A new type of noncovalent surface–π stacking interaction occurring on peroxide-modified titania nanosheets driven by vertical π-state polarization

Noncovalent π stacking of aromatic molecules is a universal form of noncovalent interactions normally occurring on planar structures (such as aromatic molecules and graphene) based on sp²-hybridized atoms. Here we reveal a new type of noncovalent surface–π stacking unusually occurring between aromatic groups and peroxide-modified titania (PMT) nanosheets, which can drive versatile aromatic adsorptions. We experimentally explore the underlying electronic-level origin by probing the perturbed changes of unoccupied Ti 3d states with near-edge X-ray absorption fine structures (NEXAFS), and find that aromatic groups can vertically attract π electrons in the surface peroxo-Ti states and increase their delocalization regions. Our discovery updates the concept of noncovalent π-stacking interactions by extending the substrates from carbon-based structures to a transition metal oxide, and presents an approach to exploit the surface chemistry of nanomaterials based on noncovalent interactions.

A new type of noncovalent surface–π stacking interaction occurring on a transition metal oxide, titania, is reported, which is different from the traditional forms on sp²-hybridized planar structures like graphene.     

Transition metal coordination polymers with polycarboxylic acid as bridging ligands: Synthesis and structure characterization of [Fe(μ4-bta)0.5(phen)(OH)]<Subscript>n</Subscript>

A new 2D (two-dimensional) coordination polymer, [Fe(μ4-bta)o.5(phen)(OH)]_n (1), has been hydrothermally synthesized with FeCl₃ 6H₂, Na₄bta (h₄bta = 1,2,4,5-benzentetracarboxylic acid), 1,10-phen (1,10-phenanthroline) and H₂O as raw materials. The crystals of the compound belong to monoclinic P2₁/n space group, a = 1.0129(2) nm, b = 0.9265(2) nm, c = 1.5696(3) nm, β=91.37(3)°V=1.4721(5) nm³,Z=3, final R₁=0.0292, wR ₂=0.0798 for 2572 [/>2σ(/)] observed reflections. The result of structure determination shows that in the compound each bta ligand is connected with four Fe³, forming a new μ4-coordination mode. Four deprotonated carboxylic groups of bta link to Fe³ ions alternatively through monodentate and bidentate coordination fashion, constructing 2D layer network. The measurement of variable temperature magnetic susceptibility indicates that there exist antiferromagnetic interactions between Fe³ ions in the compound. The TGA spectrum displays relatively fine thermal stability of the compound. In addition, IR and UV-Vis spectra of compound 1 have also been measured.     

Synthesis and antimalarial effects of 2-(3,4-dichloroanilino)-7-[[[(dialkylamino)alkyl]amino]]-5-methyl-s-triazolo[1,5-a]pyrimidines

3,4-Dichlorophenylisothioeyanate ( 10 ) was allowed to react with 2-methy1-2-thiopseudourea to give methyl 4-(3,4-dichlorophenyl)(dithioaltophanimidate ( 11 ) (41%), which upon treatment with hydrazine afforded 3-amino-5-(3,4-dichloroanilino)-s-triazole ( 12 ) (54-91%). Ring-closure with ethyl acetoacetale in acetic acid afforded 2-(3,4-dichloroanilino)-5-methyl-s-triazolo[ 1,5-α ]-pyrimidin-7-ol ( 13 ) (81%). Chlorination with phosphorus oxychloride gave 7-chloro-2-(3,4-dichloroanilino)-5-methyl-s-triazolo[1,5-α ]pyrimidine ( 14 ) (98%), which was condensed with various amines to yield the desired 2-(3,4-diehloroanilino)-7-¶[(dialkylamino)alkyl]arnino¶-5-methyl-s-triazolo[ 1,5-α]pyrimidines ( 6 a-d). The structures of the s-triazolo[ 1,5-α ]pyrimidines were based on nmr spectroscopy and ring stability considerations. Several of the amino-s-triazolo[ 1,5-α ]pyrimidines possessed antimalarial activity against P. berghei in mice.     

Thermodynamic Parameters for the Association of Fluorinated Benzenesulfonamides with Bovine Carbonic Anhydrase II

This paper describes a calorimetric study of the association of a series of seven fluorinated benzenesulfonamide ligands (C₆H_nF_5?nSO₂NH₂) with bovine carbonic anhydrase II (BCA). Quantitative structure–activity relationships between the free energy, enthalpy, and entropy of binding and pK_a and log P of the ligands allowed the evaluation of the thermodynamic parameters in terms of the two independent effects of fluorination on the ligand: its electrostatic potential and its hydrophobicity. The parameters were partitioned to the three different structural interactions between the ligand and BCA: the Zn^II cofactor–sulfonamide bond (≈65 % of the free energy of binding), the hydrogen bonds between the ligand and BCA (≈10 %), and the contacts between the phenyl ring of the ligand and BCA (≈25 %). Calorimetry revealed that all of the ligands studied bind in a 1:1 stoichiometry with BCA; this result was confirmed by ¹⁹F NMR spectroscopy and X‐ray crystallography (for complexes with human carbonic anhydrase II).     

Generic fast gradient liquid chromatography/tandem mass spectrometry techniques for the assessment of the in vitro permeability across the blood-brain barrier in drug discovery

Rapid, generic gradient liquid chromatography/tandem mass spectrometry (LC/MS/MS) assays, designed to accelerate sample analyses, have been developed to keep pace with the productivity of advanced synthetic procedures. In this study, LC/MS/MS was combined with an in vitro, cell-based, blood-brain barrier (BBB) model to evaluate the potential of new chemical entities (NCEs) to cross the BBB. This in vitro assay provides the permeability of discovery compounds across a monolayer of a primary culture of bovine brain microvessel endothelial cells in a fraction of the time that is required for in vivo studies (brain/plasma concentrations), using only 2 mg of the compound. The results are consistent with in vivo brain/plasma concentration ratio data.     

Formation of hydroxyl radical from the photolysis of frozen hydrogen peroxide

Hydrogen peroxide (HOOH) in ice and snow is an important chemical tracer for the oxidative capacities of past atmospheres. However, photolysis in ice and snow will destroy HOOH and form the hydroxyl radical (*OH), which can react with snowpack trace species. Reactions of *OH in snow and ice will affect the composition of both the overlying atmosphere (e.g., by the release of volatile species such as formaldehyde to the boundary layer) and the snow and ice (e.g., by the *OH-mediated destruction of trace organics). To help understand these impacts, we have measured the quantum yield of *OH from the photolysis of HOOH on ice. Our measured quantum yields (Phi(HOOH --> *OH)) are independent of ionic strength, pH, and wavelength, but are dependent upon temperature. This temperature dependence for both solution and ice data is best described by the relationship ln(Phi(HOOH --> *OH)) = -(684 +/- 17)(1/T) + (2.27 +/- 0.064) (where errors represent 1 standard error). The corresponding activation energy (Ea) for HOOH (5.7 kJ mol(-1)) is much smaller than that for nitrate photolysis, indicating that the photochemistry of HOOH is less affected by changes in temperature. Using our measured quantum yields, we calculate that the photolytic lifetimes of HOOH in surface snow grains under midday, summer solstice sunlight are approximately 140 h at representative sites on the Greenland and Antarctic ice sheets. In addition, our calculations reveal that the majority of *OH radicals formed on polar snow grains are from HOOH photolysis, while nitrate photolysis is only a minor contributor. Similarly, HOOH appears to be much more important than nitrate as a photochemical source of *OH on cirrus ice clouds, where reactions of the photochemically formed hydroxyl radical could lead to the release of oxygenated volatile organic compounds to the upper troposphere.     

Fast DNA sequencing up to 1,000 bases by capillary electrophoresis using poly(N,N-dimethylacrylamide) as a separation medium

Poly(N,N-dimethylacrylamide) (PDMA) with a molecular mass of 5.2 x 10(6) g/mol has been synthesized and used in DNA sequencing analysis by capillary electrophoresis (CE). A systematic investigation is presented on the effects of different separation conditions, such as injection amount, capillary inner diameter, polymer concentration, effective separation length, electric field and temperature, on the resolution. DNA sequencing up to 800 bases with a resolution (R) limit of 0.5 (and 1,000 bases with a resolution limit of 0.3) and a migration time of 96 min was achieved by using 2.5% w/v polymer, 150 V/cm separation electric field, and 60 cm effective separation length at room temperature on a DNA sample prepared with FAM-labeled--21M13 forward primer on pGEM3Zf(+) and terminated with ddCTP. Ultrafast and fast DNA sequencing up to 420 and 590 bases (R > or = 0.5) were also achieved by using 3% w/v polymer and 40 cm effective separation length with a separation electric field of 525 and 300 V/cm, and a migration time of 12.5 and 31.5 min, respectively. PDMA has low viscosity, long shelf life and dynamic coating ability to the glass surface. The unique properties of PDMA make it a very good candidate as a separation medium for large-scale DNA sequencing by capillary array electrophoresis (CAE).