Proteomics-driven progress in neurodegeneration research

Proteomics technologies have been widely used in the investigation of neurodegenerative and psychiatric disorders, and in particular in the detection of differences between healthy individuals and patients suffering from such diseases. Thus, brain and cerebrospinal fluid (CSF) samples from patients with Alzheimer's disease, Down syndrome, Pick's disease, Parkinson's disease, schizophrenia, and other disorders as well as brain and CSF from animals serving as models of neurological disorders have been analyzed by proteomics. 2-DE followed by MALDI-TOF-MS has been mainly applied as this proteomics approach provides the possibility of convenient quantification of protein levels and detection of post-translational modifications. About 330 unique proteins with deranged levels and modifications have been detected by proteomics approaches to be related to neurodegeneration and psychiatric disorders. They are mainly involved in metabolism pathways, cytoskeleton formation, signal transduction, guidance, detoxification, transport, and conformational changes. In this article, we provide a summary of the major contributions of proteomics technologies in the study of neurodegenerative and psychiatric diseases, in particular, in the detection of changes in protein levels and modifications related to these disorders.     

Detosylation of 3-amino-1-tosylindole-2-carbonitriles using DBU and thiophenol

Attempted detosylation of the 3-amino-1-(p-tosylamino)indole-2-carbonitriles 4a-c using either K₂CO₃ in EtOH or DBU in PhH at reflux gives unexpectedly the 3-(N-p-tosylamino)indole-2-carbonitriles 5a-c, respectively in high yields. Nevertheless, treatment of 1-(p-tosylamino)indoles 4a-c with thiophenol and DBU in PhH at reflux gives the detosylated 3-aminoindole-2-carbonitriles 5a-c. Reaction mechanisms supporting the tosyl migration (4→5) and the reductive detosylation (4→2) are proposed. All new compounds are fully characterised.     

Hydrogen‐bonded assemblies of 5,10,15,20‐tetrakis(4‐hydroxyphenyl)porphyrin with dimethylformamide,dimethylacetamide and water

The title free base porphyrin compound forms hydrogen‐bonded adducts with N,N‐dimethylformamide, C₄₄H₃₀N₄O₄·4C₃H₇NO, (I), a mixture of N,N‐dimethylformamide and water, C₄₄H₃₀N₄O₄·4C₃H₇NO·H₂O, (II), and a mixture of N,N‐dimethylacetamide and water, C₄₄H₃₀N₄O₄·6C₃H₇NO·2H₂O, (III). Total solvation of the four hydroxy functions of the porphyrin molecules characterizes all three compounds, thus preventing its supramolecular association into extended network architectures. In (I), the asymmetric unit consist of two five‐component adduct species, while in (III), the nine‐component entities reside on centres of inversion. This report provides the first structural characterizations of the free base tetra(hydroxyphenyl)porphyrin. It also demonstrates that the presence of strong Lewis bases, such as dimethylformamide or dimethylacetamide, in the crystallization mixture prevents direct supramolecular networking of the porphyrin ligands via O—H...O—H hydrogen bonds, due to their competing O—H...N(base) interaction with the hydroxy functions. The crystal packing of compounds (I)–(III) resembles that of other hydrogen‐bonding‐assisted tetraarylporphyrin clathrates.     

Unsolvated 5,10,15,20‐tetra‐4‐pyridylporphyrin,its sesquihydrate and its 2‐chlorophenol disolvate: conformational versatility of the ligand

Unsolvated 5,10,15,20‐tetra‐4‐pyridylporphyrin, C₄₀H₂₆N₈, (I), its sesquihydrate, C₄₀H₂₆N₈·1.514H₂O, (II), and its 2‐chlorophenol disolvate, C₄₀H₂₆N₈·2C₆H₅ClO, (III), reveal different conformational features of the porphyrin core. In (I), the latter is severely deformed from planarity, apparently in order to optimize the intermolecular interactions and efficient crystal packing of the molecular entities. The molecular framework has a C₁ symmetry. In (II), the porphyrin molecules are located on symmetry axes, preserving the marked deformation from planarity of the porphyrin core. The molecular units are interlinked into a single‐framework supramolecular architecture by hydrogen bonding to one another via molecules of water, which lie on twofold rotation axes. In (III), the porphyrin molecules are located across centres of inversion and are characterized by a planar conformation of the 24‐membered macrocyclic porphyrin ring. Two trans‐related pyridyl substituents are hydrogen bonded to the 2‐chlorophenol solvent molecules. The interporphyrin organization in (III) is similar to that observed for many other tetraarylporphyrin compounds. However, the organization observed in (I) and (II) is different and of a type rarely observed before. This study reports for the first time the crystal structure of the unsolvated tetrapyridylporphyrin.     

Quantized orbital angular momentum transfer and magnetic dichroism in the interaction of electron vortices with matter

Following the very recent experimental realization of electron vortices, we consider their interaction with matter, in particular, the transfer of orbital angular momentum in the context of electron energy-loss spectroscopy, and the recently observed dichroism in thin film magnetized iron samples. We show here that orbital angular momentum exchange does indeed occur between electron vortices and the internal electronic-type motion, as well as center-of-mass motion of atoms in the electric dipole approximation. This contrasts with the case of optical vortices where such transfer only occurs in transitions involving multipoles higher than the dipole. The physical basis of the observed dichroism is explained.     

Neural mechanisms underlying the facilitation of naming in aphasia using a semantic task: an fMRI study

ABSTRACT: BACKGROUND: Previous attempts to investigate the effects of semantic tasks on picture naming in both healthy controls and people with aphasia have typically been confounded by inclusion of the phonological word form of the target item. As a result, it is difficult to isolate any facilitatory effects of a semantically-focused task to either lexical-semantic or phonological processing. This functional magnetic resonance imaging (fMRI) study examined the neurological mechanisms underlying short-term (within minutes) and long-term (within days) facilitation of naming from a semantic task that did not include the phonological word form, in both participants with aphasia and age-matched controls. RESULTS: Behavioral results showed that a semantic task that did not include the phonological word form can successfully facilitate subsequent picture naming in both healthy controls and individuals with aphasia. The whole brain neuroimaging results for control participants identified a repetition enhancement effect in the short-term, with modulation of activity found in regions that have not traditionally been associated with semantic processing, such as the right lingual gyrus (extending to the precuneus) and the left inferior occipital gyrus (extending to the fusiform gyrus). In contrast, the participants with aphasia showed significant differences in activation over both the short- and the long-term for facilitated items, predominantly within either left hemisphere regions linked to semantic processing or their right hemisphere homologues. CONCLUSIONS: For control participants in this study, the short-lived facilitation effects of a prior semantic task that did not include the phonological word form were primarily driven by object priming and episodic memory mechanisms. However, facilitation effects appeared to engage a predominantly semantic network in participants with aphasia over both the short- and the long-term. The findings of the present study also suggest that right hemisphere involvement may be supportive rather than maladaptive, and that a large distributed perisylvian network in both cerebral hemispheres supports the facilitation of naming in individuals with aphasia.     

Controlled Diels–Alder “Click” Strategy to Access Mechanically Aligned Main-Chain Liquid Crystal Networks

Aligned liquid crystal polymers are materials of interest for electronic, optic, biological and soft robotic applications. The manufacturing and processing of these materials have been widely explored with mechanical alignment establishing itself as a preferred method due to its ease of use and widespread applicability. However, the fundamental chemistry behind the required two-step polymerization for mechanical alignment has limitations in both fabrication and substrate compatibility. In this work we introduce a new protection-deprotection approach utilizing a two-stage Diels–Alder cyclopentadiene-maleimide step-growth polymerization to enable mild yet efficient, fast, controlled, reproducible and user-friendly polymerizations, broadening the scope of liquid crystal systems. Thorough characterization of the films by DSC, DMA, POM and WAXD show the successful synthesis of a uniaxially aligned liquid crystal network with thermomechanical actuation abilities.     

Combined XPS and AFM study of cluster-containing polymers based on Rh

Rh₆- monomer and polymer-immobilized complexes have been characterized using XPS and AFM. Polymer-immobilized clusters were obtained by the reaction of Rh₆(CO)₁₅CH₃CN with copolymer of allyldiphenylphosphine and styrene. AFM study shows the change of surface morphology of the above copolymers. XPS data demonstrated the change of charge state of Rh atoms under monosubstitution of the CO-group for Rh₆- monomer complexes as well as in copolymer cluster complexe after the catalysis process of hydrogenation.