Unravelling the Time Scale of Conformational Plasticity and Allostery in Glycan Recognition by Human Galectin-1

The interaction of human galectin-1 with a variety of oligosaccharides, from di-(N-acetyllactosamine) to tetra-saccharides (blood B type-II antigen) has been scrutinized by using a combined approach of different NMR experiments, molecular dynamics (MD) simulations, and isothermal titration calorimetry. Ligand- and receptor-based NMR experiments assisted by computational methods allowed proposing three-dimensional structures for the different complexes, which explained the lack of enthalpy gain when increasing the chemical complexity of the glycan. Interestingly, and independently of the glycan ligand, the entropy term does not oppose the binding event, a rather unusual feature for protein-sugar interactions. CLEANEX-PM and relaxation dispersion experiments revealed that sugar binding affected residues far from the binding site and described significant changes in the dynamics of the protein. In particular, motions in the microsecond-millisecond timescale in residues at the protein dimer interface were identified in the presence of high affinity ligands. The dynamic process was further explored by extensive MD simulations, which provided additional support for the existence of allostery in glycan recognition by human galectin-1.     

基于有序介孔碳的氯离子选择性电极的制备及其在手持传感系统中的应用

以有序介孔碳(OMC)球为离子-电子转换层,制备了固态氯离子选择性电极,构建了基于离子敏感的场效应晶体管(ISFET)的手持式传感系统,用于检测人体血清中的氯离子。优化了OMC前驱体的碳化温度,探究了OMC形貌结构对电极传感性能的影响;电极柔性化制备后考察了其在手持系统中对氯离子的检测效果。结果表明,最优条件下,电极在5.12×10^-4~1.02 mol/L的浓度范围呈现线性响应,响应斜率为60 mV/decade。该柔性电极在手持传感系统中展现出高灵敏度和重现性,可用于人体血清样品中氯离子的检测,其回收率为96.3%~104.9%。     

可用于连续识别Cu^2+和阴离子、中性分子荧光探针的研究进展

铜(Cu)含量的高低直接影响着生命体的正常运转和自然体系的平衡.检测铜离子的方法多种多样,其中具有较高敏感度和选择性的荧光化学传感器应用更加广泛.综述了以Cu^2+为基的荧光化学传感器通过"替换"法实现了对阴离子S^2-, CN^-, H2PO4^-, PPi和I^-以及中性分子ATP、ADP和生物硫醇等的连续识别的研究进展.     

Nucleon effective mass splitting and density-dependent symmetry energy effects on elliptic flow in heavy ion collisions at E_(lab)= 0.09 ～ 1.5 GeV/nucleon

By incorporating an iso spin-dependent form of the momentum-dependent potential in the ultra-relativistic quantum molecular dynamics(UrQMD) model,we systematically investigate effects of the neutron-proton effective mass splitting m*_(n-p)=m*_n-m*_p/m and the density-dependent nuclear symmetry energy E_(sym)(ρ) on the elliptic flow v_2 in~(197)Au+~(197) Au collisions at beam energies from 0.09 to 1.5 GeV/nucleon.It is found that at higher beam energies(≥0.25 GeV/nucleon) with the approximately 75 MeV difference in slopes of the two different E_(sym)(ρ),and the variation of m*_(n-p) ranging from-0.03 to 0.03 at saturation density with isospin asymmetry δ=(ρ_n-ρ_p)/ρ-0.2,the E_(sym)(ρ) has a stronger influence on the difference in v_2 between neutrons and protons,i.e.,v_2~n-v_2~p,than m*_(n-p) has.Meanwhile,at lower beam energies(≤0.25 GeV/nucleon),v_2~n-v_2~p is sensitive to both the E_(sym)(ρ) and the m*_(n-p).Moreover,the influence of m*_(n-p) on v_2~n-v_2~p is more evident with the parameters of this study when using the soft,rather than stiff,symmetry energy.     

Heterointerface Engineering of ZnO/CdS Heterostructures through ZnS Layers for Photocatalytic Water Splitting

Solar-driven water splitting to produce clean and renewable hydrogen offers a green strategy to address the energy crisis and environmental pollution. Heterostructure catalysts are receiving increasing attention for photocatalytic hydrogen generation. ZnO/ZnS/CdS and ZnO/CdS heterostructures have been successfully designed and prepared according to two different strategies. By introducing a heterointerface layer of ZnS between ZnO and CdS, a Z scheme charge-transfer channel was promoted and achieved superior photocatalytic performance. A highest hydrogen generation rate of 156.7 μmol g⁻¹ h⁻¹ was achieved by precise control of the thickness of the heterointerface layer and of the CdS shell. These findings demonstrated that heterostructures are promising catalysts for solar-driven water splitting, and that heterointerface engineering is an effective way to improve the photocatalytic properties of heterostructures.     

An Ion-Exchangeable MOF with Reversible Dehydration and Dynamic Structural Behavior (NH4)2[Zn2(O3PCH2CH2COO)2]⋅5 H2O (BIRM-1)

(NH₄)₂[Zn₂(O₃PCH₂CH₂COO)₂]⋅5 H₂O (BIRM-1) is a new metal phosphonate material, synthesized through a simple hydrothermal reaction between zinc nitrate and 3-phosphonopropionic acid, using urea and tetraethylammonium bromide as the reaction medium. In common with other metal–organic framework materials, BIRM-1 has a large three-dimensional porous structure providing potential access to a high internal surface area. Unlike most others, it has the advantage of containing ammonium cations within the pores and has the ability to undergo cation exchange. Additionally, BIRM-1 also exhibits a reversible dehydration behavior involving an amorphization-recrystallization cycle. The ability to undergo ion exchange and dynamic structural behavior are of interest in their own right, but also increase the range of potential applications for this material. Here the crystal structure of this new metal phosphonate and its ion exchange behavior with K⁺ as an exemplar are studied in detail, and its unusual structure-reviving property reported.     

Arylpyrrolyldiketone Boron Complexes Exhibiting Various Anion‐Binding Modes Based on Dynamic Conformation Changes

Arylpyrrolyldiketone boron complexes as anion‐responsive π‐electronic molecules were synthesized by Claisen condensations of acetylpyrrole and corresponding aryl esters. The synthesized π‐electronic molecules exhibited anion‐binding behavior with various binding modes including pyrrole‐inverted and non‐inverted [1+1]‐type anion complexes as well as [2+1]‐type complexes owing to the presence of only a single pyrrole ring. Furthermore, solid‐state ion‐pairing assemblies, comprising receptor–anion complexes and countercations, were constructed based on fairly planar [2+1]‐type complexes.     

Biological applications of amide and amino acid containing synthetic macrocycles

ABSTRACT

Amino acid derived macrocycles with elaborate well-defined stereochemistry are a unique class of compounds that have been isolated from natural sources. Macrocycles like cyclosporine, octreotide, and valinomycin have been used in multiple applications, like drugs or ion sensors. Chemists have long been fascinated by the unique molecular recognition capabilities of these macrocycles and tried to design synthetic analogs with similar functions. This article is focused on reviewing current research on amide and amino acid containing macrocycles that have been developed in research laboratories for biological recognition, specifically for anion sensing, ion transport, carbohydrate sensing, and peptide sensing.     

Ligand Design to Acquire Specificity to Intended G-Quadruplex Structures

A G-quadruplex is a nucleic acid secondary structure that is adopted by guanine-rich sequences, and is considered to be relevant in various pharmacological and biological contexts. G-Quadruplexes have also attracted great attention in the field of DNA nanotechnology because of their extremely high thermal stability and the availability of many defined structures. To date, a large repertory of DNA/RNA G-quadruplex-interactive ligands has been developed by numerous laboratories. Several relevant reviews have also been published that have helped researchers to grasp the full scope of G-quadruplex research from its outset to the present. This review focuses on the G-quadruplex ligands that allow targeting of specific G-quadruplexes. Moreover, unique ligands, successful methodologies, and future perspectives in relation to specific G-quadruplex recognition are also addressed.     

Lipid Switches: Stimuli-Responsive Liposomes through Conformational Isomerism Driven by Molecular Recognition

Advancements in the field of liposomal drug carriers have culminated in greatly improved delivery properties. An important aspect of this work entails development of designer liposomes for release of contents triggered by environmental changes. The majority of these systems are driven by chemical reactions in the presence of different stimuli. However, a promising new paradigm instead focuses on molecular recognition events as the impetus for content release. In certain cases, these platforms exploit synthetic lipid switches designed to undergo conformational changes upon binding to target ions or molecules that perturb membrane assembly, thereby triggering cargo release. Examples of this approach reported thus far showcase how rational design of lipid switches can result in dramatic changes in lipid assembly properties. These strategies show great promise for opening up new pathophysiological stimuli that can be harnessed for programmed content release in drug delivery applications.