Multivalent Sialosides: A Tool to Explore the Role of Sialic Acids in Biological Processes

Sialic acids (Sias) are fascinating nine‐carbon monosaccharides that are primarily found on the terminus of the oligosaccharide chains of glycoproteins and glycolipids on cell surfaces. These Sias undergo a variety of structural modifications at their hydroxy and amine positions, thereby resulting in structural diversity and, hence, coordinating a variety of biological processes. However, deciphering the structural functions of such interactions is highly challenging, because the monovalent binding of Sias is extremely weak. Over the last decade, several multivalent Sia ligands have been synthesized to modulate their binding affinity with proteins/lectins. In this Minireview, we highlight recent developments in the synthesis of multivalent Sia probes and their potential applications. We will discuss four key multivalent families, that is, polymers, dendrimers, liposomes, and nanoparticles, and will emphasize the major parameters that are essential for the specific interactions of these molecules with proteins in biological systems.     

Effects of Ionic Dependence of DNA Persistence Length on the DNA Condensation at Room Temperature

DNA persistence length is a key parameter for quantitative interpretation of the conformational properties of DNA and related to the bending rigidity of DNA.A series of experiments pointed out that,in the DNA condensation process by multivalent cations,the condensed DNA takes elongated coil or compact globule states and the population of the compact globule states increases with an increase in ionic concentration.At the same time,single molecule experiments carried out in solution with multivalent cations(such as spermidine,spermine)indicated that DNA persistence length strongly depends on the ionic concentration.In order to revolve the effects of ionic concentration dependence of persistence length on DNA condensation,a model including the ionic concentration dependence of persistence length and strong correlation of multivalent cation on DNA is provided.The autocorrelation function of the tangent vectors is found as an effective way to detect the ionic concentration dependence of toroidal conformations.With an increase in ion concentration,the first periodic oscillation contained in the autocorrelation function shifts,the number of segment contained in the first periodic oscillation decreases gradually.According to the experiments,the average long-axis length is defined to estimate the ionic concentration dependence of condensation process further.The relation between long-axis length and ionic concentration matches the experimental results qualitatively.     

多效价树枝状糖苷配体的合成

许多生命过程如细胞间的识别、信号传递等通常依赖于细胞表面的多个配体和受体的协同作用.多效价树枝状糖基配体的合成是研究生物体内蛋白质与糖类、糖类与糖类相互作用的重要途径.本文综述了多效价树枝状糖基配体这类合成配体的最新研究进展,包括以树枝状聚合物、环糊精、糖环、芳烃和大环等为框架的多效价树枝状糖基配体的合成.     

Development of multivalent macromolecular ligands for enhanced detection of biological targets

Macromolecular conjugates enable simultaneous binding of multiple ligands on one biological entity and these polyvalent interactions can be collectively stronger than the corresponding monovalent ligands. We have synthesized macromolecules and conjugated them with a lectin (Helix Pomatia lectin, HPA), and an antibody, both with shown affinities to certain bacteria. The binding ability was studied by flow cytometry and the results showed that the affinity of the biomolecules was greatly enhanced due to the polyvalent effect.     

二次金属离子电池的研究现状*

二次电池是应用范围广泛,发展前景广阔的电化学储能器件。综述了二次金属离子电池体系的基本工作原理和研究现状,对二次金属离子电池储能技术的发展做出了展望。     

Tunable Surface Wrinkling by a Bio‐Inspired Polyamine Anion Coacervation Process that Mediates the Assembly of Polyoxometalate Nanoclusters

A bio‐inspired method is used to render controlled wrinkling surface patterns on supramolecular architectures assembled from polyoxometalate (POM) clusters. It involves a polyamine‐multivalent anion interaction generating positively charged coacervates, which while dictating the assembly of POM into spherical structures further facilitate an interesting surface morphogenesis with wrinkling patterns. This spontaneous surface wrinkling depends on the type of multivalent anion and the pH. As the polyamine‐anion interaction becomes stronger, the wrinkles turn denser with lesser depth, which eventually undergoes post‐buckling to engender a complex surface pattern. Interestingly, the order of influence exerted by different anions on the morphology follows the Hofmeister series. Moreover, the mild synthesis conditions keep the functional POM units dispersed in the sphere with a structural transformability to their lacunary form.     

Synthesis and crystallization of star‐shaped photocleavable poly(ε‐caprolactone)s

Here, we report on the synthesis and different crystallization behavior of linear‐ and star‐ PCL's containing a photocleavable linker (5‐hydroxy‐2‐nitro benzaldehyde), modulated by photochemical switching. Basis is the attachment of a photocleavable moiety close to the star‐core of a three‐arm star poly(caprolactone), so that the crystallization behavior can be controlled via a photochemical stimulus. The polymerization of ε‐caprolactone using a trivalent photocleavable initiator and stannous octanoate catalyst resulted in the synthesis of different molecular weights of star‐shaped photocleavable polymers. Various techniques like ¹H NMR and ESI‐TOF‐MS confirmed the successful synthesis of the star‐shaped polymers. Complete photocleavage is ensured via GPC, HPLC, and ESI‐TOF‐MS. DSC studies clearly indicated the enhancement in crystallinity after photocleavage of the star‐shaped poly(ε‐caprolactone)s. Hence, for the first time phototriggered crystallization behavior of PCL polymers is reported, where the confinement exerted by the star architecture is removed by photoirradiation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 642–649     

Synthesis of Oligomeric Mannosides and Their Structure‐Binding Relationship with Concanavalin A

Small glycodendrimers with α‐mannosyl ligands were synthesized by using copper‐catalyzed azide–alkyne coupling chemistry and some of these molecules were used as multivalent ligands to study the induction of concanavalin A (Con A) precipitation. The results showed that the monovalent mannose ligand could induce the precipitation of Con A. This unexpected finding initiated a series of studies to characterize the molecular basis of the ligand–lectin interaction. The atypical precipitation is found to be specific to the mannose, fluorescein moiety (FITC), and Con A. Apparently the mannose ligand binds to Con A through hydrogen‐bonding interactions, whereas the binding of FITC is mediated by hydrophobic forces.