  
Zonglin Chu ◽  
Ya Shuai ◽  
Zanru Guo ◽  
Yujun Feng
Keyword(s):  
Aqueous Solution ◽  
Molecular Weight ◽  
Surface Tension ◽  
Critical Micelle Concentration ◽  
Aqueous Media ◽  
Degree Of Polymerization ◽  
Surface Activities ◽  
H Nmr ◽  
Molecular Weight Distributions ◽  
Weight Distributions

AbstractA series of oligomeric alkylpyridinium surfactants were prepared directly in aqueous media by atom transfer radical polymerization (ATRP) of a surfmer, 4- vinyl-N-dodecylpyridinium bromide, and their surface activities were examined in comparison with the surfmer. The resulting oligomers have narrow molecular weight distributions, with polydispersity indices in the range of 1.17-1.23. By using 2-morpholinoethyl 2-bromo-2-methylpropanoate as ATRP initiator, the molecular weight of oligomeric surfactants was characterized by 1H NMR and the results were close to those obtained from GPC analysis. It was found that critical micelle concentration (CMC) of the oligomeric alkylpyridinium surfactants shifted to lower concentrations with increasing degree of polymerization (DPn), and their γ-cmc values were smaller by about 4 to 8 mN/m than that of the corresponding surfmer. Among the series of surfactants, the oligomer with highest DPn showed the greatest efficiency in lowering the surface tension in aqueous solution.

Coagulation performance of cucurbit[8]uril for the removal of azo dyes: effect of solution chemistry and coagulant dose

2018 ◽  
Vol 78 (2) ◽  
pp. 415-423 ◽  
Author(s):  
Wendong Wang ◽  
Zhiwen Chen ◽  
Kun Wu ◽  
Zongkuan Liu ◽  
Shengjiong Yang ◽  
...  
Keyword(s):  
Solution Chemistry ◽  
Color Removal ◽  
Dye Wastewater ◽  
Removal Rates ◽  
Molecular Weights ◽  
Coagulation Performance ◽  
Wide Ph Range ◽  
Ph Range ◽  
Significant Attention ◽  
Cr Removal

Abstract Dye wastewater has attracted significant attention because of its wide pH range and high content of color. In this work, the coagulation performances of cucurbit[8]uril for the removal of color from acid red 1 (AR1), orange II (OII), and Congo red (CR) dye wastewaters were investigated. Experimental results showed that color removal rates of greater than 95% for AR1, OII and CR were achieved at pH 6.0, when the dosage of cucurbit[8]uril was 1.51, 3.01 and 0.38 mmol·L−1, respectively. Under identical conditions, the color removal efficiencies of AR1 and CR were higher than OII, due to the larger molecular weights and more active hydroxyl and amino groups. Moreover, steady increases in AR1, OII and CR removal rates were recorded with increasing ionic strength. Such increases may be related to the reduction in thickness of the surface solvent membrane surrounding the dye colloids at high ionic strengths. Furthermore, Fourier transform infrared spectra demonstrated that no new bonds or functional groups were formed during coagulation, which indicates that the removal of AR1, OII and CR was primarily a physical process. The hydrogen bonds and inclusion complexes formed between cucurbit[8]uril and AR1, OII and CR contributed to the removal of color in coagulation predominantly.

scholarly journals Formation of highly quaternized N,N,N-trimethylchitosan: a chemoselective methodology in aqueous media

2019 ◽  
Vol 91 (3) ◽  
pp. 489-496 ◽  
Author(s):  
Youssouf D. Soubaneh ◽  
Steeven Ouellet ◽  
Caroline Dion ◽  
Jonathan Gagnon
Keyword(s):  
Biomedical Applications ◽  
Chemical Shifts ◽  
Aqueous Media ◽  
Acid Base ◽  
Specific Chemical ◽  
H Nmr ◽  
Low Degree ◽  
Simple Step ◽  
Carbonate Salt

Abstract N,N,N-Trimethylchitosan (TMC) represents a rare example of cationic polysaccharides and numerous studies have shown its potential in biological and biomedical applications. TMC with high degrees of quaternization (DQ) were synthesized from N-methylation of N,N-dimethylchitosan (DMC), which was obtained by reductive alkylation of high molecular weight chitosan in a simple step process and in good yields. The effects of base and solvents were evaluated on the quaternization reaction. The N-methylation of DMC was performed selectively by CH3I and carbonate in water where quaternization was achieved quantitatively with a low degree of O-methylation (17 %). Moreover, the greener procedure allows easy recovery and purification by conventional filtration as a carbonate salt, in which the anion can be exchanged by an acid-base reaction. Quantification of DQ involving 1H NMR integration of methyl peaks must be performed on protonated TMC. High field NMR spectra of TMC showed two specific chemical shifts for anomeric peaks (5.0 and 5.4 ppm) that can also be used for the determination of DQ. This latter method avoids the superimposition problems with other pyranosyl peaks.

THE VISCOSITY – MOLECULAR WEIGHT RELATION FOR POLY-levo-2,3-BUTANEDIYL o-PHTHALATE

1948 ◽  
Vol 26b (12) ◽  
pp. 783-797
Author(s):  
R. W. Watson ◽  
N. H. Grace
Keyword(s):  
Molecular Weight ◽  
High Purity ◽  
Molecular Orientation ◽  
Degree Of Polymerization ◽  
Solution Viscosity ◽  
Dilute Solution ◽  
Molecular Weights ◽  
Complex Relation ◽  
End Group ◽  
Long Chain

The inherent viscosities of dilute solutions of acidic polyesters of high purity have been compared with number average molecular weights accurately determined by end-group titration. For unfractionated resins with a degree of polymerization from 2 to 11 [Formula: see text] the viscosity – molecular weight relation is linear in chloroform at 25 °C. Where [Formula: see text], K = 1.923 × 10−5 and β = 0.0176. For fractionated polyesters from DP 5 to 8, K = 1.959 × 10−6 and β = 0.0161. For unfractionated resins with a DP > 11, molecular weights increase more rapidly than inherent viscosities. Above [Formula: see text] for fractionated resins linearity is resumed, and the slope increases. Several attempts have been made to explain this complex relation. Apparently the short chains remain linear, and the formation of anisotropic fibers at a DP close to 100 establishes a degree of molecular orientation in the long-chain superpolyesters. Isomerization of levo-diol to the diastereoisomer during polycondensation is without effect on the dilute solution viscosity of the resulting resin. Preferential degradation of the longer chains is assumed to be partially responsible for the decreasing slope from DP 11 to 65. As yet it has not been possible to assess the roles played by changes in size distribution, and variation in solvation with increasing chain length, but the data point to a curved viscosity – molecular weight relation in chloroform at 25 °C.

scholarly journals The molecular-weight-dependence of the anti-coagulant activity of heparin

1978 ◽  
Vol 175 (2) ◽  
pp. 691-701 ◽  
Author(s):  
T C Laurent ◽  
A Tengblad ◽  
L Thunberg ◽  
M Höök ◽  
U Lindahl
Keyword(s):  
Molecular Weight ◽  
Binding Sites ◽  
Random Distribution ◽  
Degree Of Polymerization ◽  
Molecular Weight Range ◽  
High Affinity ◽  
Predicted Probability ◽  
Coagulant Activity ◽  
The Relationship ◽  
Molecular Weight Fractions

It is proposed that the anti-coagulant activity of heparin is related to the probability of finding, in a random distribution of different disaccharides, a dodecasaccharide with the sequence required for binding to antithrombin. It is shown that this probability is a function of the degree of polymerization of heparin. The hypothesis has been been tested with a series of narrow-molecular-weight-range fractions ranging from 5,600 to 36,000. The fractions having mol.wts. below 18,000 (comprising 85% of the original preparation) followed the predicted probability relationship as expressed by the proportion of molecules capable of binding to antithrombin. The probability that any randomly chosen dodecasaccharide sequence in heparin should bind to antithrombin was calculated to 0.022. The fraction with mol.wt. 36,000 contained proteoglycan link-region fragments, which may explain the deviation of the high-molecular-weight fractions from the hypothetical relationship. The relationship between anti-coagulant activity and molecular weight cannot be explained solely on the basis of availability of binding sites for antithrombin. The activity of high-affinity heparin (i.e. molecules containing high-affinity binding sites for antithrombin), determined either by a whole-blood clotting procedure or by thrombin inactivation in the presence of antithrombin, thus remained dependent on molecular weight. Possible explanations of this finding are discussed. One explanation could be a requirement for binding of thrombin to the heparin chain adjacent to antithrombin.

A nuclear magnetic resonance study of the equilibria and kinetics of the reaction of penicillamine with cystine and related disulfides

1985 ◽  
Vol 63 (8) ◽  
pp. 2225-2231 ◽  
Author(s):  
Yvon Theriault ◽  
Dallas L. Rabenstein
Keyword(s):  
Random Distribution ◽  
Ph Dependence ◽  
Thiol Group ◽  
Nuclear Magnetic Resonance Study ◽  
Mercaptoacetic Acid ◽  
Exchange Reactions ◽  
H Nmr ◽  
Mixed Disulfide ◽  
Ph Range ◽  
Kinetics Of

The thiol/disulfide exchange reactions of penicillamine (PSH) with cystine and several related disulfides (RSSR) have been studied by 1H nmr. The reactions take place in two steps:[Formula: see text]The equilibria and kinetics of the reactions of PSH with cystine were characterized over the pH range 5–8, while the reactions with the disulfides of cysteamine, homocysteine, 2-mercaptoethanol, mercaptoacetic acid, 3-mercaptopropionic acid, and mercaptosuccinic acid were studied at neutral pH. From the pH dependence of the rate of the reaction of PSH with cystine, the reactive species are identified as penicillamine with its amino group protonated and its thiol group deprotonated and cystine and penicillamine–cysteine mixed disulfide with their amino groups protonated. For all the disulfides studied, the extent to which the first reaction occurs is within a factor of 2–3 of that predicted by a random distribution, while the extent to which the second reaction occurs is considerably less than for a random distribution. This is attributed to steric effects due to the two methyl groups next to the sulfur of penicillamine.

scholarly journals Poly(glycolide) multi-arm star polymers: Improved solubility via limited arm length

2010 ◽  
Vol 6 ◽  
Author(s):  
Florian K Wolf ◽  
Anna M Fischer ◽  
Holger Frey
Keyword(s):  
Molecular Weight ◽  
Ring Opening ◽  
Biomedical Applications ◽  
Weight Control ◽  
Glycolic Acid ◽  
Polymer Melt ◽  
Degree Of Polymerization ◽  
Star Block Copolymers ◽  
Grafting From ◽  
Low Solubility

Due to the low solubility of poly(glycolic acid) (PGA), its use is generally limited to the synthesis of random copolyesters with other hydroxy acids, such as lactic acid, or to applications that permit direct processing from the polymer melt. Insolubility is generally observed for PGA when the degree of polymerization exceeds 20. Here we present a strategy that allows the preparation of PGA-based multi-arm structures which significantly exceed the molecular weight of processable oligomeric linear PGA (<1000 g/mol). This was achieved by the use of a multifunctional hyperbranched polyglycerol (PG) macroinitiator and the tin(II)-2-ethylhexanoate catalyzed ring-opening polymerization of glycolide in the melt. With this strategy it is possible to combine high molecular weight with good molecular weight control (up to 16,000 g/mol, PDI = 1.4–1.7), resulting in PGA multi-arm star block copolymers containing more than 90 wt % GA. The successful linkage of PGA arms and PG core via this core first/grafting from strategy was confirmed by detailed NMR and SEC characterization. Various PG/glycolide ratios were employed to vary the length of the PGA arms. Besides fluorinated solvents, the materials were soluble in DMF and DMSO up to an average arm length of 12 glycolic acid units. Reduction in the T g and the melting temperature compared to the homopolymer PGA should lead to simplified processing conditions. The findings contribute to broadening the range of biomedical applications of PGA.

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