Enantioselective addition of phenylacetylene to aldehydes catalyzed by a d-glucosamine-derived sulfonamide-titanium complex

We present the synthesis of β-hydroxy sulfonamides derived from d-glucosamine and their application as ligands in titanium tetraisopropoxide promoted enantioselective addition of phenylacetylene to benzaldehyde and selected aromatic and aliphatic aldehydes. The N-3,5-bis(trifluoromethyl)benzenesulfonamido-d-glucosamine derivative was chosen as the most efficient ligand for this addition. The reaction is highly enantioselective for several aromatic aldehydes and enantiomeric excesses up to 92% were obtained.     

Brownian dynamics simulations on CPU and GPU with BD_BOX

There has been growing interest in simulating biological processes under in vivo conditions due to recent advances in experimental techniques dedicated to study single particle behavior in crowded environments. We have developed a software package, BD_BOX, for multiscale Brownian dynamics simulations. BD_BOX can simulate either single molecules or multicomponent systems of diverse, interacting molecular species using flexible, coarse-grained bead models. BD_BOX is written in C and employs modern computer architectures and technologies; these include MPI for distributed-memory architectures, OpenMP for shared-memory platforms, NVIDIA CUDA framework for GPGPU, and SSE vectorization for CPU.     

Synthesis,molecular characterisation,and in vivo study of platinum(IV) coordination compounds against B16 mouse melanoma tumours

A novel platinum(IV) coordination compound with 6-mercaptopurine (6-Hmp) has been synthesised and characterised by IR and NMR spectroscopy. Spectroscopic parameters indicate the presence of two chelate (S-6, N-7) monodeprotonated ligands and two chloride ions in the coordination sphere of [PtCl₂(6-mp)₂] · H₂O (I). Two Pt(IV) coordination compounds, [PtCl₂(6-mp)₂] · H₂O (I) and [PtCl₄(dbtp)₂] (II), were used in the in vivo test against B16 mouse melanoma tumours. Cytotoxic activity of compound II against the tumour cells was found to be high (LC₁₀ = 2.6 μM, LC₅₀ = 17.0 μM, LC₉₀ = 58.0 μM) compared to that of cisplatin.     

Unequal siblings: Adverse characteristics of naphtalene‐based hoveyda‐type second generation initiators in ring opening metathesis polymerization

A family of four different Hoveyda‐type initiators bearing a π‐extended carbene ligand was characterized regarding the activity in ring opening metathesis polymerization. One of the initiators shows high activity at ambient temperature, similar to the second generation Hoveyda–Grubbs catalyst and is even suited for the controlled polymerization of certain norbornene derivatives. The other family members exhibit a pronounced latency at room temperature, and polymerization can be triggered by heat. The scope of these initiators in the thermally triggered polymerizations of norbornene derivatives in general and dicyclopentadiene in particular was disclosed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Mechanisms of fibrinogen adsorption at solid substrates

Adsorption of fibrinogen, modeled as a linear chain of touching beads of various sizes, was theoretically studied using the random sequential adsorption (RSA) model. The adsorption process was assumed to consist of two steps: (i) formation of an irreversibly bound fibrinogen monolayer under the side-on orientation, which is independent of the bulk protein concentration and (ii) formation of the reversibly bound, end-on monolayer, whose coverage was dependent on the bulk concentration. Calculation based on the RSA model showed that the maximum surface concentration of the end-on (reversible) monolayer equals N(⊥∞) = 6.13 × 10(3) μm(-2) which is much larger than the previously found value for the side-on (irreversible) monolayer, equal to N(∞) = 2.27 × 10(3) μm(-2). Hence, the maximum surface concentration of fibrinogen in both orientations is determined to be 8.40 × 10(3) μm(-2) corresponding to the protein coverage of 5.70 mg m(-2) assuming 20% hydration. Additionally, the surface blocking function (ASF) was determined for the end-on fibrinogen adsorption, approximated for the entire range of coverage by the interpolating polynomial. For the coverage approaching the jamming limit, the surface blocking function (ASF) was shown to vanish proportionally to (θ(⊥∞) - θ(⊥))(2). These calculation allowed one to theoretically predict adsorption isotherms for the end-on regime of fibrinogen and adsorption kinetics under various transport conditions (diffusion and convection). Using these theoretical results, a quantitative interpretation of experimental data obtained by TIRF and ellipsometry was successfully performed. The equilibrium adsorption constant for the end-on adsorption regime was found to be 8.04 × 10(-3) m. On the basis of this value, the depth of the adsorption energy minimum, equal to -17.4 kT, was predicted, which corresponds to ΔG = -41.8 kJ mol(-1). This is in accordance with adsorption energy derived as the sum of the van der Waals and electrostatic interactions. Besides having significance for predicting fibrinogen adsorption, theoretical results derived in this work also have implications for basic science providing information on mechanisms of anisotropic protein molecule adsorption on heterogeneous surfaces.     

Synthesis of unsymmetrical alkyl acetals via addition of primary alcohols to allyl ethers mediated by ruthenium complexes

Abstract  

Ru-catalyzed synthesis of mixed alkyl–alkyl acetals via addition of primary alcohols to allyl ethers has been extended to include long-chain and/or functionalized substrates. The catalytic systems for these reactions were generated from RuCl₂(PPh₃)₃ and [RuCl₂(1,5-COD)]_x and phosphines [PPh₃ or P(p-chlorophenyl)₃] or SbPh₃. Of particular importance is the almost quantitative elimination of transacetalization. The addition proceeds through allyl complexes, not via isomerization of allyl ethers––subsequent addition of ROH to vinyl ethers.     

Thiol-functionalized anthraquinones: mass spectrometry and electrochemical studies

Abstract  

In this work, the synthesis of various thiol-functionalized anthraquinone compounds is presented. The studied compounds were characterized by mass spectrometry and the main fragmentation pathways are discussed. The compounds studied formed stable self-assembled monolayers (SAMs) in the gold surface. The parameters for the reduction processes in the gold surface of the studied new anthraquinones were determined by cyclic voltamperometry tests.     

Multiresidue determination of 160 pesticides in wines employing mixed-mode dispersive-solid phase extraction and gas chromatography-tandem mass spectrometry

A new multiresidue method for the efficient screening, identification and quantification of over 160 pesticides belonging to different chemical classes in red, rose and white wines have been developed. The analysis was based on gas chromatographic-tandem quadrupole mass spectrometric determination (GC-QqQ-MS/MS). An optimization strategy involved the selection of buffering conditions and sorbents for dispersive-solid phase extraction (dispersive-SPE) in order to achieve acceptably high recoveries and reduce co-extractives in the final extracts. As a result, the optimized procedure allowed us to obtain consistent recoveries of the target pesticides including problematic ones such as captan, chlorothalonil, dichlofluanid, folpet and tolylfluanid. The attained recoveries were typically between 80 and 110% (89% on average) with RSD values typically lower than 10% (8% on average) at three spiking levels of 0.01, 0.05 and 0.2 mg kg⁻¹. Linearity was studied in the range between 0.005 and 0.2 mg kg⁻¹ using pesticide standards prepared both in pure solvent and in the presence of matrix, showing coefficients of determination (R²) higher than 0.99 for all the pesticides except for desmedipham, thiabendazole and thiamethoxam in pure solvent. The study of the ratio of the slopes obtained in solvent and in matrix provided information about the matrix effects, which was <10%, 10-20% and >20% for 33, 36 and 31% of the studied pesticides, respectively. To improve accuracy, matrix matched standards were always used for calculation of the quantification results. The expanded uncertainties were estimated by using a “top-down” approach as being 17% on average (coverage factor k = 2, confidence level 95%). Finally, the method was used with success to detect and quantify pesticide residues in commercial wines.     

Stability and structure of mixed-ligand metal ion complexes that contain Ni2+, Cu2+, or Zn2+, and Histamine, as well as adenosine 5'-triphosphate (ATP4-) or uridine 5'-triphosphate (UTP(4-): an intricate network of equilibria

With a view on protein–nucleic acid interactions in the presence of metal ions we studied the “simple” mixed‐ligand model systems containing histamine (Ha), the metal ions Ni²⁺, Cu²⁺, or Zn²⁺ (M²⁺), and the nucleotides adenosine 5′‐triphosphate (ATP^4?) or uridine 5′‐triphosphate (UTP^4?), which will both be referred to as nucleoside 5′‐triphosphate (NTP^4?) . The stability constants of the ternary M(NTP)(Ha)^2? complexes were determined in aqueous solution by potentiometric pH titrations. We show for both ternary‐complex types, M(ATP)(Ha)^2? and M(UTP)(Ha)^2?, that intramolecular stacking between the nucleobase and the imidazole residue occurs and that the stacking intensity is approximately the same for a given M²⁺ in both types of complexes: The formation degree of the intramolecular stacks is estimated to be 20 to 50 %. Consequently, in protein–nucleic acid interactions imidazole–nucleobase stacks may well be of relevance. Furthermore, the well‐known formation of macrochelates in binary M²⁺ complexes of purine nucleotides, that is, the phosphate‐coordinated M²⁺ interacts with N7, is confirmed for the M(ATP)^2? complexes. It is concluded that upon formation of the mixed‐ligand complexes the M²⁺? N7 bond is broken and the energy needed for this process corresponds to the stability differences determined for the M(UTP)(Ha)^2? and M(ATP)(Ha)^2? complexes. It is, therefore, possible to calculate from these stability differences of the ternary complexes the formation degrees of the binary macrochelates: The closed forms amount to (65±10) %, (75±8) %, and (31±14) % for Ni(ATP)^2?, Cu(ATP)^2?, and Zn(ATP)^2?, respectively, and these percentages agree excellently with previous results obtained by different methods, confirming thus the internal validity of the data and the arguments used in the evaluation processes. Based on the overall results it is suggested that M(ATP)^2? species, when bound to an enzyme, may exist in a closed macrochelated form only, if no enzyme groups coordinate directly to the metal ion.