Introduction to the Special Issue: Preparation, Physicochemical Properties and Application of Natural Plant Polysaccharides.

As natural products, plant polysaccharides have been demonstrated to induce a variety of biological activities by numerous epidemiological investigations and interventional studies, including immunomodulation and antioxidant, antibacterial, antitumor, hypolipidemic, hypoglycemic processes, etc [...].

The structural and functional characteristics of soluble dietary fibers modified from tomato pomace with increased content of lycopene.

The tomato pomace, a by-product of tomato processing, was rich in nutrients such as lycopene (Lyc), vitamins, phenols and soluble dietary fibers (SDF). Homogenization combined with enzymatic hydrolysis (HE) was firstly applied to obtain HE-pomace. The yield of Lyc was raised by 57.2% after HE treatment by the optimal condition. The extraction rate of HE-SDF was increased by 73.4%. In order to clarify the relationship between the SDF and the release of Lyc, SDFs were characterized by structural analysis and morphological determination. The results suggested that HE-SDF possessed smaller molecular weight and loose microstructure with shorter chains. It implied that the degradation of dietary fiber led to the release of Lyc molecules. Besides, HE-SDF exhibited stronger capacity of water-holding, glucose adsorption and bile acid binding. In conclusion, HE treatment possessed the potential to be applied as an excellent modification method, which improved the nutritional and economic value of tomato pomace.

Inhibition Mechanism of L-Cysteine on Maillard Reaction by Trapping 5-Hydroxymethylfurfural.

The Maillard reaction (MR) can affect the color, flavor, organoleptic properties, and nutritional value of food. Sometimes, MR is undesirable due to lowering the nutrient utilization, producing harmful neo-formed compounds, etc. In this case, it is necessary to control MR. Some chemical substances, such as phenolic acid, vitamins, aminoguanidine, and thiols extracted from garlic or onion, can effectively prevent MR. In this study, L-cysteine (L-cys) was found to inhibit MR after screening 10 sulfhydryl compounds by comparing their ability to mitigate browning. The inhibition mechanism was speculated to be related to the removal of 5-hydroxymethylfurfural (HMF), a key mid-product of MR. The reaction product of HMF and L-cys was identified and named as 1-dicysteinethioacetal-5-hydroxymethylfurfural (DCH) according to the mass spectrum and nuclear magnetic resonance spectrum of the main product. Furthermore, DCH was detected in the glutamic-fructose mixture after L-cys was added. In addition, the production of DCH also increased with the addition of L-cys. It also was worth noting that DCH showed no cell toxicity to RAW 264.7 cells. Moreover, the in vitro assays indicated that DCH had anti-inflammatory and antioxidant activities. In conclusion, L-cys inhibits MR by converting HMF into another adduct DCH with higher safety and health benefits. L-cys has the potential to be applied as an inhibitor to prevent MR during food processing and storage.

Production, structure and morphology of exopolysaccharides yielded by submerged fermentation of Antrodia cinnamomea.

Carbon and nitrogen sources in culture medium of Antrodia cinnamomea were optimized to eliminate the interference of exterior macromolecules on exopolysaccharide (EPS) yield by submerged fermentation. The results suggested that culture medium containing 50 g/L of glucose and 20 g/L of yeast extract as the optimal carbon and nitrogen sources could produce 1.03 g/L of exopolysaccharides. After purification, two heteropolysaccharides (AC-EPS1 and AC-EPS2) were obtained and characterized to provide the basic structure information. As the main component of the produced EPS, AC-EPS2 (accounting for 89.63%) was mainly composed of galactose (87.42%) with Mw (molecular weight) and R.M.S. (root-mean-square) radius of 1.18 × 105 g/mol and 25.3 nm, respectively. Furthermore, the spherical and flexible chain morphologies of EPS were observed in different solvents by TEM. The structural and morphological information of purified EPS were significant for further study on their structure-activity relationship and related applications.

Gelling and bile acid binding properties of gelatin-alginate gels with interpenetrating polymer networks by double cross-linking.

Interpenetrating polymer network (IPN) is an effective method to improve functional properties of hydrogels by forming cross-linking networks. In this study, the gelatin-alginate gels formed by the combination of enzymatic and ionic cross-linking were called IPN gels. Meanwhile, the gels with the treatment of only transglutaminase (TG) or Ca2+ were named as G-semi-IPN and A-semi-IPN, respectively. The formation of semi-IPN and IPN was confirmed by studies on rheology, thermodynamics and micro-morphology. The results showed that the IPN gels had improved gelling properties and structural stability. The functional properties of different gelatin-alginate gels were also investigated. It was firstly found that the IPN gels could enhance mechanical properties, decrease swelling capacity and had better bile acid binding capacity. These results of gelatin-alginate gels provide references and novel prospects of IPN for the application in the field of food industry.

Polysaccharides-protein interaction of psyllium and whey protein with their texture and bile acid binding activity.

Dietary fiber is a group of important food polysaccharides, which may improve gastrointestinal function and alter the bioavailability and nutritional value of other food components. The interaction mechanism of psyllium fiber (PSY) and whey protein (WP) and the influence on the characteristics of polysaccharides and protein were investigated. The results of circular dichroism spectra and differential scanning calorimetry analysis showed that PSY could protect WP by increasing its melting temperature. The textural profiles implied that WP could improve the edibility of the psyllium fiber. The IR spectrum and colorimetric assay indicated the product of Maillard reaction between psyllium and whey protein with the heating condition. The SEM showed that the structure of the mixture became stronger with higher temperature. Furthermore, the mixture with the ratio of WP/PSY as 1:2 had three times of the bile acid binding ability of PSY, which could be developed as a nutraceutical additive with prevention of hyperlipidemia.

A new heteropolysaccharide from the seed husks of Plantago asiatica L. with its thermal and antioxidant properties.

A new heteropolysaccharide (PMH) with a molecular weight of 1.4 × 103 kDa was isolated from the seed husks of Plantago asiatica L. The monosaccharide composition of PMH was determined as glucose, xylose, arabinose, rhamnose, galactose and galacturonic acid with a molar ratio of 1.0 : 1.8 : 2.4 : 3.8 : 4.9 : 8.5. The backbone of PMH consisted of 1,4-ß-d-GalpA with the side chains mainly composed of 1,3-α-d-Galp and 1,2-α-d-Galp which were attached to the O-3 of GlapA. The thermal analysis using the Flynn-Wall-Ozawa (FWO) method revealed that PMH had an apparent activation energy (Ea) of 173.1 kJ mol-1. PMH experienced a major decomposition during the heating process at a temperature of 91.1 °C with a dry weight loss of 31.1%. Moreover, PMH exhibited stronger antioxidant ability than commercial psyllium, partially due to its higher content of uronic acid. The results suggested that PMH could be used in functional foods due to its structural, thermal and antioxidant characteristics.

Formation of 3-MCPD Fatty Acid Esters from Monostearoyl Glycerol and the Thermal Stability of 3-MCPD Monoesters.

Formation of 3-monochloropropanediol (3-MCPD) esters from monostearoyl glycerol (MSG) was investigated under high temperature and low moisture conditions. Different organic and inorganic chlorides, including lindane, KCl, CaCl2, NaCl, MgCl2, AlCl3, CuCl2, MnCl2, SnCl2, ZnCl2, and FeCl3, were evaluated for their potential to react with MSG to form 3-MCPD and glycidyl esters at 120 and 240 °C using a UPLC-Q-TOF MS analysis. The results indicated that different chlorine compounds differed in their capacity to react with MSG and formed different products including 3-MCPD mono- and diesters, distearoylglycerol, and glycidyl esters. According to electron spin resonance (ESR) and Fourier transform infrared (FT-IR) spectroscopies, free radical mediated formation mechanisms involving either five-membered or six-membered cyclic acyloxonium free radicals (CAFR) from monoacylglycerol (MAG) were proposed. Tandem quadrupole-time-of-flight (Q-TOF) MS and MS/MS analyses confirmed the free radical mechanisms. In addition, the results from the present study showed that 3-MCPD monoester could be degraded upon thermal treatment and suggested a possible catalytic role of Fe3+ under the experimental conditions.

Liposome-like nanocapsules of dual drug-tailed betaine for cancer therapy.

A novel dual drug-tailed betaine conjugate amphiphile has been firstly synthesized in which the polar headgroup is derived from glycine betaine and the hydrophobic tails are chlorambucil molecules. The newly prepared conjugate undergoes self-assembly to form stable liposome-like nanocapsules as an effective carrier with high drug loading capacity. The nanocapsules showed higher cytotoxic effects to cancer cell lines than those of free chlorambucil in vitro, and inhibited tumor growth effectively in vivo. This strategy that utilizes new dual drug-tailed betaine conjugate amphiphile to construct a self-assembled nanoparticle drug delivery system may have great potential in cancer chemotherapy.

A novel alkaline hemicellulosic heteroxylan isolated from alfalfa (Medicago sativa L.) stem and its thermal and anti-inflammatory properties.

A novel hemicellulosic polysaccharide (ACAP) was purified from the cold alkali extraction of alfalfa stems and characterized as a heteroxylan with a weight-average molecular weight of 7.94 × 10(3) kDa and a radius of 58 nm. Structural analysis indicated that ACAP consisted of a 1,4-linked ß-D-Xylp backbone with 4-O-MeGlcpA and T-L-Araf substitutions at O-2 and O-3 positions, respectively. Transmission electron microscopy (TEM) examination revealed the entangled chain morphology of ACAP molecules. The evaluation of thermal degradation property revealed a primary decomposition temperature range of 238.8-314.0 °C with an apparent activation energy (Ea) and a pre-exponential factor (A) of 220.0 kJ/mol and 2.81 × 10(24)/s, respectively. ACAP also showed significant inhibitory activities on IL-1ß, IL-6, and COX-2 gene expressions in cultured RAW 264.7 mouse macrophage cells. These results suggested the potential utilization of ACAP in functional foods and dietary supplement products.

Liposomes assembled from a dual drug-tailed phospholipid for cancer therapy.

We report a novel dual drug-tailed phospholipid which can form liposomes as a combination of prodrug and drug carrier. An amphiphilic dual chlorambucil-tailed phospholipid (DCTP) was synthesized by a straightforward esterification. With two chlorambucil molecules as hydrophobic tails and one glycerophosphatidylcholine molecule as a hydrophilic head, the DCTP, a phospholipid prodrug, undergoes assembly to form a liposome without any additives by the thin lipid film technique. The DCTP liposomes, as an effective carrier of chlorambucil, exhibited a very high loading capacity and excellent stability. The liposomes had higher cytotoxic effects to cancer cell lines than free DCTP and chlorambucil. The in vivo antitumor activity assessment indicated that the DCTP liposomes could inhibit the tumor growth effectively. This novel strategy of dual drug-tailed phospholipid liposomes may be also applicable to other hydrophobic anticancer drugs which have great potential in cancer therapy.

Separating four diastereomeric pairs of dihydroflavonol glycosides from Engelhardia roxburghiana using high performance counter-current chromatography.

Four pairs of diastereomers were successfully isolated and separated from the water extract of Engelhardia roxburghiana by high performance counter-current chromatography (HPCCC) using a two-step procedure. The diastereomers were initially separated by a two-phase solvent system composed of n-hexane-n-butanol-0.1% trifluoroacetic acid (1:2:3, v/v/v) and followed by the same solvent system using hydroxypropyl-ß-cyclodextrin (HP-ß-CD) as an additive. The chromatographic conditions, elution mode, and concentrations of the additive were refined. The two-step HPCCC isolation yielded 43.7mg (2S, 3S)-astilbin, 27.6mg (2R, 3R)-astilbin, 5.9mg (2S, 3R)-astilbin, 4.8mg (2R, 3S)-astilbin, 6.9mg (2S, 3S)-engelitin, 3.1mg (2R, 3R)-engelitin, 8.2mg (2S, 3R)-engelitin, and 6.0mg (2R, 3S)-engelitin from 384mg crude extract in four runs with purities of 99.3%, 96.2%, 99.8%, 99.9%, 97.0%, 96.5%, 96.1%, and 96.8%, respectively. The present study revealed that HP-ß-CD can be used as an additive in HPCCC to effectively improve the resolution of the diastereomers. The established HPCCC method may serve as an approach to obtain high purity diastereomers on a large scale.

A novel alkali extractable polysaccharide from Plantago asiatic L. Seeds and its radical-scavenging and bile acid-binding activities.

A new acidic polysaccharide (PLP) was isolated and characterized from Plantago asiatic L. seeds by hot alkali extraction and chromatographic purification using DEAE cellulose and Sephacryl S-400 columns. PLP has a molecular weight of 1.15 × 10(6) Da, and a monosaccharide composition of xylose (Xyl), arabinose (Ara), glucuronic acid (GlcA), and galactose (Gal) in a molar ratio of 18.8:7.2:6.1:1. The results of methylation analysis, FT-IR, and 1D and 2D NMR indicated that PLP was a highly branched heteroxylan of ß-1,4-linked Xylp backbone with three α-GlcAp-(1→3)-Araf attached to the O-3 position and one α-T-linked-GlcAp and one α-Araf-(1→5)-Araf attached to the O-2 position every eight monosaccharide residues. PLP exhibited scavenging abilities against hydroxyl, peroxyl anion, and DPPH radicals in vitro and showed significant binding capacities against cholic and chenodeoxycholic acids, suggesting its possible cholesterol-lowering activity. The results demonstrated the potential use of PLP in functional foods and nutraceuticals.

Preparation of novel cross-linked and octylated caseinates using a biphasic enzymatic procedure and their functional properties.

A novel microbial transglutaminase-catalyzed aqueous-organic biphasic reaction system was successfully developed to prepare caseinate derivatives by cross-linking and incorporating nonpolar octyl tails for the first time. SDS-PAGE and (1)H NMR analysis confirmed that cross-linking and octyl conjugation occurred simultaneously. The octyl substitution degree (SD) was measured by (1)H NMR and used as an index to determine a suitable reaction condition. It was found that at the condition of 0.125% (w/v) protein concentration and 6 h of reaction time, the modified caseinate had the highest SD of 28.96%. The modified caseinate also had an increased surface hydrophobicity, better emulsifying activity, and improved thermal and salt stabilities. However, its emulsion stability or in vitro enzymatic digestibility was slightly lower than that of the native caseinate.

Partial least-squares-discriminant analysis differentiating Chinese wolfberries by UPLC-MS and flow injection mass spectrometric (FIMS) fingerprints.

Lycium barbarum L. fruits (Chinese wolfberries) were differentiated for their cultivation locations and the cultivars by ultraperformance liquid chromatography coupled with mass spectrometry (UPLC-MS) and flow injection mass spectrometric (FIMS) fingerprinting techniques combined with chemometrics analyses. The partial least-squares-discriminant analysis (PLS-DA) was applied to the data projection and supervised learning with validation. The samples formed clusters in the projected data. The prediction accuracies by PLS-DA with bootstrapped Latin partition validation were greater than 90% for all models. The chemical profiles of Chinese wolfberries were also obtained. The differentiation techniques might be utilized for Chinese wolfberry authentication.

Characterization of a novel alkali-soluble heteropolysaccharide from tetraploid Gynostemma pentaphyllum Makino and its potential anti-inflammatory and antioxidant properties.

A novel polysaccharide (GPP-S), with a molecular mass of 1.2 × 10(6) Da, was isolated from the tetraploid Gynostemma pentaphyllum Makino by alkali extraction followed by purifications using DEAE and Sephacryl S-400 column chromatographies. The monosaccharide composition of GPP-S was determined as rhamnose, arabinose, glucose, and galactose with a molar ratio of 1.00:3.72:19.49:7.82. The structural analysis suggested that the backbone of GPP-S is (1→4)-linked-glucose and (1→6)-linked-galactose with a (1→4,6)-linked-glucose branch every six monosaccharide residues. The terminals were 1-)-α-arabinose, glucuronic acid, and other monosaccharides. GPP-S exhibited scavenging capacities against hydroxyl, peroxyl, and DPPH(•) radicals in vitro. GPP-S also had inhibitory activities on IL-1ß, IL-6, and COX-2 gene expressions in RAW 264.7 mouse macrophage cells. These results suggested that GPP-S could be developed as a bioactive ingredient for functional foods and dietary supplements.

Cationic ß-lactoglobulin nanoparticles as a bioavailability enhancer: comparison between ethylenediamine and polyethyleneimine as cationizers.

Cationic ß-lactoglobulin (CBLG) was synthesized by two strategies: extensive conjugation of ethylenediamine (EDA) and limited cationization with polyethyleneimine (PEI). Both methods provided CBLG with satisfactory water solubility and resistance to peptic digestion. Compared with EDA-derived CBLG (C-EDA), PEI-derived CBLG (C-PEI) exhibited a higher zeta potential (54.2 compared to 32.4mV for C-EDA), which resulted in significantly elevated mucoadhesion (439% and 118% higher than BLG and C-EDA, respectively) in a quartz crystal microbalance (QCM) study. In addition, PEI caused reduced conformational disruption on BLG compared to EDA as evidenced by FTIR measurement. This character, together with the steric hindrance provided by PEI, caused a phenomenal reduction in tryptic digestibility by at least 75% compared to C-EDA. In the presence of aqueous acetone, C-PEI aggregated spontaneously into nanoparticles with average size of 140 nm and narrow size distribution. These merits made C-PEI a useful material that provides desirable solubility and protection for orally administrated nutraceuticals or drugs.

Simultaneous HPLC quantification of five major triterpene alcohol and sterol ferulates in rice bran oil using a single reference standard.

A high performance liquid chromatography (HPLC) method was developed for simultaneous quantification of five major triterpene alcohol and sterol ferulates in rice bran oils (RBO) with a single internal standard, cycloartenyl ferulate. The five compounds are cycloartenyl ferulate (1), 24-methylene cycloartanyl ferulate (2), campesteryl ferulate (3), sitosteryl ferulate (4) and stigmastanyl ferulate (5). All five compounds had good linear concentration-measurement relationships (r(2) ≥ 0.9995) and possessed similar relative response factors. The relative deviation of this method was less than 2.5% for intra- and inter-day assays, and the average recovery varied from 95.1% to 99.4%. The new method was validated by comparing the amount of 24-methylene cycloartanyl ferulate (2) in 17 RBO samples obtained with this method and that with an external standard method. This method was also successfully applied to determine five major triterpene alcohol and sterol ferulates in 17 batches of RBO samples. The results demonstrated that the present method could be utilised for quality control of RBO since some of the reference standards are not commercially available.

Fabrication, characterization and antimicrobial activities of thymol-loaded zein nanoparticles stabilized by sodium caseinate-chitosan hydrochloride double layers.

Thymol-loaded zein nanoparticles stabilized with sodium caseinate (SC) and chitosan hydrochloride (CHC) were prepared and characterized. The SC stabilized nanoparticles had well-defined size range and negatively charged surface. Due to the presence of SC, the stabilized zein nanoparticles showed a shift of isoelectric point from 6.18 to 5.05, and had a desirable redispersibility in water at neutral pH after lyophilization. Coating with CHC onto the SC stabilized zein nanoparticles resulted in increased particle size, reversal of zeta potential value from negative to positive, and improved encapsulation efficiency. Both thymol-loaded zein nanoparticles and SC stabilized zein nanoparticles had a spherical shape and smooth surface, while the surfaces of CHC-SC stabilized zein nanoparticles seemed rough and had some clumps. Encapsulated thymol was more effective in suppressing gram-positive bacterium than un-encapsulated thymol for a longer time period.

Identification and quantification of phytochemical composition and anti-inflammatory, cellular antioxidant, and radical scavenging activities of 12 Plantago species.

Twenty-eight seed samples of 12 Plantago species were investigated for their chemical compositions and anti-inflammatory, cellular antioxidant, and radical scavenging properties. A new UPLC-UV procedure was developed and applied to quantify acteoside and geniposidic acid, the characteristic constituents of the genus Plantago. The amounts of acteoside and geniposidic acid ranged from 0.07 to 15.96 mg/g and from 0.05 to 10.04 mg/g in the tested samples, respectively. Furthermore, 26 compounds were tentatively identified by UPLC/Q-TOF-MS analysis. The Plantago samples significantly differed in their phytochemical compositions. The extracts of Plantago seeds also showed inhibitory effects on LPS-induced IL-1ß, IL-6, and COX-2 mRNA expression in RAW 264.7 mouse macrophage cells. Additionally, significant variations were observed among different samples on cellular antioxidant activities in HepG2 cells, as well as DPPH and hydroxyl radical scavenging capacities. The results from this study may be used to promote the use of the genus Plantago in improving human health.