Calorimetric measurement of the CH/pi interaction involved in the molecular recognition of saccharides by aromatic compounds

Can a benzene molecule differentiate between two isomeric carbohydrates? It is generally accepted that two factors govern molecular recognition: complementarity and preorganization. Preorganization requires the presence of cavities for positioning the host's groups of complementary nature to those of the guest. This study shows that, in fact, groups should be complementary to recognize each other (for the case presented here, it is controlled by the CH/pi interaction) but preorganization is not essential. Since weak interactions have their origin in dispersion forces, they also have impact on the enthalpic term of the free energy, so it was considered that their participation can be demonstrated by measuring the energy involved. For recognition to happen, two conditions must be satisfied: specificity and associated stabilizing energy. In this study we evaluated the heat of dissolution of different carbohydrates such as methyl 2,3,4,6-tetra-O-methyl-alpha-d-mannopyranoside and methyl 2,3,4,6-tetra-O-methyl-beta-d-galactopyranoside using different aromatic solvents. The solvation enthalpies in benzene were -78.8 +/- 3.9 and -88.7 +/- 5.5 kJ mol(-1) for each carbohydrate, respectively; and these values yielded a CH/pi energy of interaction of 9.9 kJ mol(-1). In addition, NMR studies of the effect of the addition of benzene to chloroform solutions of the two carbohydrates showed that benzene specifically interacts with the hydrogen atoms of the pyranose ring at positions 3, 4, and 5 located on the alpha face of the methyl-beta-galactoside, so it is, in fact, able to recognize it. Thus, the interactions between carbohydrates and the aromatic residues of proteins occur in the absence of the confinement generated by the protein structure. By experimentally measuring the energy associated with this interaction and comparing it to theoretical calculations, it was also possible to unequivocally determine the existence of CH/pi interactions between carbohydrates and proteins.     

Effects of surfactant and polymerization method on the synthesis of magnetic colloidal polymeric nanoparticles

The addition of superparamagnetic iron nanoparticles into polystyrene matrix allows for the modification of the physical properties as well as the implementation of new features in the hybrid nanomaterials. These materials have excellent potential for biomedical and bioengineering applications. Nevertheless, it is necessary to achieve a good dispersion of magnetic nanoparticles for its successful incorporation into polymer particles. This can be obtained through the use of a stabilizer, which provides stability against aggregation. In this work, magnetic nanoparticles were dispersed using different stabilizers. Subsequently, ferrofluids stabilized using the mixture of ABEX/IGEPAL and acrylic acid (AA) were used to synthesize PS-Fe₃O₄ nanocomposites, through miniemulsion and emulsion polymerization conventional techniques. Semicontinuous and batch processes were compared, by varying surfactants and their concentrations. The PS-Fe₃O₄ nanoparticles were characterized by dynamic light scattering, scanning electron microscopy, Raman spectroscopy, and vibrating sample magnetometer. Magnetic nanoparticle dispersions show better results when the anionic and nonionic surfactants are used as a mixture rather than when used alone. Results of DLS showed that the semicontinuous process allowed obtaining monodisperse materials, whereas polidisperse systems are generated in batch process. Raman spectroscopy confirmed the presence of magnetite and polystyrene in the nanocomposites. PS-Fe₃O₄ nanoparticles showed superparamagnetic behavior with final magnetization of around 0.01 emu/g and low coercivity, properties that make them suitable for applications in wide fields of technology. Particle size (Dz), was lower than 300 nm in all cases. Moreover, the use of AA as stabilizer allows enhancing the PS-Fe₃O₄ composite properties. These findings showed that particle size, morphology, and agglomeration are directly influenced by the concentration and the type of surfactant employed.     

Effect of the Addition of Alginate and/or Tetracycline on Brushite Cement Properties

Calcium phosphate cements have the advantage that they can be prepared as a paste that sets in a few minutes and can be easily adapted to the shape of the bone defect, which facilitates its clinical application. In this research, six formulations of brushite (dicalcium phosphate dihydrated) cement were obtained and the effect of the addition of sodium alginate was analyzed, such as its capacity as a tetracycline release system. The samples that contain sodium alginate set in 4 or 5 min and showed a high percentage of injectability (93%). The cements exhibit compression resistance values between 1.6 and 2.6 MPa. The drug was released in a range between 12.6 and 13.2% after 7 days. The antimicrobial activity of all the cements containing antibiotics was proven. All samples reached values of cell viability above 70 percent. We also observed that the addition of the sodium alginate and tetracycline improved the cell viability.     

Molecular tuning in highly fluorescent dithieno[3,2-b:2',3'-d]pyrrole-based oligomers: effects of N-functionalization and terminal aryl unit

A series of eight conjugated oligomers consisting of central dithieno[3,2-b:2',3'-d]pyrroles (DTPs) end-capped with either thienyl or phenyl groups have been prepared from N-alkyl-, N-aryl-, and N-acyl-dithieno[3,2-b:2',3'-d]pyrroles via Stille and Suzuki cross-coupling. The DTP-based quaterthiophene, N-phenyl-2,6-bis(2-thienyl)dithieno-[3,2-b:2',3'-d]pyrrole was characterized via X-ray crystallography and was found to crystallize in the orthorhombic space group Pna2(1) with a = 10.8666(3) ?, b = 22.8858(6) ?, c = 7.4246(2) ?, and Z = 4. The full oligomeric series was thoroughly investigated via photophysical, electrochemical, and DFT calculations in order to correlate the cumulative effects of both aryl end-groups and N-functionalization on the resulting optical and electronic properties. Through such molecular tuning, it was found to be possible to modulate the HOMO energy by as much as 0.32 V and to generate highly fluorescent oligomers with solution fluorescence efficiencies as high as 92%.     

Optimization of Two Eco-Friendly Extractions of Black Medick (Medicago lupulina L.) Phenols and Their Antioxidant,Cosmeceutical, α-Glucosidase and α-Amylase Inhibitory Properties

Medicago lupulina is an ancient edible plant from the Fabaceae family. In this work, two eco-friendly methods for extraction of bioactive phenolics from M. lupulina were developed using mixtures of water with two non-toxic, skin- and environmentally-friendly polyol solvents: glycerol and polypropylene glycol. Ultrasound-assisted extractions were optimized using a Box–Behnken design. The independent variables were the concentration of organic solvent in water (X₁), extraction temperature (X₂) and time (X₃), while the response was phenolic content. The optimum conditions for extraction of polyphenols were (X₁, X₂, X₃): (45%, 70 °C, 60 min) and (10%, 80 °C, 60 min) for glycerol and polypropylene glycol extraction, respectively. The extracts prepared at optimum conditions were rich in phenolic compounds, mainly derivatives of apigenin, kaempferol, luteolin, quercetin, caffeic and ferulic acid, as well as coumestrol. Their cosmeceutical and antidiabetic activity was tested. Both extracts demonstrated notable antioxidant, anti-lipoxygenase and anti-α-amylase activity. In addition to those activities, the glycerol extract efficiently inhibited protein coagulation, elastase and α-glucosidase activity. Glycerol present in the extract displayed enzyme-inhibiting activity in several assays and supported the action of the bioactive constituents. Thus, the optimized glycerol extract is a desirable candidate for direct incorporation in antidiabetic food supplements and cosmeceutical products.     

Enantiodivergent Chemoenzymatic Dynamic Kinetic Resolution: Conversion of Racemic Propargyl Alcohols into Both Enantiomers

Natural lipases typically recognize enantiomers of alcohols based on the size differences of substituents near the carbinol moiety and selectively react with the R enantiomers of secondary alcohols. Therefore, lipase-catalyzed dynamic kinetic resolution (DKR) of racemic secondary alcohols produces only R enantiomers. We report herein a method for obtaining S enantiomers by DKR of secondary 3-(trialkylsilyl)propargyl alcohols by using a well-known R-selective Pseudomonas fluorescens lipase in combination with a racemization catalyst VMPS4, in which the silyl group reverses the size relationship of substituents near the carbinol moiety. We have already reported R-selective DKR of the corresponding propargyl alcohols without substituents on the ethynyl terminal carbon, and the presence of an easily removable silyl group has enabled us to produce both enantiomers of propargyl alcohols in high chemical yields and with high enantiomeric excess. In addition, immobilization of the lipase on Celite was found to be important for achieving a high efficiency of the DKR.     

Cladonia verticillaris (lichen) can exhibit defense mechanisms against Rn-222 under controlled conditions

Journal of Radioanalytical and Nuclear Chemistry - This study aimed to evaluate the effects of the Rn-222 progeny on the lichen Cladonia verticillaris under controlled conditions. The results...     

On some nonlocal evolution equations in Banach spaces

This note is concerned with the initial value problem for the abstract nonlocal equation where A is a maximal monotone operator from a reflexive Banach space E to its dual E^*, while B is a nonlocal maximal monotone operator from . Under proper boundedness and coercivity assumptions on the operators, a solution is achieved by means of a discretization argument. Uniqueness and continuous dependence are also discussed and we prove some estimates for the discretization error. Finally, we deal with the approximation of linear Volterra integrodifferential operators.     

Using integer programming techniques for the solution of an experimental design problem

Latin hypercube sampling is often used to estimate the distribution function of a complicated function of many random variables. In so doing, it is typically necessary to choose a permutation matrix which minimizes the correlation among the cells in the hypercube layout. This problem can be formulated as a generalized, multi-dimensional assignment problem. For the two-dimensional case, we provide a polynomial algorithm. For higher dimensions, we offer effective heuristic and bounding procedures.Supported in part by a grant from the National Institute of Standards and Technology (60NANB9D-0974).Supported in part by grants from the Office of Naval Research (N00014-90-J-1324) and the Air Force Office of Scientific Research (F49 620-90-C-0022).Research partially performed while visiting the Department of Mathematics, Brunel University, Uxbridge, England.     

Absence of Differential Correlations Between the Wave Equations for Upper-Lower One-Index Twistor Fields Borne by the Infeld-van derWaerden Spinor Formalisms for General Relativity

It is pointed out that the wave equations for any upper-lower one-index twistor fields which take place in the frameworks of the Infeldvan der Waerden γε-formalisms must be formally the same. The only reason for the occurrence of this result seems to be directly related to the fact that the spinor translation of the traditional conformal Killing equation yields twistor equations of the same form. It thus appears that the conventional torsionless devices for keeping track in the γ-formalism of valences of spinor differential configurations turn out not to be useful for sorting out the typical patterns of the equations at issue.