Bis[2‐(2‐hydroxyethyl)pyridinium] μ‐decavanadato‐bis[pentaaquamanganate(II)] tetrahydrate

The structure of the title compound, (C₇H₁₀NO)₂[Mn₂V₁₀O₂₈(H₂O)₁₀]·4H₂O or (C₅H₄NHCH₂CH₂OH)₂[{Mn(H₂O)₅}₂V₁₀O₂₈]·4H₂O, at 293 (2) K has triclinic (P) symmetry. The asymmetric unit consists of one half of a decavanadate anion of C_i symmetry, one [Mn(H₂O)₅]²⁺ group, one 2‐(2‐hydroxyethyl)pyridinium cation and two solvent water molecules. The decavanadate ion bridges between two [Mn(H₂O)₅]²⁺ groups, thus forming a dodecanuclear complex unit. Complex units are connected via a hydrogen‐bonding network, forming supramolecular layers lying in the (001) plane. Cations and solvent water molecules are located between these layers.     

Na6Si2O7 – The Missing Structural Link among Alkali Pyrosilicates

The crystal structure of sodium pyrosilicate (Na₆Si₂O₇) was solved from single crystal diffraction data and refined to an R index of 0.051 for 17034 independent reflections. The compound is triclinic with space group P (a = 5.8007(8) Å, b = 11.5811(15) Å, c = 23.157(3) Å, α = 89.709(10)°, β = 88.915(11)°, γ = 89.004(11)°, V = 1555.1(4) Å³, Z = 8, D_x = 2.615 g · cm^–3, μ(Mo‐K_α) = 7.94 cm^–1). A characteristic feature of the crystals is a twinning by reticular pseudo‐merohedry, which simulates a much larger monoclinic C centered lattice (V′ = 6220 Å³, Z = 32). The twin element corresponds to a twofold rotation axis running parallel to the [0 direction of the triclinic cell. The compound belongs to the group of sorosilicates, i.e. it is based on [Si₂O₇] groups, which are arranged in layers parallel to (100). Charge compensation within the structure is accomplished by monovalent sodium cations distributed among 24 crystallographically independent positions. They are coordinated by four to six nearest oxygen neighbors. Most of the coordination polyhedra can be approximately described as distorted tetrahedra or tetragonal pyramids. An alternative understanding of Na₆Si₂O₇ can be gained if the tetrahedrally coordinated sodium atoms are considered for the construction of a framework. Actually, each four of the dimers within a single slice are linked by a more or less distorted [NaO₄] tetrahedron. The resulting structural motif is similar to the one that can be observed in melilites, where linkage between the T₂O₇ (T: Al, Si) moieties is provided by [MgO₄]‐ (as in akermanite, Ca₂Mg[Si₂O₇]) or [AlO₄] tetrahedra (as in gehlenite, Ca₂Al[AlSiO₇]). By sharing common edges, the [NaO₄] tetrahedra in Na₆Si₂O₇ are forming columns running parallel to 25 . The resulting framework contains tunnels in which the more irregularly coordinated sodium cations are incorporated.     

Computational Study of the Interactions between Benzene and Crystalline Ice Ih: Ground and Excited States

Ground‐state geometries of benzene on crystalline ice cluster model surfaces (I_h) are investigated. It is found that the binding energies of benzene‐bound ice complexes are sensitive to the dangling features of the binding sites. We used time‐dependent DFT to study the UV spectroscopy of benzene, ice clusters, and benzene–ice complexes, by employing the M06‐2X functional. It is observed that the size of the ice cluster and the dangling features have minor effects on the UV spectral characteristics. Benzene‐mediated electronic excitations of water towards longer wavelengths (above 170 nm) are noted in benzene‐bound ice clusters, where the cross‐section of photon absorption by water is negligible, in good agreement with recent experimental results (Thrower et al., J. Vac. Sci. Technol. A, 2008, 26 , 919–924). The intensities of peaks associated with water excitations in benzene–ice complexes are found to be higher than in isolated ice clusters. The π→π* electronic transition of benzene in benzene–ice complexes undergoes a small redshift compared with the isolated benzene molecule, and this holds for all benzene‐bound ice complexes.     

Fast and selective synthesis of novel cyclic sulfamide HIV-1 protease inhibitors under controlled microwave heating

A novel and highly selective silver-promoted monobenzylation method was developed to promote synthesis of nonsymmetrical sulfamide-based HIV-1 inhibitors. Microwave-accelerated palladium-catalyzed N-amide arylation- and aminocarbonylation reactions were employed for rapid and reliable compound generation. With this class of inhibitory agents, six active inhibitors were identified, the most potent inhibitor possessing a K_i-value of 20 nM.     

Ammonium 1‐hydroxy‐2‐(2‐pyridinio)ethane‐1,1‐diyldiphosphonate dihydrate and potassium 1‐hydroxy‐2‐(2‐pyridinio)ethane‐1,1‐diyldiphosphonate dihydrate

The crystal structures of the title compounds, ammonium risedronate dihydrate, NH₄⁺·C₇H₁₀NO₇P₂⁻·2H₂O, (I), and potassium risedronate dihydrate, K⁺·C₇H₁₀NO₇P₂⁻·2H₂O, (II), have been determined from single‐crystal X‐ray data collected at 120 K. Compound (I) forms a three‐dimensional hydrogen‐bonded network which connects the ammonium and risedronate ions and the water mol­ecules. In compound (II), the K⁺ ions are seven‐coordinated in a capped distorted trigonal prism. The coordination polyhedra form chains by corner‐sharing, and these chains are connected by phosphon­ate groups into layers in the ac plane. The layers are stacked and connected by hydrogen bonds in the b direction. The risedronate conformation is determined by intra­molecular inter­actions fine‐tuned by crystal packing effects. All H‐atom donors in both structures are involved in hydrogen bonding, with D⋯A distances between 2.510 (2) and 3.009 (2) Å.     

Thermodynamics and kinetics of DNA nanotube polymerization from single-filament measurements

DNA nanotubes provide a programmable architecture for molecular self-assembly and can serve as model systems for one-dimensional biomolecular assemblies. While a variety of DNA nanotubes have been synthesized and employed as models for natural biopolymers, an extensive investigation of DNA nanotube kinetics and thermodynamics has been lacking. Using total internal reflection microscopy, DNA nanotube polymerization was monitored in real time at the single filament level over a wide range of free monomer concentrations and temperatures. The measured polymerization rates were subjected to a global nonlinear fit based on polymerization theory in order to simultaneously extract kinetic and thermodynamic parameters. For the DNA nanotubes used in this study, the association rate constant is (5.99 ± 0.15) × 10⁵ M^–1 s^–1, the enthalpy is 87.9 ± 2.0 kcal mol^–1, and the entropy is 0.252 ± 0.006 kcal mol^–1 K^–1. The qualitative and quantitative similarities between the kinetics of DNA nanotubes, actin filaments, and microtubules polymerization highlight the prospect of building complex dynamic systems from DNA molecules inspired by biological architecture.     

Site-Specific Radioiodination of HER2-Targeting Affibody Molecules using 4-Iodophenethylmaleimide Decreases Renal Uptake of Radioactivity

Affibody molecules are small scaffold-based affinity proteins with promising properties as probes for radionuclide-based molecular imaging. However, a high reabsorption of radiolabeled Affibody molecules in kidneys is an issue. We have shown that the use of ¹²⁵I-3-iodo-((4-hydroxyphenyl)ethyl)maleimide (IHPEM) for site-specific labeling of cysteine-containing Affibody molecules provides high tumor uptake but low radioactivity retention in kidneys. We hypothesized that the use of 4-iodophenethylmaleimide (IPEM) would further reduce renal retention of radioactivity because of higher lipophilicity of radiometabolites. An anti-human epidermal growth factor receptor type 2 (HER2) Affibody molecule (Z_HER2:2395) was labeled using ¹²⁵I-IPEM with an overall yield of 45±3 %. ¹²⁵I-IPEM-Z_HER2:2395 bound specifically to HER2-expressing human ovarian carcinoma cells (SKOV-3 cell line). In NMRI mice, the renal uptake of ¹²⁵I-IPEM-Z_HER2:2395 (24±2 and 5.7±0.3 % IA g⁻¹at 1 and 4 h after injection, respectively) was significantly lower than uptake of ¹²⁵I-IHPEM-Z_HER2:2395 (50±8 and 12±2 % IA g⁻¹at 1 and 4 h after injection, respectively). In conclusion, the use of a more lipophilic linker for the radioiodination of Affibody molecules reduces renal radioactivity.     

Dipole active vibrations and dipole moments of N2 and O2 physisorbed on a metal surface

We have, in infrared reflection absorption measurements, observed narrow dipole active absorption lines associated with the fundamental internal vibrational transitions of N(2) and O(2) physisorbed at 30 K on the chemically inert Pt(111)(1 x 1)H surface. Such transitions are forbidden for free homonuclear molecules and become dipole active at a metal surface due to polarization induced surface dipole moments. The measurements show that the internal stretch vibration frequencies are lowered by 7-8 cm(-1) relative to the gas phase values. The measured static and dynamic dipole moments are in the ranges of 0.06-0.07 and 0.001-0.002 D, respectively. We find that good estimates of the induced dynamic as well as the static dipole moments can in general be obtained from a van der Waals model but that the ratios of the measured static and dynamic moments indicates a need for a refinement of the dipole moment function.     

Characterization of Plasma-Polymerized 4-vinyl Pyridine with Silver Nanoparticles on Poly(ethylene terephthalate) Film for Anti-Microbial Properties

4-vinyl pyridine was polymerized on poly(ethylene terephthalate) (PET) film by using lower energy pulsed AC plasma under low pressure in Ar atmosphere. The plasma polymerized coating was characterized by ATR Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). Different thicknesses of poly(4-vinyl pyridine) coating under different plasma polymerization conditions were studied. Silver nanoparticles with diameter around 50nm deposit were precipitated on the poly(4-vinyl pyridine) coating by UV irradiation in Silver nitride water solution, in order to enhance the anti-microbial properties. Different kinds of modified PET films were tested for anti-microbial properties against yeast (Debaryomyces hansenii) by using microbiological analyser µ-4200 and direct microscopic count method.     

Oxidation of UO2(s) in aqueous solution

In this review the kinetics and mechanism of oxidative dissolution of UO₂(s), mainly under conditions of relevance for the safety assessment of a deep geological repository for spent nuclear fuel, are discussed. Rate constants for the elementary processes involved (oxidation of UO₂ and dissolution of oxidized UO₂) are used to calculate the rates of oxidative UO₂(s) dissolution under various conditions (type of oxidant, oxidant concentration and HCO₃ ⁻/CO₃ ²⁻ concentration) for which experimental data are also available. The calculated rates are compared to the corresponding experimental values under the assumption that the experimental numbers reflect the steady-state conditions of the system. The agreement between the calculated rates and the corresponding experimental ones is very good, in particular for the higher rates. In general, the calculated rates are somewhat higher than the experimental numbers. This can be due partly to the use of initial concentrations rather than steady-state concentrations in the calculations. The kinetic data are also used to quantitatively discuss the dynamics of spent nuclear fuel dissolution under deep geological repository conditions.