Two-Dimensional Coordination Networks from Cyclic Dipeptides.

Peptide-based biomimetic nanostructures and metal-organic coordination networks on surfaces are two promising classes of hybrid materials which have been explored recently. However, despite the great versatility and structural variability of natural and synthetic peptides, the two directions have so far not been merged in fabrication of metal-organic coordination networks using peptides as building blocks. Here we demonstrate that cyclic peptides can be used as ligands to form highly ordered, two-dimensional, peptide-based metal-organic coordination networks. The networks are formed on a Au(111) surface through coadsorption of cyclic dialanine with Cu-adatoms under Ultra-High Vacuum (UHV) conditions. Scanning Tunneling Microscopy (STM) in combination with X-ray Photoelectron spectroscopy (XPS) has been utilized to characterize the network structures at submolecular resolution and expound the chemical changes involved in network coordination. The networks involve a motif of three cyclic dialanine molecules coordinating to a central Cu-adatom. Interestingly the networks expose pores functionalized by the side chain of the cyclic peptide, suggesting a general method to form functionalized porous metal-organic networks on surfaces.

Influence of CH···N Interaction in the Self-Assembly of an Oligo(isoquinolyne-ethynylyne) Molecule with Distinct Conformational States.

Molecular conformational flexibility can play an important role in supramolecular self-assembly on surfaces, affecting not least chiral molecular assemblies. To explicitly and systematically investigate the role of molecular conformational flexibility in surface self-assembly, we synthesized a three-bit conformational switch where each of three switching units on the molecules can assume one of two distinct binary positions on the surface. The molecules are designed to promote C-H···N type hydrogen bonds between the switching units. While supramolecular self-assembly based on strong hydrogen-bonding interactions has been widely explored, less is known about the role of such weaker directional interactions for surface self-assembly. The synthesized molecules consist of three nitrogen-containing isoquinoline (IQ) bits connected by ethynylene spokes and terminated by tert-butyl (tBu) groups. Using high-resolution scanning tunnelling microscopy, we investigate the self-assembly of the IQ-tBu molecules on a Au(111) surface under ultrahigh-vacuum conditions. The molecules form extended domains of brick-wall structure where the molecular backbones are packed regularly but without selection of specific molecular conformations. However, statistical analysis of the extended network demonstrates alignment/correlation for the orientations of the switching units indicating specific interactions. The primary interaction motifs in the structure are quantified from DFT calculations, showing that the brick-wall structure is indeed stabilized by two types of weak C-H···N bonds, involving either aromatic hydrogens on the IQ groups or nonaromatic hydrogens on the tBu groups. Analysis of the C-H···N interactions in the brick-wall structure explains the observed distribution and alignment of molecular conformations as well as the overall organization of the molecular surface structures.

Uygur medicine Xipayi Kui Jie'an affects gene expression profiles in intestinal tissue lesions in a rat model of ulcerative colitis.

BACKGROUND: The aim of this study was to investigate the mechanisms underlying the therapeutic effect of Uygur medicine KJA on UC in a rat model. METHODS: UC was induced in Wistar rats by application of 2, 4-dinitrochlorobenzene and acetic acid and were then treated with three different doses of KJA, and normal saline as control. After treatment for 20 days, the gene expression profile of colonic tissue was analyzed by microarray and verified by quantitative real-time RT-PCR. RESULTS: Animals treated with the three different doses of KJA were compared with normal saline controls, wherein microarray analysis identified 1991, 2163, and 1677 differentially expressed genes respectively, of which 444 genes were raised and 670 genes were decrease spliced together in the three doses tested. The KEGG pathway analyses found commonly raised genes related to several different biological functions. Interesting genes included TRL2, IL-1ß, TGF-ß1, and NF-κB were confirmed by quantitative PCR. CONCLUSIONS: The therapeutic effect of KJA on UC is likely explained by specific effects on the expression of genes, which are the effector molecules known to be involved in the development of UC. Further studies on differentially expressed genes will help explain the mechanism of action of Uygur medicine KJA.

Chiral induction with chiral conformational switches in the limit of low "sergeants to soldiers" ratio.

Molecular-level insights into chiral adsorption phenomena are highly relevant within the fields of asymmetric heterogeneous catalysis or chiral separation and may contribute to understand the origins of homochirality in nature. Here, we investigate chiral induction by the "sergeants and soldiers" mechanism for an oligo(phenylene ethynylene) based chiral conformational switch by coadsorbing it with an intrinsically chiral seed on Au(111). Through statistical analysis of scanning tunneling microscopy (STM) data, we demonstrate successful chiral induction with a very low concentration of seeding molecules down to 3%. The microscopic mechanism for the observed chiral induction is suggested to involve nucleation of the intrinsically chiral seeds, allowing for effective transfer and amplification of chirality to large numbers of soldier target molecules.