Rapid method for the isolation of the mature collagen cross-links, hydroxylysylpyridinoline and lysylpyridinoline

Hydroxylysylpyridinoline (HP) and lysylpyridinoline (LP) are two non-reducible cross-links of mature collagen which are formed by a sequence of post-translational modifications. HP is a derivative of three residues of hydroxylysine and is present in almost all mature tissues (e.g., tendons, vessel walls, cartilage, teeth and bone). LP is a derivative of two residues of hydroxylysine and one residue of lysine and is present only in dentine and bone. Neither cross-link is found in normal human skin. HP and LP were purified from commercially available bone gelatine (“ossein hydrolysate”) by preparative reversed-phase HPLC and the degree of purity was verified by amino acid determination ( > 98% dry mass). Hydroxylysylpyridinoline and lysylpyridinoline are promising markers in urine of collagen resorption because their levels in urine should reflect only the breakdown of collagen fibres of skeletal tissues. The two components were used as external standards and the determination of HP and LP in urine provides a good means for the specific evaluation of pathological conditions associated with increased bone resorption, e.g., high turnover post-menopausal osteoporosis.     

Theoretical Study of the Distortion from Regular Tetrahedral Structure of M(NH2)4 Complexes

Theoretical study on tetrakis-amido complexes (M(NR₂)₄, M = Ti, V, Cr, and Mo; R = H, Me) is presented. At first a rough investigation of the potential energy surface indicates that all stationary points are of S ₄ or D ₂ symmetry depending on the coupled rotations of the NR₂ groups. Qualitative correlation diagrams are calculated within S ₄ or D ₂ symmetry constraint between two limiting structures of D ₂ d symmetry. DFT (B3LYP) calculations on these two paths are presented for unsubstituted complexes (R = H) and the various minima are optimized and characterized. These results are discussed in the light of the correlation diagrams. Finally, optimization of the different minima has been performed on substituted species (R = Me) and the theoretical results are shown to be in good agreement with the experimental structural determination when available.     

Liquid chromatography/electrospray ionization mass spectrometry for the characterization of twenty-three flavonoids in the extract of Dalbergia odorifera

A method incorporating high-performance liquid chromatography (HPLC) with electrospray ionization and tandem mass spectrometry, with parallel analysis by HPLC with UV detection using a diode-array detector, was developed for the qualitative characterization of flavonoids in D. odorifera. Twenty-three flavonoids, including six isoflavones, six neoflavones, four isoflavanones, three flavanones, two chalcones, one isoflavanonol and one pterocarpan, were unambiguously identified by comparing their retention times, UV and MS spectra with those of authentic compounds. Furthermore, the collision-induced dissociations of the [M-H]- ions were studied to clarify the MS behavior of the different types of flavonoids. In negative ion ESI-MS all the flavonoids yielded prominent [M-H]- ions in the first order mass spectra. Fragments involving losses of CH3*, H2O, CO, C2H2O, and CO2 were observed in the MS/MS spectra. Each of the seven types of flavonoid showed characteristic MS/MS fragmentation patterns. The isoflavanones, flavanones and chalcones were observed to undergo retro-Diels-Alder fragmentations. The spectra of almost all the neoflavonoids unexpectedly exhibited only [M-H-CH3]-* radical anions as base peaks without any further fragmentation. Substitution positions also remarkably influenced the fragmentation behavior, which could assist in distinction among the flavonoid isomers. The fragmentation rules deduced here could aid in the characterization of other flavonoids of these types.     

X-ray crystal structures of three nonbenzodiazepinic ligands for the benzodiazepine receptor sites: SR95926, CMW1842, and L16317:nab initio MO study of the electronic properties

The crystal structures ofp-methoxyphenyl-3-triazolo [4,3-a] isoquinoline (SR95926),p-methoxyphenyl-3-triazolophtalazine (CMW1842), andp-methoxyphenyl-3-N-dimethoxyethylamino-6-triazolophtalazine (L16317) have been solved by direct methods from single-crystal X-ray diffraction data, and refined by full-matrix least squares. SR95926: monoclinic,P2₁/n,a=20.950(3),b=6.769(1),c=9.465(2) Å,=100.90(1)°. CMW1842: triclinic,P¯1,a=8.784(1),b=9.160(4),c=8.555(1) Å,=99.10(2),=93.90(1), =106.77(1)°. L16317: monoclinic,P2₁/_n,a=20.124(3),b=9.586(1),c=10.788(1) Å,=91.91(1)°. FinalR factors are 0.034, 0.037, and 0.053, respectively. Experimental geometries were used to perform STO-3Gab initio molecular-orbital calculations. A relationship between the electronic pattern within the molecules and the affinity of the benzodiazepine receptor sites is pointed out.     

A grothendieck factorization theorem on 2-convex schatten spaces

We prove that for every bounded linear operatorT:C ^2p →H(1≤p<∞,H is a Hilbert space,C ^{2 p} p is the Schatten space) there exists a continuous linear formf onC ^p such thatf≥0, ‖f‖(C _C ^p)*=1 and $$\forall x \in C^{2p} , \left\| {T(x)} \right\| \leqslant 2\sqrt 2 \left\| T \right\|< f\frac{{x * x + xx*}}{2} > 1/2$$ . Forp=∞ this non-commutative analogue of Grothendieck’s theorem was first proved by G. Pisier. In the above statement the Schatten spaceC ^2p can be replaced byE _E ² whereE ⁽²⁾ is the 2-convexification of the symmetric sequence spaceE, andf is a continuous linear form onC _E. The statement can also be extended toL _E{(su2)}(M, τ) whereM is a Von Neumann algebra,τ a trace onM, E a symmetric function space.     

On strong summability of multiple Fourier series and smoothness properties of functions

_n —n- — ƒ()L _v (T _n ), 1f, - -. -.     

Nuclear structure and chemical effects in internal conversion of the 35 keVM1+E2 transition in125Te

The relative conversion line intensities of the 35 keV transition in¹²⁵Te were measured using the 50 cm π√2 iron-yoke magnetic spectrometer. The transition was proved to be ofM1+(8.7±1.5)×10^?4 E2 multipolarity, the magnetic component being affected by the nuclear structure with λ=2.4±1.4. The conversion intensity ratio,0/N ₁ , was determined to be 0.115+0.005 for both Ag¹²⁵ I and Cu¹²⁵ I sources. It is in accordance with previous measurements for the Zn^125m Te and Pb^125m Te sources and differs from those for the^125mTeO₂ and Na₂H ₄ ^125m TeO₆ ones. The conversion coefficients were calculated for 32 configurations of the valence shell of free tellurium atom and ions and were compared with the experimental results.