Synthesis and Application of Methyl N,O-Hydroxylamine Muramyl Peptides

The innate immune system's interaction with bacterial cells plays a pivotal role in a variety of human diseases. Carbohydrate units derived from a component of bacterial cell wall, peptidoglycan (PG), are known to stimulate an immune response. Nonetheless, access to modified late-stage peptidoglycan intermediates is limited due to their synthetic complexity. A method to rapidly functionalize PG fragments is needed to better understand the natural host–PG interactions. Here methyl N,O-hydroxylamine linkers are incorporated onto a synthetic PG derivative, muramyl dipeptide (MDP). The modification of MDP maintained the ability to stimulate a nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) immune response dependent on the expression of nucleotide-binding oligomerization domain-containing protein 2 (Nod2). Intrigued by this modification's maintenance of biological activity, several applications were explored. Methyl N,O-hydroxylamine MDP was amendable to N-hydroxylsuccinimide (NHS) chemistry for bioconjugation to fluorophores as well as a self-assembled monolayer for Nod2 surface plasmon resonance analysis. Finally, linker incorporation was applicable to larger PG fragments, both enzymatically generated from Escherichia coli or chemically synthesized. This methodology provides rapid access to PG probes in one step and allows for the installation of a variety of chemical handles to advance the molecular understanding of PG and the innate immune system.     

Unusual Two-Step Assembly of a Minimalistic Dipeptide-Based Functional Hypergelator

Self-assembled peptide hydrogels represent the realization of peptide nanotechnology into biomedical products. There is a continuous quest to identify the simplest building blocks and optimize their critical gelation concentration (CGC). Herein, a minimalistic, de novo dipeptide, Fmoc-Lys(Fmoc)-Asp, as an hydrogelator with the lowest CGC ever reported, almost fourfold lower as compared to that of a large hexadecapeptide previously described, is reported. The dipeptide self-assembles through an unusual and unprecedented two-step process as elucidated by solid-state NMR and molecular dynamics simulation. The hydrogel is cytocompatible and supports 2D/3D cell growth. Conductive composite gels composed of Fmoc-Lys(Fmoc)-Asp and a conductive polymer exhibit excellent DNA binding. Fmoc-Lys(Fmoc)-Asp exhibits the lowest CGC and highest mechanical properties when compared to a library of dipeptide analogues, thus validating the uniqueness of the molecular design which confers useful properties for various potential applications.     

L-丙氨酰-L-酪氨酸二肽化学合成研究

以L-酪氨酸和L-丙氨酸为原料,苄氧羰基保护丙氨酸,甲酯保护酪氨酸,EDCI-HOBt法合成丙酪二肽,总摩尔收率（以酪氨酸计）为42%,结构经IR、APCI-MS、NMR表征。     

Sugar replacement in sweetened bakery goods

This review presents the state‐of‐the‐art concerning the application of natural and artificial high‐intensity sweeteners, fructans and bulking agents such as polyols as sugar replacers in sweet‐baked goods and their effects on product characteristics. The recent much publicised attention given to weight gain of the population and its consequences on the occurrence of diet‐related diseases in developed countries has influenced the food manufacturers attempts to provide the consumer with reduced energy products. The replacement of sucrose in sweet bakery products by alternative natural or artificial sweeteners can be a challenging issue. Sucrose as a main ingredient in sweet bakery products contributes, aside from providing sweetness, to numerous processing and product characteristics. Intense sweeteners have a high sweetness compared with sucrose but lack in their contribution to the body of the product, whereas the replacement of sucrose with bulking sweeteners may result in products with a similar body but a lack in taste and flavour.     

Oral and intestinal digestion of oligosaccharides as potential sweeteners: A systematic evaluation

The utilisation of oligosaccharides by oral microorganisms and intestinal enzymes are important factors in determining their effectiveness as alternative sweeteners. In this study, classes of naturally occurring sugars were assessed using in vitro models for oral and intestinal digestibility, in order to test the influence of chemical structure on functional properties. Amongst the classes of sucrose isomers, α-glucobioses, β-glucobioses and sucrose-based oligosaccharides, structures were identified that were not utilised by the common oral bacterium Streptococcus mutans, and would therefore contribute to the non-cariogenic potential of a sweetener. Analysis of the rate and products of digestion by a rat glucosidase mixture was used to determine the relative intestinal digestibility. The results showed that oligosaccharides containing a (1 → 6)-β-Glc group, including gentiobiose and gentiobiitol, together with melezitose, a sucrose-derived oligosaccharide containing a α-Glc-(1 → 3)-Fru moiety were resistant to digestion by both S. mutans and mammalian intestinal enzymes, highlighting their potential as dietary sugar substitutes.     

一种新型二肽甜味剂的合成及表征

以3-环己基-L-丙氨酸、Boc-L-天冬氨酸-4-苄酯为原料合成二肽L-天冬氨酰-3-环己基-L-丙氨酸-1-甲酯(Ⅰ),以3-羟基-4-甲氧基苯甲醛为原料经过Witting反应、H2还原和DIBAL-H还原三步反应合成3-羟基-4-甲氧基苯丙醛(Ⅱ),然后Ⅰ与Ⅱ在氢气、Pd/C催化作用下进行还原氨化反应,得到目标产物N-[3-(3-羟基-4-甲氧基苯基)丙基]-α-L-天冬氨酰-3-环己基-L-丙氨酸-1-甲酯(Ⅲ),总产率为47%。产物的结构采用IR、~1HNMR、~(13)CNMR和HRMS进行表征,并验证其甜度约为蔗糖的25000倍。合成终产物的最佳工艺条件为:n(Ⅱ)∶n(Ⅰ)=1∶1,Pd/C催化剂用量为反应物总重的10%,体积分数80%的甲醇水溶液为溶剂,反应温度35℃,反应时间20 h。     

UV-induced Persulfate Oxidation of Organic Micropollutants in Water Matrices

ABSTRACT

The efficacies of UV photolysis, UV-activated persulfate (UV/PS), and combined UV/Fe²⁺-activated persulfate (UV/PS/Fe²⁺) systems for degrading of different organic micropollutants in ultrapure water and groundwater were examined and compared. The studied micropollutants belonging to the different classes involved an artificial sweetener acesulfame K (ACE), beta-lactam antibiotic amoxicillin (AMX), and endocrine disrupting compound 4-nonylphenol (NP). Among the studied systems, the UV/PS/Fe²⁺ process showed the highest performance both in degradation and in mineralization of ACE (UVA-induced systems; k_app = 0.126 1/min and 80.3% TOC removal) and AMX (UVC-induced systems; k_app = 1.383 1/min and 85.4% TOC removal), followed by the UV/PS process. In the case of NP trials, the application of UVC/PS systems was the most promising, and after careful adjustment of oxidant concentration, it demonstrated a considerable improvement in the target compound degradation (at a NP/PS molar ratio of 1/4 k_app = 0.024 1/min) compared with the UVC photolysis (k_app = 0.016 1/min). Irrespective of the applied UV-induced treatment process, the efficacy of target compounds degradation was lower in groundwater as compared with ultrapure water trials.     

Redesigning a sweet protein: increased stability and renaturability

Monellin is one of two natural proteins from African berrieswith potent sweet taste. Monellin is the smaller of the two,and consists of two peptides. The protein loses sweetness whenheated above 50°C under acidic pH. Based on the crystalstructure of monellin we have fused the two chains into a singlechain using several different linkers copied and ‘transplanted’from the same molecule. One of the newly designed proteins isas potently sweet as the natural one, is more stable upon temperatureor pH changes, and renatures easily even after heating to 100°Cat low pH.     

蔗糖改性制备的甜味剂

蔗糖是最常见的营养性双糖,蔗糖的大量食用对糖尿病患者等特殊人群有一定的影响。而将蔗糖进行生物改性,得到的功能性的甜味剂,不仅仍具有味甜又具有功能性,拓宽用途,适用人群更广;而进行物理改性可满足特殊应用要求。     

几种糖醇类甜味剂在调配型酸乳饮料中的应用研究

对几种糖醇类甜味剂在调配型酸乳饮料中的应用与蔗糖进行了对比研究，发现结晶麦芽糖醇、液体麦芽糖醇均可作为良好的蔗糖替代品生产无糖调配型酸乳饮料。