A general method for the synthesis of nanostructured large-surface-area materials through the self-assembly of functionalized nanoparticles

A general synthetic method for the preparation of nanostructured materials with large surface area was developed by using nanoparticle building blocks. The preparation route involves the self-assembly of functionalized nanoparticles in a liquid-crystal phase. These nanoparticles are functionalized by using difunctional amino acid species to provide suitable interactions with the template. Optimum interactions for self-assembly of the nanoparticles in the liquid-crystal phase were achieved with one -NH2 group anchored to the nanoparticle surface per 25 A(2). To maximize the surface area of these materials, the wall thicknesses are adjusted so that they are composed of a monolayer of nanoparticles. To form such materials, numerous parameters have to be controlled such as the relative volume fraction of the nanoparticles and the template and size matching between the hydrophilic component of the copolymer and nanoparticles. The surface functionalization renders our synthetic route independent of the nanoparticles and allows us to prepare a variety of nanostructured composite materials that consist of a juxtaposition of different discrete oxide nanoparticles. Examples of such materials include CeO2, ZrO2, and CeO2-Al(OH)3 composites.     

An efficient newton-like method for molecular mechanics energy minimization of large molecules

Techniques from numerical analysis and crystallographic refinement have been combined to produce a variant of the Truncated Newton nonlinear optimization procedure. The new algorithm shows particular promise for potential energy minimization of large molecular systems. Usual implementations of Newton's method require storage space proportional to the number of atoms squared (i.e., O(N²)) and computer time of O(N³). Our suggested implementation of the Truncated Newton technique requires storage of less than O(N^1.5) and CPU time of less than O(N²) for structures containing several hundred to a few thousand atoms. The algorithm exhibits quadratic convergence near the minimum and is also very tolerant of poor initial structures. A comparison with existing optimization procedures is detailed for cyclohexane, arachidonic acid, and the small protein crambin. In particular, a structure for crambin (662 atoms) has been refined to an RMS gradient of 3.6 × 10^?6 kcal/mol/Å per atom on the MM2 potential energy surface. Several suggestions are made which may lead to further improvement of the new method.     

Solvation effects with a photoresponsive two-component 12-hydroxystearic acid-azobenzene additive organogel

A "light-triggerable" azobenzene amine derivative (additive 1) was synthesized and then introduced into organogels of 12-hydroxystearic acid (HSA) in the molar ratio of 1:3. The organogels (HSA/1) consisting of additive 1 and HSA were analyzed by (1)H nuclear magnetic resonance (NMR), Fourier transform-infrared (FT-IR), and X-ray diffraction (XRD). The homogeneity of the gel networks was observed using field emission scanning electron microscopy (FE-SEM). Additive 1 formed a complex with HSA in HSA organogels due to salification between the terminal amine group of additive 1 and the carboxylic acid group of HSA. Additive 1 in the gels of HSA/1 showed the potential for photo-isomerization, and we achieved a reversible control of HSA/1 sol-gel transition in toluene by the alternating irradiation with UV and visible light. Interestingly, the opposite phenomenon was observed in CHCl(3) system, namely, the orange solution of HSA/1 in CHCl(3) was turned to a red-transparent gel by exposure to UV light.     

Probing the Presence of Multiple Metal-Metal Bonds in Technetium Chlorides by X-ray Absorption Spectroscopy: Implications for Synthetic Chemistry

The cesium salts of [Tc(2)X(8)](3-) (X = Cl, Br), the reduction product of (n-Bu(4)N)[TcOCl(4)] with (n-Bu(4)N)BH(4) in THF, and the product obtained from reaction of Tc(2)(O(2)CCH(3))(4)Cl(2) with HCl(g) at 300 °C have been characterized by extended X-ray absorption fine structure (EXAFS) spectroscopy. For the [Tc(2)X(8)](3-) anions, the Tc-Tc separations found by EXAFS spectroscopy (2.12(2) ? for both X = Cl and Br) are in excellent agreement with those found by single-crystal X-ray diffraction (SCXRD) measurements (2.117[4] ? for X = Cl and 2.1265(1) ? for X = Br). The Tc-Tc separation found by EXAFS in these anions is slightly shorter than those found in the [Tc(2)X(8)](2-) anions (2.16(2) ? for X = Cl and Br). Spectroscopic and SCXRD characterization of the reduction product of (n-Bu(4)N)[TcOCl(4)] with (n-Bu(4)N)BH(4) are consistent with the presence of dinuclear species that are related to the [Tc(2)Cl(8)](n-) (n = 2, 3) anions. From these results, a new preparation of (n-Bu(4)N)(2)[Tc(2)Cl(8)] was developed. Finally, EXAFS characterization of the product obtained from reaction of Tc(2)(O(2)CCH(3))(4)Cl(2) with HCl(g) at 300 °C indicates the presence of amorphous α-TcCl(3). The Tc-Tc separation (i.e., 2.46(2) ?) measured in this compound is consistent with the presence of Tc═Tc double bonds in the [Tc(3)](9+) core.     

1-Phosphanorbornadienes in Enantioselective Catalysis

Recent developments in the chemisty of 1-phosphanorbornadienes are reviewed. Due to their bicyclic structure with a non-racemisable phosphorus atom at the bridgehead, they are ideally suited to enantioselective catalysis as transition metal complexes. Amongst this family, two enantiopure species play a special role, i.e., the so-called BIPNOR, a 2,2'-bis-1,1'-phosphanorbornadienyl ( 1 ), and a 2-formyl-1-phosphanorbornadiene ( 2 ). BIPNOR displays high enantioselectivities for a range of rhodium-catalyzed reactions. The carboxyaldehyde ( 2 ) is an ideal starting point for the synthesis of a series of enantiopure chelating 1-phosphanorbornadienes whose structures can be optimized for various catalytic enantioselective reactions. Examples of both approaches are given.     

Clustering and Filtering Tandem Mass Spectra Acquired in Data-Independent Mode

Data-independent mass spectrometry activates all ion species isolated within a given mass-to-charge window (m/z) regardless of their abundance. This acquisition strategy overcomes the traditional data-dependent ion selection boosting data reproducibility and sensitivity. However, several tandem mass (MS/MS) spectra of the same precursor ion are acquired during chromatographic elution resulting in large data redundancy. Also, the significant number of chimeric spectra and the absence of accurate precursor ion masses hamper peptide identification. Here, we describe an algorithm to preprocess data-independent MS/MS spectra by filtering out noise peaks and clustering the spectra according to both the chromatographic elution profiles and the spectral similarity. In addition, we developed an approach to estimate the m/z value of precursor ions from clustered MS/MS spectra in order to improve database search performance. Data acquired using a small 3 m/z units precursor mass window and multiple injections to cover a m/z range of 400–1400 was processed with our algorithm. It showed an improvement in the number of both peptide and protein identifications by 8 % while reducing the number of submitted spectra by 18 % and the number of peaks by 55 %. We conclude that our clustering method is a valid approach for data analysis of these data-independent fragmentation spectra. The software including the source code is available for the scientific community.

Assessing indoor air exposures using passive sampling with bioanalytical methods for estrogenicity and aryl hydrocarbon receptor activity

Passive air sampling was undertaken using polyurethane foam passive air samplers at three types of locations, including indoors (six offices) at buildings in the central business district (CBD) and at a private suburban home (indoor and outdoor) located 9 km from the CBD in Brisbane, Queensland, Australia. Estrogenic (E-SCREEN—MCF7-BOS) and aryl hydrocarbon receptor (AhR) (CAFLUX—H4G1.1c2) activity were assessed for samples collected from each of these locations. The samples were tested either as crude extracts (“untreated”) or were subjected to H₂SO₄ silica gel (“treated”) for each location in order to determine whether chemicals, which are not resistant to this treatment like polycyclic aromatic hydrocarbons, potentially account for the observed activity. In most cases, H₂SO₄ treatment resulted in a statistically significant reduction of potency for both endpoints, suggesting that chemicals less resistant to treatment may be responsible for much of the detected biological activity in these locations. Estrogenic potency measurements (<0.22–185 pg m⁻³) were highest in the indoor offices, followed by the indoor suburban home and finally the outdoor suburban home (which was not estrogenic). Total AhR activity for crude extracts (1.3–10 pg m⁻³) however was highest for the outdoor suburban home site. Levels of polycyclic aromatic hydrocarbons were monitored indoors and outdoors at the suburban home. At that location, polycyclic aromatic hydrocarbon air concentrations were on average approximately two times higher outdoor than indoor, while AhR potency was five times higher outdoor than indoor. No significant correlation was found between the estrogenic and AhR activity (P = 0.88) for the sites in this study. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Chicken egg yolk cytoplasmic proteome,mined via combinatorial peptide ligand libraries

The use of combinatorial peptide ligand libraries (CPLLs), containing hexapeptides terminating with a primary amine, or modified with a terminal carboxyl group, or with a terminal tertiary amine, allowed discovering and identifying a large number of previously unreported egg yolk proteins. Whereas the most comprehensive list up to date [K. Mann, M. Mann, Proteomics, 8 (2008) 178–191] tabulated about 115 unique gene products in the yolk plasma, our findings have more than doubled this value to 255 unique protein species. From the initial non-treated egg yolk it was possible to find 49 protein species; the difference was generated thanks to the use of the three combined CPLLs. The aberrant behaviour of some proteins, upon treatment via the CPLL method, such as proteins that do not interact with the library, is discussed and evaluated. Simplified elution protocols from the CPLL beads are taken into consideration, of which direct elution in a single step via sodium dodecyl sulphate desorption seems to be quite promising. Alternative methods are suggested. The list of egg yolk components here reported is by far the most comprehensive at present and could serve as a starting point for isolation and functional characterization of proteins possibly having novel pharmaceutical and biomedical applications.     

Changes in lipid distribution in E. coli strains in response to norfloxacin

Bacterial resistance to antibiotics has become an increasing threat, requiring not only the development of new targets in drug discovery, but more importantly, a better understanding of cellular response. In the current study, three closely related Escherichia coli strains, a wild type (MG1655) and an isogenic pair derived from the wild type (DPB635 and DPB636) are studied following exposure to sub lethal concentrations of antibiotic (norfloxacin) over time. In particular, genotype similarities between the three strains were assessed based on the lipid regulation response (e.g. presence/absence and up/down regulation). Lipid identification was performed using direct surface probe analysis (matrix‐assisted laser desorption/ionization, MALDI), coupled to high‐resolution mass spectrometry (Fourier transform ion cyclotron resonance mass spectrometry, FT‐ICR MS) followed by statistical analysis of variability and reproducibility across batches using internal standards. Inspection of the lipid profile showed that for the MG1655, DPB635 and DPB636 E. coli strains, a similar distribution of the altered lipids was observed after exposure to norfloxacin antibiotic (e.g. fatty acids and glycerol phospholipids are up and down regulated, respectively). Additionally, variations in the lipid distribution resemble the extent to which each strain can combat the antibiotic exposure. That is, the topA66 topoisomerase I mutation of DPB636 translates into diminished response related to antibiotic sensitivity when compared to MG1655 and the DPB635 strains. Copyright © 2015 John Wiley & Sons, Ltd.     

Copper and iron complexes as visible‐light‐sensitive photoinitiators of polymerization

The utilization of visible lights for the fabrication of polymeric materials is recognized as a promising and environmentally friendly approach. This process relies on the photochemical generation of reactive species (e.g., radicals, radical cations, or cations) from well‐designed photoinitiators (PIs) or photoinitiating systems (PISs) to initiate the polymerization reactions of different monomers (acrylates, methacrylates, epoxides, and vinyl ethers). In spite of the fact that metal complexes such as ruthenium‐ or iridium‐based complexes have found applications in organic and polymer synthesis, the search of other low‐cost metal‐based complexes as PISs is emerging and attracting increasing attentions. Particularly, the concept of the photoredox catalysis has appeared recently as a unique tool for polymer synthesis upon soft conditions (use of light emitting diodes and household lamp). This highlight focuses on recently designed copper and iron complexes as PI catalysts in the application of photoinduced polymerizations (radical, cationic, interpenetrated polymer networks, and thiol‐ene) or controlled radical polymerization under visible light irradiation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2673–2684