Iterative In Situ Click Chemistry Creates Antibody‐like Protein‐Capture Agents

Special agents for protein capture : Iterative in situ click chemistry (see scheme for the tertiary ligand screen) and the one‐bead–one‐compound method for the creation of a peptide library enable the fragment‐based assembly of selective high‐affinity protein‐capture agents. The resulting ligands are water‐soluble and stable chemically, biochemically, and thermally. They can be produced in gram quantities through copper(I)‐catalyzed cycloaddition.

     

Total domination in 2‐connected graphs and in graphs with no induced 6‐cycles

A set S of vertices in a graph G is a total dominating set of G if every vertex of G is adjacent to some vertex in S. The minimum cardinality of a total dominating set of G is the total domination number γ_t(G) of G. It is known [J Graph Theory 35 (2000), 21–45] that if G is a connected graph of order n > 10 with minimum degree at least 2, then γ_t(G) ≤ 4n/7 and the (infinite family of) graphs of large order that achieve equality in this bound are characterized. In this article, we improve this upper bound of 4n/7 for 2‐connected graphs, as well as for connected graphs with no induced 6‐cycle. We prove that if G is a 2‐connected graph of order n > 18, then γ_t(G) ≤ 6n/11. Our proof is an interplay between graph theory and transversals in hypergraphs. We also prove that if G is a connected graph of order n > 18 with minimum degree at least 2 and no induced 6‐cycle, then γ_t(G) ≤ 6n/11. Both bounds are shown to be sharp. © 2008 Wiley Periodicals, Inc. J Graph Theory 60: 55–79, 2009     

On-demand electrochemical activation of the click reaction on self-assembled monolayers on gold presenting masked acetylene groups

We report on a new surface modification method for grafting a "dynamic" property for on-demand activation of the click reaction. Our approach utilizes the acetylene group masked with dicobalt hexacarbonyl, Co(2)(CO)(6), which is not reactive toward the click reaction. Electrochemical treatment reveals the acetylene group on the selected region, which is then used as a chemical handle for surface functionalization via the click reaction with an azide-containing molecule. Electrochemical and chemical conversions on the surface were verified by cyclic voltammetry, X-ray photoelectron spectroscopy, and fluorescence spectroscopy. We have demonstrated immobilization of an azide-modified RGD peptide and promotion of cell adhesion/migration to the region of electrochemical induction.     

Size and composition control of Pt-In nanoparticles prepared by seed-mediated growth using bimetallic seeds

A two-step method has been developed for precise size and composition control of bimetallic Pt-In nanoparticles. Very small (1.62 nm) PtIn seed nanoparticles with 1:1 metal ratio were prepared in the absence of capping agents followed by growth of Pt on their surface in the presence of oleyl amine as reducing and stabilizing agent. Nanoparticles with bulk compositions of Pt(4)In, Pt(3)In, and Pt(2)In could be synthesized with average diameter smaller than 3 nm. TEM, EDX, and XPS provided evidence for homogeneous growth without separate nucleation of pure platinum nanoparticles in the reaction solution. Pt(3)In nanoparticles were deposited onto SiO(2) surface by incipient wetness impregnation. Temperature-induced changes in the particle surface were monitored by in situ IR spectroscopy and CO adsorption. It was found that surface alloy composition of the particles could be tuned by using oxidizing or reducing atmospheres.     

Extraction and validation of substructure profiles for enriching compound libraries

Compounds known to be potent against a specific protein target may potentially contain a signature profile of common substructures that is highly correlated to their potency. These substructure profiles may be useful in enriching compound libraries or for prioritizing compounds against a specific protein target. With this objective in mind, a set of compounds with known potency against six selected kinases (2 each from 3 kinase families) was used to generate binary molecular fingerprints. Each fingerprint key represents a substructure that is found within a compound and the frequency with which the fingerprint occurs was then tabulated. Thereafter, a frequent pattern mining technique was applied with the aim of uncovering substructures that are not only well represented among known potent inhibitors but are also unrepresented among known inactive compounds and vice versa. Substructure profiles that are representative of potent inhibitors against each of the 3 kinase families were thus extracted. Based on our validation results, these substructure profiles demonstrated significant enrichment for highly potent compounds against their respective kinase targets. The advantages of using our approach over conventional methods in analyzing such datasets and its application in the mining of substructures for enriching compound libraries are presented.     

FeCl3-mediated synthesis of fullerenyl esters as low-LUMO acceptors for organic photovoltaic devices

C(60) reacted with aromatic and aliphatic carboxylic acids in the presence of inexpensive FeCl(3) at room temperature to produce hydroxyfullerenyl esters C(60)(OCOR)(OH) in up to 68% isolated yield. The hydroxyl group was utilized in functional group transformations to obtain a diester derivative C(60)(OCOAr)(OCOPh) (Ar = 2,6-xylyl) and a siloxyl derivative C(60)(OCOAr)(OSiMe(3)). The diester and siloxyl derivatives were found to possess low-lying LUMO levels were utilized in organic photovoltaic devices showing 1.3% power conversion efficiency.     

Solution‐processible polymer solar cells fabricated on a papery substrate

We report on solution‐processible polymer solar cells (PSCs) fabricated on a papery substrate using carton. Highly conductive PEDOT:PSS was used as a bottom anode and planarization layer, and a semi‐transparent top cathode was applied. This research could be an important approach to the development of all‐solution‐processible papery PSCs as well as paper electronics.

     

Teleportation and dense coding with genuine multipartite entanglement

We present an explicit protocol E0 for faithfully teleporting an arbitrary two-qubit state via a genuine four-qubit entangled state. By construction, our four-partite state is not reducible to a pair of Bell states. Its properties are compared and contrasted with those of the four-party Greenberger-Horne-Zeilinger and W states. We also give a dense coding scheme D0 involving our state as a shared resource of entanglement. Both D0 and E0 indicate that our four-qubit state is a likely candidate for the genuine four-partite analogue to a Bell state.     

In situ AP/MALDI-MS characterization of anchored matrix metalloproteinases

Several different procedures are available for the immobilization of proteins on solid supports, as many advantages derive from this approach, such as the possibility to develop new protein solid-state assays. Enzymes that are anchored on gold surfaces can interact with several different molecules in a tag-free environment, opening the way to surface plasmon resonance (SPR) investigations. Nevertheless, it is often important to know the identity of the affinity-retained analyte, and mass spectrometric analysis, via its unique molecular mass identification, represents a very valuable complementary method. There are many pieces of evidence to suggest that matrix metalloproteinases (MMPs) are involved in normal and pathological processes, including embryogenesis, wound healing, inflammation, arthritis and cancer, but presumably also exhibiting other functions. The search for new inhibitors of MMPs has prompted research towards the development of new solid-state assays for the rapid evaluation of MMP activity. We have already reported the possibility of measuring the activity of MMP-1 anchored on solid support by coupling SPR with ESI-MS analysis. In this work, we show the in situ atmospheric pressure (AP) MALDI-MS characterization of MMPs anchored on a gold chip with known surface coverage. The study extends the MS analysis to different proteins, and sequence coverage is reported for different digestion and MS procedures.