Enzymatic cross-linking of β-casein and its impact on digestibility and allergenicity

Protein modification via enzymatic cross-linking is an attractive way for altering food structure so as to create products with increased quality and nutritional value. These modifications are expected to affect not only the structure and physico-chemical properties of proteins but also their physiological characteristics, such as digestibility in the GI-tract and allergenicity. Protein cross-linking enzymes such as transglutaminases are currently commercially available, but also other types of cross-linking enzymes are being explored intensively. In this study, enzymatic cross-linking of β-casein, the most abundant bovine milk protein, was studied. Enzymatic cross-linking reactions were performed by fungal Trichoderma reesei tyrosinase (TrTyr) and the performance of the enzyme was compared to that of transglutaminase from Streptoverticillium mobaraense (Tgase). Enzymatic cross-linking reactions were followed by different analytical techniques, such as size exclusion chromatography -Ultra violet/Visible multi angle light scattering (SEC-UV/Vis-MALLS), phosphorus nuclear magnetic resonance spectroscopy (31P-NMR), atomic force (AFM) and matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF MS). The research results showed that in both cases cross-linking of β-casein resulted in the formation of high molecular mass (MM ca. 1 350 kg mol-1), disk-shaped nanoparticles when the highest enzyme dosage and longest incubation times were used. According to SEC-UV/Vis-MALLS data, commercial β-casein was cross-linked almost completely when TrTyr and Tgase were used as cross-linking enzymes. In the case of TrTyr, high degree of cross-linking was confirmed by 31P-NMR where it was shown that 91 % of the tyrosine side-chains were involved in the cross-linking. The impact of enzymatic cross-linking of β-casein on in vitro digestibility by pepsin was followed by various analytical techniques. The research results demonstrated that enzymatically cross-linked β-casein was stable under the acidic conditions present in the stomach. Furthermore, it was found that cross-linked β-casein was more resistant to pepsin digestion when compared to that of non modified β-casein. The effects of enzymatic cross-linking of β-casein on allergenicity were also studied by different biochemical test methods. On the basis of the research results, enzymatic cross-linking decreased allergenicity of native β-casein by 14 % when cross-linked by TrTyr and by 6 % after treatment by Tgase. It can be concluded that in addition to the basic understanding of the reaction mechanism of TrTyr on protein matrix, the research results obtained in this study can have high impact on various applications like food, cosmetic, medical, textile and packing sectors.

Allergenic Cross-Reactivity between Parthenium and Ragweed Pollen Allergens

Cross-reactivity of allergens from the pollen of the Compositae weeds, Parthenium hysterophorus (American feverfew) and Ambrosia (ragweed), in 2 groups of patients with different geographic distributions was studied. Parthenium-sensitive Indian patients, who were never exposed to ragweed, elicited positive skin reactions with ragweed pollen extracts. A significant correlation in the RAST scores of Parthenium and ragweed-specific IgE was observed with the sera of Parthenium and ragweed-sensitive Indian and US patients, respectively. RAST inhibition experiments demonstrated that the binding of IgE antibodies in the sera of ragweed-sensitive patients to short (Wl) and giant (W3) ragweed allergen discs could be inhibited by up to 94% by Parthenium pollen extracts. Similar inhibition (up to 82%) was obtained when the sera of Parthenium rhinitis patients were incubated with ragweed allergen extracts. A dose-dependent proliferation of lymphocytes from a Parthenium-sensitive rhinitis patient with elevated levels of both Parthenium and ragweed-specific IgE was observed when incubated with Parthenium and ragweed pollen extracts. A 1.6-fold higher proliferation, however, was observed with Parthenium pollen extract at a concentration of 100 µg/ml. These results suggest that shared epitopes present on Parthenium and ragweed pollen allergens are recognized by both Indian and US patients sensitized by exposure to Parthenium and ragweed pollen, respectively. The high degree of cross-reactivity between Parthenium and ragweed pollen allergens suggests that individuals sensitized to Parthenium may develop type-I hypersensitivity reactions to ragweed and vice versa when they travel to regions infested with the weed to which they had not been previously exposed.

Azide and Alkyne Terminated Polybutadiene Binders: Synthesis, Cross-linking, and Propellant Studies

In composite solid propellants, the fuel and oxidizer are held together by a polymer binder. Among the different types of polymeric binders used in solid propellants, hydroxyl terminated polybutadiene (HTPB) is considered as the most versatile. HTPB is conventionally cured using isocyanates to form polyurethanes. However, the incompatibility of isocyanates with energetic oxidizers such as ammonium dinitramide and hydrazinium nitroformate, the short pot life of the propellant slurry, and undesirable side reactions with moisture are limiting factors which adversely affect the mechanical properties of HTPB based propellant. With an aim of resolving these problems, HTPB was chemically transformed to azidoethoxy carbonyl amine terminated polybutadiene and propargyloxy carbonyl amine terminated polybutadiene by adopting appropriate synthesis strategies and characterizing them by spectroscopic and chromatographic techniques. This is the first report on 1,3-dipolar addition reaction involving azide and alkyne end groups for cross-linking HTPB. The blend of these two polymers underwent curing under mild temperature (60 degrees C) conditions through 1,3-dipolar cycloaddition reaction resulting in triazoletriazoline networks. The curing parameters were studied using differential scanning calorimetry. The kinetic parameter, viz., activation energy, was computed to be 107.6 kJ/mol, the preexponential factor was 2.79 x 10(12) s-(1), and the rate constant at 60 degrees C was computed to be 3.64 x 10-(5) s-(1). The cure profile at a given temperature was predicted using the kinetic parameters. Rheological studies revealed that the gel time for curing through the 1,3-dipolar addition is 280 min compared to 120 min for curing through the urethane route. The mechanical properties of the resultant cured polybutadiene network were superior to those of polyurethanes. The cured triazolinetriazole polymer network exhibited biphasic morphology with two glass transitions (T-g) at -56 and 42 degrees C in contrast to the polyurethane which exhibited a single transition at -60 degrees C. This was corroborated by associated morphological changes observed by scanning probe microscopy. The propellant processed using this binder has the advantages of improved pot life as indicated by the end of the mix viscosity which is 165 Pas as compared with 352 Pas for the polyurethane system along with a slow build- up rate. The mechanical properties of the propellant are superior to polyurethane with an improvement of 14% in tensile strength, 22% enhancement in elongation at break, and 12% in modulus.

Cross-section fluctuations in open microwave billiards and quantum graphs: The counting-of-maxima method revisited

The fluctuations exhibited by the cross sections generated in a compound-nucleus reaction or, more generally, in a quantum-chaotic scattering process, when varying the excitation energy or another external parameter, are characterized by the width Gamma(corr) of the cross-section correlation function. Brink and Stephen Phys. Lett. 5, 77 (1963)] proposed a method for its determination by simply counting the number of maxima featured by the cross sections as a function of the parameter under consideration. They stated that the product of the average number of maxima per unit energy range and Gamma(corr) is constant in the Ercison region of strongly overlapping resonances. We use the analogy between the scattering formalism for compound-nucleus reactions and for microwave resonators to test this method experimentally with unprecedented accuracy using large data sets and propose an analytical description for the regions of isolated and overlapping resonances.

A chemoselective alpha-aminoxylation of aryl ketones: a cross dehydrogenative coupling reaction catalysed by Bu4NI

Tetrabutyl ammonium iodide (TBAI) catalyzed alpha-aminoxylation of ketones using aq. TBHP as an oxidant has been accomplished. We have shown that the CDC (cross dehydrogenative coupling) reactions of ketones with N-hydroxyimidates such as N-hydroxysuccinimide (NHSI), N-hydroxyphthalimide (NHPI), N-hydroxybenzotriazole (HOBt) and 1-hydroxy-7-azabenzotriazole (HOAt) lead to the corresponding oxygenated products in good to moderate yields. The application of this method has been demonstrated by transforming a few coupled products into synthetically useful intermediates and products.

Numerical Investigation On Detonation Cell Evolution In A Channel With Area-Changing Cross Section

The two-dimensional cellular detonation propagating in a channel with area-changing cross section was numerically simulated with the dispersion-controlled dissipative scheme and a detailed chemical reaction model. Effects of the flow expansion and compression on the cellular detonation cell were investigated to illustrate the mechanism of the transverse wave development and the cellular detonation cell evolution. By examining gas composition variations behind the leading shock, the chemical reaction rate, the reaction zone length, and thermodynamic parameters, two kinds of the abnormal detonation waves were identified. To explore their development mechanism, chemical reactions, reflected shocks and rarefaction waves were discussed, which interact with each other and affect the cellular detonation in different ways.

Nuclear reactions leading to energy levels of Ar37 and K37

In view of recent interest in the Cl³⁷ (ʋ solar’^e-)Ar³⁷ reaction cross section, information on some aspects of mass 37 nuclei has been obtained using the K³⁹ (d, ∝) Ar³⁷ and Cl³⁵ (He³, p) Ar³⁷ reactions. Ar³⁷ levels have been found at 0, 1.41, 1.62, 2.22, 2.50, 2.80, 3.17, 3.27, 3.53, 3.61, 3.71, (3.75), (3.90), 3.94, 4.02, (4.21), 4.28, 4.32, 4.40, 4.45, 4.58, 4.63, 4.74, 4.89, 4.98, 5.05, 5.10, 5.13, 5.21, 5.35, 5.41, 5.44, 5.54, 5.58, 5.67, 5.77, and 5.85 MeV (the underlined values correspond to previously tabulated levels). The nuclear temperature calculated from the Ar³⁷ level density is 1.4 MeV. Angular distributions of the lowest six levels with the K³⁹ (d, ∝) Ar³⁷ reaction at E_d = 10 MeV indicate a dominant direct interaction mechanism and the inapplicability of the 2I + 1 rule of the statistical model. Comparison of the spectra obtained with the K³⁹ (d, ∝) Ar³⁷ and Cl³⁵ (He³, p) Ar³⁷ reactions leads to the suggestion that the 5.13-MeV level is the T = 3/2 Cl³⁷ ground state analog. The ground state Q-value of the Ca⁴⁰ (p, ∝) K³⁷ reaction has been measured: -5179 ± 9 keV. This value implies a K³⁷ mass excess of -24804 ± 10 keV. Description of a NMR magnetometer and a sixteen-detector array used in conjunction with a 61-cm double-focusing magnetic spectrometer are included in appendices.

Reggeization of some unequal mass processes involving higher spins : the reactions pion-nucleon going to (V,Nucleon), pion-nucleon going to (V,delta-hyperon), and photon-proton going to (positive pion,neutron)

Recent theoretical developments in the reggeization of inelastic processes involving particles with high spin are incorporated into a model of vector meson production. A number of features of experimental differential cross sections and density matrices are interpreted in terms of this model.

The method chosen for reggeization of helicity amplitudes first separates kinematic zeros and singularities from the parity-conserving amplitudes and then applies results of Freedman and Wang on daughter trajectories to the remaining factors. Kinematic constraints on helicity amplitudes at t = 0 and t = (M – M_Δ)² are also considered.

It is found that data for reactions of types πN→VN and πN→VΔ are consistent with a model of this type in which all kinematic constraints at t = 0 are satisfied by evasion (vanishing of residue functions). As a quantitative test of the parametrization, experimental differential cross sections of vector meson production reactions dominated by pion trajectory exchange are compared with the theory. It is found that reduced residue functions are approximately constant, once the kinematic behavior near t = (M – M_Δ)² has been removed.

The alternative possibility of conspiracy between amplitudes is also discussed; and it is shown that unless conspiracy is present, some amplitudes allowed by angular momentum conservation will not contribute with full strength in the forward direction. An example, γp→π⁺n in which the data for dσ/dt indicate conspiracy, is studied in detail.

Inelastic K+p reactions at incident momenta from 1.37 GeV/c to 2.17 GeV/c

A number of recent experiments have suggested the possibility of a highly inelastic resonance in K⁺p scattering. To study the inelastic K⁺p reactions, a 400 K exposure has been taken at the L.R.L. 25 inch bubble chamber. The data are spread over seven K⁺ momenta between 1.37 and 2.17 GeV/c.

Cross-sections have been measured for the reaction K⁺p → pK°π+ which is dominated by the quasi-two body channels K∆ and K*N. Both these channels are strongly peripheral, as at other momenta. The decay of the ∆ is in good agreement with the predictions of the rho-photon analogy of Stodolsky and Sakurai. The data on the K*p channel show evidence of both pseudo scalar and vector exchange.

Cross-sections for the final state pK⁺π+π- shows a strong contribution from the quasi-two body channel K*∆. This reaction is also very peripheral even at threshold. The decay angular distributions indicate the reaction is dominated as at higher momenta by a pion exchange mechanism. The data are also in good agreement with the quark model predictions of Bialas and Zalewski for the K* and ∆ decay.

Magnetic Cross-Linked Enzyme Aggregates (mCLEAs) of Candida antarctica Lipase: An Efficient and Stable Biocatalyst for Biodiesel Synthesis

Enzyme-catalyzed production of biodiesel is the object of extensive research due to the global shortage of fossil fuels and increased environmental concerns. Herein we report the preparation and main characteristics of a novel biocatalyst consisting of Cross-Linked Enzyme Aggregates (CLEAs) of Candida antarctica lipase B (CALB) which are covalently bound to magnetic nanoparticles, and tackle its use for the synthesis of biodiesel from non-edible vegetable and waste frying oils. For this purpose, insolubilized CALB was covalently cross-linked to magnetic nanoparticles of magnetite which the surface was functionalized with –NH2 groups. The resulting biocatalyst combines the relevant catalytic properties of CLEAs (as great stability and feasibility for their reutilization) and the magnetic character, and thus the final product (mCLEAs) are superparamagnetic particles of a robust catalyst which is more stable than the free enzyme, easily recoverable from the reaction medium and reusable for new catalytic cycles. We have studied the main properties of this biocatalyst and we have assessed its utility to catalyze transesterification reactions to obtain biodiesel from non-edible vegetable oils including unrefined soybean, jatropha and cameline, as well as waste frying oil. Using 1% mCLEAs (w/w of oil) conversions near 80% were routinely obtained at 30°C after 24 h of reaction, this value rising to 92% after 72 h. Moreover, the magnetic biocatalyst can be easily recovered from the reaction mixture and reused for at least ten consecutive cycles of 24 h without apparent loss of activity. The obtained results suggest that mCLEAs prepared from CALB can become a powerful biocatalyst for application at industrial scale with better performance than those currently available.

Dependence of the cross sections for Ir isotopes on the values of Qgg in the heavy ion collision

197Au were irradiated with 47 MeV/u 12C ions. Iridium was produced via the multinucleon transfer reactions in bombardments of 197Au with 12C. and was separated radiochemically from Au and the mixture of the reaction products. The γ radioactivities of Ir isotopes were measured by using a HPGe detector. The production cross sections of Ir isotopes were determined from activities of Ir isotopes at the end of bombardment and the other relative data. It has been found that the cross sections for neutron-rich iso...

Production of heavy and superheavy nuclei in massive fusion reactions

Within the framework of a dinuclear system (DNS) model, the evaporation-residue excitation functions and the quasi-fission mass yields in the 48Ca induced fusion reactions are investigated systematically and compared with available experimental data. Maximal production cross sections of superheavy nuclei based on stable actinide targets are obtained. Isotopic trends in the production of the superheavy elements Z = 110, 112–118 based on the actinide isotopic targets are analyzed systematically. Optimal evaporation channels and combinations as well as the corresponding excitation energies are proposed. The possible factors that influencing the isotopic dependence of the production cross sections are analyzed. The formation of the superheavy nuclei based on the isotopes U with different projectiles are also investigated and calculated.

Production mechanism of superheavy nuclei in massive fusion reactions

Within the concept of the dinuclear system (DNS), a dynamical model is proposed for describing the formation of superheavy nuclei in complete fusion reactions by incorporating the coupling of the relative motion to the nucleon transfer process. The capture of two heavy colliding nuclei, the formation of the compound nucleus and the de-excitation process are calculated by using an empirical coupled channel model, solving a set of microscopically derived master equations numerically and applying statistical theory, respectively.Fusion-fission reactions and evaporation residue excitation functions of synthesizing superheavy nuclei (SHN)are investigated systematically and compared them with available experimental data. The possible factors that affecting the production cross sections of SHN are discussed in this workshop.

Neutron-proton bremsstrahlung from intermediate energy heavy-ion reactions as a probe of the nuclear symmetry energy?

Hard photons from neutron-proton bremsstrahlung in intermediate energy heavy-ion reactions are examined as a potential probe of the nuclear symmetry energy within a transport model. Effects of the symmetry energy on the yields and spectra of hard photons are found to be generally smaller than those due to the currently existing uncertainties of both the in-medium nucleon-nucleon cross sections and the photon production probability in the elementary process pn -> pn gamma. Very interestingly, nevertheless, the ratio of hard photon spectra R-1/2(gamma) from two reactions using isotopes of the same element is not only approximately independent of these uncertainties but also quite sensitive to the symmetry energy. For the head-on reactions of Sn-132 + Sn-124 and Sn-112 + Sn-112 at E-beam/A = 50 MeV, for example, the R-1/2(gamma) displays a rise up to 15% when the symmetry energy is reduced by about 20% at rho = 1.3 rho(0) which is the maximum density reached in these reactions. (C) 2008 Elsevier B.V. All rights reserved.

Dynamical analysis on heavy-ion fusion reactions near Coulomb barrier

The shell correction is proposed in the improved isospin dependent quantum molecular dynamics (Im-IQMD) model, which plays an important role in heavy-ion fusion reactions near Coulomb barrier. By using the ImIQMD model, the static and dynamical fusion barriers, dynamical barrier distribution in the fusion reactions are analyzed systematically. The fusion and capture excitation functions for a series of reaction systems are calculated and compared with experimental data. It is found that the fusion cross sections for neutron-rich systems increase obviously, and the strong shell effects of two colliding nuclei result in a decrease of the fusion cross sections at the sub-barrier energies. The lowering of the dynamical fusion barriers favors the enhancement of the sub-barrier fusion cross sections, which is related to the nucleon transfer and the neck formation in the fusion reactions.