Determination of differences in ultrasound parameters for patellar tendons in males with unilateral patellar tendinopathy-An ancillary analysis of data from two randomized controlled trials.

PURPOSE: To investigate power Doppler (PD) activity and tendon structure (between the injured and contralateral limb) in patients with unilateral patellar tendinopathy (PT) using ultrasonography (US). Secondly, the aim was to determine the intra-rater reliability of the PD activity and tendon structure. METHODS: This study analyzed US baseline data from 57 male participants with symptomatic unilateral PT who had been enrolled in one of two randomized clinical trials. Data were analyzed to examine if systematic differences existed between injured and contralateral limbs using Fiji ImageJ. RESULTS: The PD activity of the symptomatic tendon was larger 25.6 (Q1 = 14.9; Q3 = 41.6) mm2 than the asymptomatic 0 (Q1 = 0.0; Q3 = 0.0) mm2 (p < 0.001). There was a significantly greater tendon thickness at the proximal (2.5 mm 95% CI [2.0; 3.0]), mid (0.8 mm 95% CI [0.5; 1.1]), and distal (0.2 mm 95% CI [0.1; 0.4]) part of the tendon for the symptomatic compared to the asymptomatic tendon. Intra-rater reliability for PD activity and tendon structure ranged from moderate-to-excellent (0.74; 0.99). CONCLUSION: These results provide mean estimates for tendon thickness of symptomatic and asymptomatic tendons, that can be used for clinicians to reliably estimate pathological tendon thickness.

The charge density distribution in a model compound of the catalytic triad in serine proteases.

Combined low temperature (28(1) K) X-ray and neutron diffraction measurements were carried out on the co-crystallised complex of betaine, imidazole, and picric acid (1). The experimental charge density was determined and compared with ab initio theoretical calculations at the B3LYP/6-311G(d,p) level of theory. The complex serves as a model for the active site in, for example, the serine protease class of enzymes, the so-called catalytic triad. The crystal contains three short strong N-H...O hydrogen bonds (HBs) with dN...O < 2.7 A. The three HBs have energies above 13 kcalmol(-1), although the hydrogen atoms are firmly localized in the "nitrogen wells". This suggests that low-barrier hydrogen bonding in catalytic enzyme reactions may be a sufficient, but not a necessary, condition for obtaining transition-state stabilization. Structural analysis (e.g., covalent N-H bond lengthening) indicates that the hydrogen bond between H3A and 08 of imidazole and betaine respectively (HB2) is slightly stronger than the bond between H1A and O1A of imidazole and picric acid (HB1), although HB1 is shorter than HB2: (dN...O(HB1)= 2.614(1) A, dN...O(HB2) = 2.684(1) A, dH...O(HB1) = 1.630(1) A, dH...O(HB2)= 1.635(1) A, dN-H(HB1) = 1.046(1) A, dN-H(HB2) = 1.057(1) A). Furthermore, the charge density analysis reveals that HB2 has a larger covalent character than HB1, with considerable polarization of the density towards the acceptor atom. The Gatti and Bader source function (S) is introduced to the analysis of strong HBs. The source function is found to be a sensitive measure for the nature of a hydrogen bond, and comparison with low-barrier and single-well hydrogen bonding systems (e.g., benzoylacetone and nitromalonamide) shows that the low-barrier hydrogen bond (LBHB) state is characterized by an enormously increased hydrogen atom source contribution to the bond critical point in the HB. In this context, HB2 can be characterized as intermediate between localized HBs and delocalized LBHBs.

On the electronic nature of low-barrier hydrogen bonds in enzymatic reactions.

The electronic nature of low-barrier hydrogen bonds (LBHBs) in enzymatic reactions is discussed based on combined low temperature neutron and x-ray diffraction experiments and on high level ab initio calculations by using the model substrate benzoylacetone. This molecule has a LBHB, as the intramolecular hydrogen bond is described by a double-well potential with a small barrier for hydrogen transfer. From an "atoms in molecules" analysis of the electron density, it is found that the hydrogen atom is stabilized by covalent bonds to both oxygens. Large atomic partial charges on the hydrogen-bonded atoms are found experimentally and theoretically. Therefore, the hydrogen bond gains stabilization from both covalency and from the normal electrostatic interactions found for long, weak hydrogen bonds. Based on comparisons with other systems having short-strong hydrogen bonds or LBHBs, it is proposed that all short-strong and LBHB systems possess similar electronic features of the hydrogen-bonded region, namely polar covalent bonds between the hydrogen atom and both heteroatoms in question.

Experimental evidence for the existence of non-nuclear maxima in the electron-density distribution of metallic beryllium. A comparative study of the maximum entropy method and the multipole refinement method.

The electron-density distribution (EDD) of metallic beryllium has been derived from the structure factors of Larsen & Hansen [(1984). Acta Cryst. B40, 169-179] using the maximum entropy method (MEM). Subsequent topological analysis reveals non-nuclear maxima (NNM) in the EDD. Plots of the gradient field of the electron density illustrates this finding. A possible critical-point network for the hexagonal close-packed (h.c.p.) structure of beryllium is suggested. It is thus demonstrated that it is possible to obtain detailed topological information about the electron density in metallic beryllium without the use of a structural model. In order to test the findings of the MEM, the same set of structure factors were analysed using the multipole refinement method (MRM). Use of the MRM also reveals NNM. The results of the two different approaches to electron-density analysis are contrasted and discussed. Expressed within the framework of the theory of atoms in molecules, our results suggest that the h.c.p. structure of beryllium has no Be atoms directly bonded to other Be atoms. The structure is held together through a three-dimensional network of bonds between the NNM and Be atoms as well as between different NNM. The topological analysis thus reveals that the beryllium structure has important interactions connecting Be atoms of different basal plane layers. The breaking of these interactions when forming a surface may explain the abnormally large expansion of the inter-layer distance in the beryllium surface structure.

Charge distribution in the light-atom mineral kernite.

A charge density analysis of accurate x-ray data for the mineral kernite Na(2)B(4)O(6)(OH)(2). 3H(2)O indicates that the sodium and boron atoms have partial positive charges of 0.4 to 0.5 unit and 0.4 to 0.7 unit, respectively, whereas the oxygen atoms have negative charges of about 0.4 to 0.5 unit. The best agreement with the intensities and with the experimental scale factor is obtained with contracted molecule-optimized atomic orbitals. Difference density maps based on high-order parameters show more density in B-O than in Na-O bonds, thus supporting the covalent nature of the bonds between boron and oxygen atoms.