Structural characterisation by ESI-MS of feruloylated arabino-oligosaccharides synthesised by chemoenzymatic esterification

The chemoenzymatic synthesis of feruloylated arabino-oligosaccharides has been achieved, using a feruloyl esterase type C from Sporotrichum thermophile (StFaeC).The structure of the feruloylated products was confirmed by ESI-MS(n).     

Logging damage and injured tree mortality in tropical forest management

Using insights from the forest ecology literature, we analyze the effect of injured trees on stand composition and carbon stored in above‐ground biomass and the implications for forest management decisions. Results from a Faustmann model with data for a tropical forest on Kalimantan show that up to 50% of the basal area of the stand before harvest can consist of injured trees. Considering injured trees leads to an increase in the amount of carbon in above‐ground biomass of up to 165%. These effects are larger under reduced impact logging than under conventional logging. The effects on land expectation value and cutting cycle are relatively small. The results suggest that considering injured trees in models for tropical forest management is important for the correct assessment of the potential of financial programs to store carbon and conserve forest ecosystem services in managed tropical forests, such as reducing emissions from deforestation and forest degradation and payment for ecosystem services. Recommendations for Resource Managers

• Considering the role of injured trees is important for managing tropical forests
• These trees can cover up to 50% of basal area and contain more than 50% of the carbon stored in above‐ground biomass
• Reduced impact logging leads to a larger basal area of injured trees and more carbon stored in injured trees than conventional logging
• Injured trees play an important role when assessing the potential for carbon storage in the context of payment for forest ecosystem services.

     

A short review and an empirical method for estimating the absorbed enthalpy of formation and the absolute enthalpy of dried microbial biomass for use in studies on the thermodynamics of microbial growth

Calculations are made using the equations Δ_r G = Δ_r H − TΔ_r S and Δ_r X = Δ_r H − Δ_r Q where Δ_r X represents the free energy change when the exchange of absorbed thermal energy with the environment is represented by Δ_r Q. The symbol Q has traditionally represented absorbed heat. However, here it is used specifically to represent the enthalpy listed in tabulations of thermodynamic properties as (H _T  − H ₀) at T = 298.15 K, the reason being that for a given substance TS equals 2.0 Q for solid substances, with the difference being greater for liquids, and especially gases. Since Δ_r H can be measured, and is tangibly the same no matter what thermodynamics are used to describe a reaction equation, a change in the absorbed heat of a biochemical growth process system as represented by either Δ_r Q or TΔ_r S would be expected to result in a different calculated value for the free energy change. Calculations of changes in thermodynamic properties are made which accompany anabolism; the formation of anabolic, organic by-products; catabolism; metabolism; and their respective non-conservative reactions; for the growth of Saccharomyces cerevisiae using four growth process systems. The result is that there is only about a 1% difference in the average quantity of free energy conserved during growth using either Eq. 1 or 2. This is because although values of TΔ_r S and Δ_r Q can be markedly different when compared to one another, these differences are small when compared to the value for Δ_r G or Δ_r X.     

Finite-Time Universality in Nonequilibrium CFT

Recently, remarkably simple exact results were presented about the dynamics of heat transport in the local Luttinger model for nonequilibrium initial states defined by position-dependent temperature profiles. We present mathematical details on how these results were obtained. We also give an alternative derivation using only algebraic relations involving the energy-momentum tensor which hold true in any unitary conformal field theory (CFT). This establishes a simple universal correspondence between initial temperature profiles and the resulting heat-wave propagation in CFT. We extend these results to larger classes of nonequilibrium states. It is proposed that such universal CFT relations provide benchmarks to identify nonuniversal properties of nonequilibrium dynamics in other models.     

Numerical Approximation of Uncertain Nonlinear Systems

We address qualitative characteristics of dynamical systems and their approximation using set–valued numerical methods, where we aim at robust results. In this spirit, model uncertainties are incorporated into the problem formulation as outcomes of an external stochastic process. The systems under consideration are described in terms of finite state Markov chains. An example serves to illustrate the procedure. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

High Loading Efficiency and Controlled Release of Bioactive Immunotherapeutic Proteins Using Vaterite Nanoparticles

Nanoparticles may limit off-tumor/on-target ubiquitous activation of signaling by protein-based drugs. However, many challenges still exist in the design of a nanoparticle for protein delivery. In this study, conditions to establish vaterite nanoparticles as a pH-sensitive drug delivery system (DDS) for encapsulated protein drugs are comprehensively evaluated. Low coprecipitation pH of vaterite and protein prevents protein denaturation and yields high loading efficiency. Unprotected vaterite recrystallizes in aqueous solutions within 3 h to calcite and releases the loaded protein completely, but surface-modified particles with carboxyl groups containing polymers prove stable for more than 5 months. Notably, modification of vaterite with sulfonated polymers increases the loading of cationic proteins by a multiple. A system is developed for vaterite exposure to (pH) conditions under body-like-flow rates, with the dissolution of vaterite and simultaneous release of active proteins at tumor microenvironmental pH reaching up to 80% and only 20% at physiological pH within 2 h. Importantly, the immunomodulatory protein tumor necrosis factor preserves its native structure and fully retains functional activity in vitro after release from the particles. In conclusion, the studies described here provide a framework for the development of vaterite-based DDS as a carrier for bioactive protein-based therapeutics.     

Dissipative soliton resonance in a passively mode-locked fiber laser

The phenomenon of dissipative soliton resonance (DSR) predicts that an increase of pulse energy by orders of magnitude can be obtained in laser oscillators. Here, we prove that DSR is achievable in a realistic ring laser cavity using nonlinear polarization evolution as the mode-locking mechanism, whose nonlinear transmission function is adjusted through a set of waveplates and a passive polarizer. The governing model accounts explicitly for the arbitrary orientations of the waveplates and the polarizer, as well as the gain saturation in the amplifying medium. It is shown that DSR is achievable with realistic laser settings. Our findings provide an excellent design tool for optimizing the mode-locking performance and the enhancement of energy delivered per pulse by orders of magnitude.     

Ethynyl and Propynylpyrene Inhibitors of Cytochrome P450

Abstract  

The single-crystal X-ray structures and in vivo activities of three aryl acetylenic inhibitors of cytochromes P450 1A1, 1A2, 2A6, and 2B1 have been determined and are reported herein. These are 1-ethynylpyrene, 1-propynylpyrene, and 4-propynylpyrene. To investigate electronic influences on the mechanism of enzyme inhibition, the experimental electron density distribution of 1-ethynylpyrene has been determined using low-temperature X-ray diffraction measurements, and the resulting net atomic charges compared with various theoretical calculations. A total of 82,390 reflections were measured with Mo Kα radiation to a (sinθ/λ)_max = 0.985 Å⁻¹. Averaging symmetry equivalent reflections yielded 8,889 unique reflections. A least squares refinement procedure was used in which multipole parameters were added to describe the distortions of the atomic electron distributions from spherical symmetry. A map of the model electron density distribution of 1-ethynylpyrene was obtained. Net atomic charges calculated from refined monopole population parameters yielded charges that showed that the terminal acetylenic carbon atom (C18) is more negative than the internal carbon (C17). Net atomic charges calculated by ab initio, density functional theory, and semi-empirical methods are consistent with this trend suggesting that the terminal acetylenic carbon atom is more likely to be the site of oxidation. This is consistent with the inhibition mechanism pathway that results in the formation of a reactive ketene intermediate. This is also consistent with assay results that determined that 1-ethynylpyrene acts as a mechanism-based inhibitor of P450s 1A1 and 1A2 and as a reversible inhibitor of P450 2B1. Crystallographic data: 1-ethynylpyrene, C₁₈H₁₀, P2₁/c, a = 14.571(2) Å, b = 3.9094(5) Å, c = 20.242(3) Å, β = 105.042(2)°, V = 1,113.5(2) Å³; 1-propynylpyrene, C₁₉H₁₂, P2₁/n, a = 8.970(2) Å, b = 10.136(1) Å, c = 14.080(3) Å, β = 99.77(2)°, V = 1,261.5(4) Å³; 4-propynylpyrene, C₁₉H₁₂, Pbca, a = 9.904(1) Å, b = 13.174(2) Å, c = 19.401(1) Å, V = 2,531.4(5) Å³.     

Determination of Albuterol Enantiomers in Animal Tissue Matrices by LC–MS/MS: Application in Therapeutic Myoanabolic Studies

Albuterol (salbutamol) is a widely used medication in respiratory disease including asthma and chronic obstructive airways disease; however, like other beta2-agonists, it also exerts some extrapulmonary effects on muscle and fat. Surprisingly, there have been relatively few reports of albuterol tissue distribution, and the distribution of individual albuterol enantiomers into tissue has not been reported. The method presented here explores the use of an HPLC tandem mass spectrometry (LC–MS/MS) system (LTQ Orbitrap hybrid mass spectrometer) with deuterated standard and solid-phase extraction to determine low levels of albuterol enantiomers in tissue. The lower limit of quantification (LLOQ) was 0.156 ng g⁻¹, with a precision RSD <15% for both enantiomers. The assay was linear over the calibration range of LLOQ-10.0 ng g⁻¹ in muscle tissue (r ² > 0.98). The assay was successfully applied to pharmacokinetic studies in rats and mice. By utilizing a deuterated internal standard and LC–MS/MS detection, this assay can be used to measure albuterol enantiomers in muscle tissue. This assay has also identified that albuterol uptake appears to be stereoselective, and enantioselective assays are clearly warranted for myoanabolic studies involving administration of racemic-albuterol.

     

An efficient anti-aliasing spectral continuous window shifting technique for PIV

A new sub-pixel correlation peak locating algorithm for PIV analysis is introduced. The method is theoretically consistent with the method of continuously shifting interrogation sub-windows by fractional displacements, which has proven to be an effective way to reduce the bias error associated with integer pixel aliasing, or peak-locking. However the proposed algorithm performs continuous window shifting in the spatial frequency domain using the shift property of the Fourier transform, thus it is equivalent to interpolating the original digital image with the Fourier transform reconstruction. Synthetic and real PIV images are used to test the new algorithms performance relative to that of traditional (non-iterative) peak-finding methods and other peak-locking reduction algorithms, such as the continuous window shifting technique. The resultant bias error of the proposed algorithm is smaller (by an order of magnitude in some cases), and importantly, the periodic nature of the bias error, the characteristic signature of peak-locking, is eliminated as long as the discrete particle images have been sampled at a rate greater than the Nyquist sampling frequency. Moreover, this new algorithm is shown to be computationally efficient and it converges faster than the competing algorithms.