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.     

New BODIPY derivatives as OFF-ON fluorescent chemosensor and fluorescent chemodosimeter for Cu2+: cooperative selectivity enhancement toward Cu2+

New 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) derivatives (1 and 2) were synthesized as an "off-on" fluorescent chemosensor and fluorescent chemodosimeter for Cu2+ and Pb2+. Compound 1 displayed selective and large chelation enhanced fluorescence effects with Pb2+ and Cu2+ among the metal ions examined. On the other hand, compound 2, a fluorescent chemodosimeter, effectively recognized Cu2+ via a selective hydrolysis of the acetyl group.     

A Compound Algorithm of Denoising Using Second-Order and Fourth-Order Partial Differential Equations

In this paper, we propose a compound algorithm for the image restoration. The algorithm is a convex combination of the ROF model and the LLT model with a parameter function 6. The numerical experiments demonstrate that our compound algorithm is efficient and preserves the main advantages of the two models. In particular, the errors of the compound algorithm in L2 norm between the exact images and corresponding restored images are the smallest among the three models. For images with strong noises, the restored images of the compound algorithm are the best in the corresponding restored images. The proposed algorithm combines the fixed point method, an improved AMG method and the Krylov acceleration. It is found that the combination of these methods is efficient and robust in the image restoration.     

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     

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.

     

Effects of poloxamer on the gelation of silk fibroin

The influence of the concentration of poloxamer 407, the pH and the temperature on the gelation of silk fibroin (SF) were studied. It was found that the gelation of SF occurred in the presence of poloxamer at pH value of 7.0 while gelation of SF itself did not occur. The gelation time of SF was shortened with increasing the poloxamer concentration and the temperature. The sol‐gel transition of SF became reversible with an addition of poloxamer. From infrared (IR) and circular‐dichroism (CD) spectroscopy measurements, it was found that a conformational change of the SF in the SF/poloxamer system from random coil to β‐structure was accelerated after forming a polymer complex with the poloxamer. The crystallinity of the poloxamer was reduced by SF from X‐ray diffraction measurements.     

1,3-和1,4-环己亚硝酸二酯电子轰击解离的结构效应

烷基亚硝酸二酯是一种重要的亚硝化剂,也是大气中NO_x污染物的来源之一,近年来引起了人们的广泛关注. 烷基亚硝酸二酯中两个ONO官能团对分子反应活性的影响以及在化学反应中的作用尚不清楚. 本文用电子碰撞电离质谱研究了1,3-环己亚硝酸二酯和1,4-环己亚硝酸二酯的解离过程. 实验结果发现两种结构异构体的分解产物不同：除了亚硝酸酯的特征碎片NO⁺(m/z=30)外,对于1,3-异构体,碎片离子m/z=43和71的丰度最高;而对于1,4-异构体,电子碰撞电离质谱谱图中解离产物m/z=29、57、85和97的强度较大. 对中性分子、分子离子以及中间产物的结构和电荷计算结果显示,1,3-环己亚硝酸二酯的分解清楚地显示出两步解离机制,即母体阳离子M⁺首先失去一个NO,然后中间离子(M-NO)⁺通过两个αC-βC键的断裂打开六元碳环;对于1,4-环己亚硝酸二酯,除了两步分解机制之外,还可以直接从母体阳离子M⁺发生αC-βC键的裂解. 研究结果有助于理解在大气反应及亚硝化合成反应中烷基亚硝酸二酯的分子结构对反应历程的影响.