Simple inexpensive boron electrophiles for direct arene borylation

Electrophilic direct borylation is facilitated, and arene substrate scope enhanced, by using electrophiles derived from inexpensive reagents; specifically an amine, BCl(3) and AlCl(3).     

Electron-nuclear dynamics in a quantum dot under nonunitary electron control

We introduce a method for solving the problem of an externally controlled electron spin in a quantum dot interacting with host nuclei via the hyperfine interaction. Our method accounts for generalized (nonunitary) evolution effected by external controls and the environment, such as coherent lasers combined with spontaneous emission. As a concrete example, we develop the microscopic theory of the dynamics of nuclear-induced frequency focusing as first measured in Science 317, 1896 (2007); we find that the nuclear relaxation rates are several orders of magnitude faster than those quoted in that work.     

Convenient one-pot syntheses of 1,2-dithiole-3-thiones and 3-imino-1,2-dithioles from terminal alkynes

The reaction of acetylide anions with carbon disulfide or phenyl isothiocyanate followed by addition of sulfur in the presence of a protonating agent such as a primary amine or alcohol affords 1,2-dithiole-3-thiones or 3-imino-1,2-dithioles in good to excellent yields.     

s-Block metal complexes of a bulky, donor-functionalized allyl ligand

Crystallographic and NMR spectroscopic studies on allyl complexes of lithium, potassium and magnesium containing an O-donor functionality are described.     

Borylated porphyrins: 5,10,15,20‐tetrakis(5,5‐dimethyl‐1,3,2‐dioxaborinan‐2‐yl)porphyrin nitrobenzene disolvate

The title compound, C₆₄H₆₆B₄N₄O₈·2C₆H₅NO₂, is a nitrobenzene solvate of a meso‐tetraphenylporphyrin species with unconventional peripheral boronic ester substituents. The porphyrin units reside in the crystal on centers of inversion and exhibit a channel clathrate‐type structure, wherein molecules of nitrobenzene are accommodated in tunnels of width 7–8 Å that propagate through the crystal parallel to the b axis between layers of tightly offset‐stacked porphyrins. The scientific significance of the reported results is twofold. They describe the synthetic route to newly functionalized building blocks for the formulation of porphyrin‐based supramolecular assemblies, namely the corresponding tetraboronic acid derivative; the title compound represents an essential intermediate in this process. They reveal also that channel‐type clathrates can be formed not only with the parent tetraphenylporphyrins but also with their laterally extended derivatives.     

Self-assembly of stable monomolecular nucleic acid lipid particles with a size of 30 nm

The design of efficient nucleic acid complexes is key to progress in genetic research and therapies based on RNA interference. For optimal transport within tissue and across extracellular barriers, nucleic acid carriers need to be small and stable. In this Article, we prepare and characterize mono-nucleic acid lipid particles (mono-NALPs). The particles consist of single short double-stranded oligonucleotides or single siRNA molecules each encapsulated within a closed shell of a cationic-zwitterionic lipid bilayer, furnished with an outer polyethylene glycol (PEG) shield. The particles self-assemble by solvent exchange from a solution containing nucleic acid mixed with the four lipid components DOTAP, DOPE, DOPC, and DSPE-PEG(2000). Using fluorescence correlation spectroscopy, we monitor the formation of mono-NALPs from short double-stranded oligonucleotides or siRNA and lipids into monodisperse particles of approximately 30 nm in diameter. Small angle neutron and X-ray scattering and transmission electron microscopy experiments substantiate a micelle-like core-shell structure of the particles. The PEGylated lipid shell protects the nucleic acid core against degradation by nucleases, sterically stabilizes the mono-NALPs against disassembly in collagen networks, and prevents nonspecific binding to cells. Hence, PEG-lipid shielded mono-NALPs are the smallest stable siRNA lipid system possible and may provide a structural design to be built upon for the development of novel nucleic acid delivery systems with enhanced biodistribution in vivo.     

Formation of a hydrogen-bonded heptazine framework by self-assembly of melem into a hexagonal channel structure

Self-assembly of melem C(6)N(7)(NH(2))(3) in hot aqueous solution leads to the formation of hydrogen-bonded, hexagonal rosettes of melem units surrounding infinite channels with a diameter of 8.9 ?. The channels are filled with strongly disordered water molecules, which are bound to the melem network through hydrogen bonds. Single-crystals of melem hydrate C(6)N(7)(NH(2))(3)?xH(2)O (x≈2.3) were obtained by hydrothermal treatment of melem at 200 °C and the crystal structure (R ?3c, a=2879.0(4), c=664.01(13) pm, V=4766.4(13)×10(6) pm(3), Z=18) was elucidated by single-crystal X-ray diffraction. With respect to the structural similarity to the well-known adduct between melamine and cyanuric acid, the composition of the obtained product was further analyzed by solid-state NMR spectroscopy. Hydrolysis of melem to cyameluric acid during syntheses at elevated temperatures could thus be ruled out. DTA/TG studies revealed that, during heating of melem hydrate, water molecules can be removed from the channels of the structure to a large extent. The solvent-free framework is stable up to 430 °C without transforming into the denser structure of anhydrous melem. Dehydrated melem hydrate was further characterized by solid-state NMR spectroscopy, powder X-ray diffraction, and sorption measurements to investigate structural changes induced by the removal of water from the channels. During dehydration, the hexagonal, layered arrangement of melem units is maintained whereas the formation of additional hydrogen bonds between melem entities requires the stacking mode of hexagonal layers to be altered. It is assumed that layers are shifted perpendicular to the direction of the channels, thereby making them inaccessible for guest molecules.     

Novel Hydrophobic Biodegradable Ester-Polymers Obtained via Azlactone Chemistry

Biodegradable polymers having a potential for constructing resorbable therapeutical micro- and nano-containers were synthesized by interaction of bis-azlactones with bis-(L-leucine)-1,6-hexylene diester/1,6-diamino hexane either separately or as comonomers. The thermograms (DSC) all of them showed a wide endothermal peak within 55–120 °C with a maximum ranged from 86 °C to 96 °C. The peak was assigned to the melting of hydrophobic domains formed by aromatic terephthalic acid fragments in the polymeric backbones. Preliminary in vitro study showed that the ester-bonds containing polymers obtained are biodegradable – α-chymotrypsin catalyzed ester bonds hydrolysis rates ranged within 0.02–0.34 µmole/min.     

An XML format for benchmarks in High School Timetabling

The High School Timetabling Problem is amongst the most widely used timetabling problems. This problem has varying structures in different high schools even within the same country or educational system. Due to lack of standard benchmarks and data formats this problem has been studied less than other timetabling problems in the literature. In this paper we describe the High School Timetabling Problem in several countries in order to find a common set of constraints and objectives. Our main goal is to provide exchangeable benchmarks for this problem. To achieve this we propose a standard data format suitable for different countries and educational systems, defined by an XML schema. The schema and datasets are available online.     

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.