Two polymorphs of a beta-lactam (trans-13-azabicyclo[10.2.0]tetradecan-14-one). Concomitant crystal polymorphism and isostructurality

Two polymorphs of trans-13-azabicyclo[10.2.0]tetradecan-14-one display a unique example of isostructurality, differing only in the orientation of a given hydrogen bond with respect to the beta-lactam bond. This slight difference can be attributed to the twofold rotation of the carbocyclic macroring of C2 symmetry, which in the crystal structure is hardly noticeable.     

LC-SSI-MS techniques as efficient tools for characterization of nonvolatile phenolic compounds of a special Hungarian wine

The utility of high-performance liquid chromatography-mass spectrometry using electrospray (ESI) and sonic spray (SSI) ionization for the characterization of nonvolatile phenolic compounds is tested using the special Hungarian wine Tokaj aszu of 1983 vintage. Besides caffeic-, ferrulic-, chlorogenic-, and 3,4-dimethoxycinnamic acids; 3,4-dimethoxycinnamoyl-, ferruloyl-, and galloyl-glucose; gentisic acid-beta-D-glucoside; theogallin; and resveratrol-3-O-beta-D-glucoside, 26 flavonoids can be identified. It is shown that because of its higher sensitivity, SSI is a more powerful tool for characterization and monitoring of nonvolatile phenolic compounds than ESI.     

Role of differential scanning calorimetry (DSC) in the staging of COPD

Chronic obstructive pulmonary disease (COPD) is an imminent public health catastrophe. A proper severity marker is desperately needed to reflect the progress of the disease in a stage-specific manner (GOLD I–IV/A–D). The aim of the study was testing the applicability of thermodynamic analysis of blood, identifying different stages of COPD patients against each other and healthy controls. Sera from 63 COPD patients were investigated using differential scanning calorimetry (DSC). Patients formed four groups according to their GOLD severity stages, and smoking or ex-smoking subgroups were further analysed. In total, 18 GOLD A, 17 GOLD B, 16 GOLD C and 12 GOLD D patients’ DSC characteristics were investigated. Nine healthy sera (smoker and non-smoker controls) were evaluated using the same methodology. Enthalpy and melting parameters of severe COPD patients are significantly different from those in the early stages and from healthy subjects. There are clearly visible trends in both features in all stages as COPD progresses. The thermal denaturation parameters are significantly different between the smokers and non-smokers in advanced COPD stages (C&D). Healthy controls do not differ significantly according to their smoking status. The new thermophysical method described here has a potential to be applicable as a stage and/or symptom score of the individual COPD patients. Longitudinal studies are needed to monitor DSC changes of the same patients during progression and/or stagnation.     

Rice straw and energy reed fibers reinforced phenol formaldehyde resin polymeric biocomposites

Cellulose - Herein, natural fiber (energy reeds and rice straw) reinforced with phenol formaldehyde (PF) polymeric resin biocomposites are developed and reported in this study. The dimensions of...     

Z- and E-selective Horner–Wadsworth–Emmons reactions

In the present work, we determined and evaluated the stereochemical outcome of the Horner–Wadsworth–Emmons (HWE) reaction of 2-oxoalkylphosphonates with different ester functions (bis(2,2,2-trifluoroethyl), 2,2,2-trifluoroethyl methyl, dimethyl) and side chains (aliphatic, aromatic) with three different aldehydes (benzaldehyde, THP- and PPB-protected Corey aldehydes) under two reaction conditions. The “trans” protocol is generally used in the E-selective HWE reactions, while “cis” protocol promotes the Z-selectivity.     

Differentiability of quasi-conformal maps on the jungle gym

We obtain a result on the quasi-conformal self-maps of jungle gyms, a divergence-type group. If the dilatation is compactly supported, then the induced map on the boundary of the covering disc is differentiable with non-zero derivative on a set of Hausdorff dimension .

As one of the corollaries, we show that there are quasi-symmetric homeomorphisms over divergence-type groups such that for all sets the Hausdorff dimension of and cannot both be less than . This shows an important difference between finitely generated and divergence-type groups.

     

Lower bound on the profile of degree pairs in cross-intersecting set systems

We raise the following problem. For natural numbers m, n ≥ 2, determine pairs d′, d″ (both depending on m and n only) with the property that in every pair of set systems A, B with |A| ≤ m, |B| ≤ n, and A ∩ B ≠ 0 for all A ∈ A, B ∈ B, there exists an element contained in at least d′ |A| members of A and d″ |B| members of B. Generalizing a previous result of Kyureghyan, we prove that all the extremal pairs of (d′, d″) lie on or above the line (n − 1) x + (m − 1) y = 1. Constructions show that the pair (1 + ɛ / 2n − 2, 1 + ɛ / 2m − 2) is infeasible in general, for all m, n ≥ 2 and all ɛ > 0. Moreover, for m = 2, the pair (d′, d″) = (1 / n, 1 / 2) is feasible if and only if 2 ≤ n ≤ 4. The problem originates from Razborov and Vereshchagin’s work on decision tree complexity. Research supported in part by the Hungarian Research Fund under grant OTKA T-032969.     

Metal-metal electronic coupling in syn and anti stereoisomers of mixed-valent (FeCp)2-, (RhL2)2-, and (FeCp)(RhL2)-as-indacenediide ions

The extent of metal-metal electronic coupling was quantified for a series of syn and anti stereoisomers of (FeCp)(2)-, (RhL(2))(2)- and (FeCp)(RhL(2))- (L(2)=1,5-cyclooctadiene (cod), L=CO) as-indacenediide mixed-valent ions by spectroelectrochemical and DFT studies. The effect of the syn/anti orientation of the metal units with respect to the planar aromatic ligand indicates that electron transfer occurs through the bridge rather than through space. The nature of the metal was found to be crucial: while homobimetallic diiron species are localised valence-trapped ions (Class II), the dirhodium analogues are almost delocalised mixed-valent ions (borderline and Class III). Finally, despite their redox asymmetry, even in the heterobimetallic iron-rhodium as-indacenediide complexes, strong metal-metal coupling is present. In fact, oxidation of the iron centre is accompanied by electron transfer from rhodium to iron and formation of a reactive 17-electron rhodium site. syn and anti Fe-Rh as-indacenediide complexes are rare examples of heterobimetallic systems which can be classified as borderline Class II/Class III species.     

Prediction of protein disorder at the domain level

Intrinsically disordered/unstructured proteins exist in a highly flexible conformational state largely devoid of secondary structural elements and tertiary contacts. Despite their lack of a well defined structure, these proteins often fulfill essential regulatory functions. The intrinsic lack of structure confers functional advantages on these proteins, allowing them to adopt multiple conformations and to bind to different binding partners. The structural flexibility of disordered regions hampers efforts solving structures at high resolution by X-ray crystallography and/or NMR. Removing such proteins/regions from high-throughput structural genomics pipelines would be of significant benefit in terms of cost and success rate. In this paper we outline the theoretical background of structural disorder, and review bioinformatic predictors that can be used to delineate regions most likely to be amenable for structure determination. The primary focus of our review is the interpretation of prediction results in a way that enables segmentation of proteins to separate ordered domains from disordered regions.     

Towards proteomic approaches for the identification of structural disorder

Intrinsically unstructured/disordered proteins (IUPs) and protein domains lack a well-defined three-dimensional structure under physiological conditions. Structural disorder imparts advantages in many non-conventional functions, which poses a significant challenge to our understanding of the structure-function relationship of proteins. The general appreciation of this fact, however, is hampered by the large gap in our knowledge on IUPs, as we have biophysical data on less than 500 of them, whereas bioinformatic predictions suggest at least several thousand such proteins in the human proteome alone. Thus, proteomic-scale identification and characterization of IUPs will need to be implemented to fill this gap and advance our knowledge in this important field. In this review we give an insight into the various rationales of proteomic efforts of identifying IUPs, and survey the handful of attempts that combined enrichment of extracts for IUPs by heat- or acid treatment with a subsequent two-dimensional electrophoresis/mass spectrometry identification. Advantages and drawbacks of the various approaches are outlined in anticipation of future inventions in the field that will hopefully elevate IUP research to the truly proteomic level.