A nondestructive method for age determination of fossile bone

Using neutron activation the nitrogen and fluorine contents in fossile bones could be measured relative to main constituents of the inorganic bone material (phosphorus and calcium). By determining the ratio of N and F a relative and absolute age determination was possible. The method is relatively simple, quick, cheap and nondestructive.     

Acoustic Measures and Self-reports of Vocal Fatigue by Female Teachers

This study investigated the relation of symptoms of vocal fatigue to acoustic variables reflecting type of voice production and the effects of vocal loading. Seventy-nine female primary school teachers volunteered as subjects. Before and after a working day, (1) a 1-minute text reading sample was recorded at habitual loudness and loudly (as in large classroom), (2) a prolonged phonation on [a:] was recorded at habitual speaking pitch and loudness, and (3) a questionnaire about voice quality, ease, or difficulty of phonation and tiredness of throat was completed. The samples were analyzed for average fundamental frequency (F0), sound pressure level (SPL), and phonation type reflecting alpha ratio (SPL [1-5 kHz]-SPL [50 Hz-1 kHz]). The vowel samples were additionally analyzed for perturbation (jitter and shimmer). After a working day, F0, SPL, and alpha ratio were higher, jitter and shimmer values were lower, and more tiredness of throat was reported. The average levels of the acoustic parameters did not correlate with the symptoms. Increase in jitter and mean F0 in loud reading correlated with tiredness of throat. The results seem to suggest that, at least among experienced vocal professionals, voice production type had little relevance from the point of view of vocal fatigue reported. Differences in the acoustic parameters after a vocally loading working day mainly seem to reflect increased muscle activity as a consequence of vocal loading.     

Binding H2, N2, H-, and BH3 to transition-metal sulfur sites: synthesis and properties of [RuL(PR3)(N2Me2S2)] Complexes (L=eta2-H2, H-, BH3; R=Cy, iPr)

The reactions of [Ru(N₂)(PR₃)(‘N₂Me₂S₂’)] [‘N₂Me₂S₂’=1,2‐ethanediamine‐N,N′‐dimethyl‐N,N′‐bis(2‐benzenethiolate)(2?)] [ 1 a (R=iPr), 1 b (R=Cy)] and [μ‐N₂{Ru(N₂)(PiPr₃)(‘N₂Me₂S₂’)}₂] ( 1 c ) with H₂, NaBH₄, and NBu₄BH₄, intended to reduce the N₂ ligands, led to substitution of N₂ and formation of the new complexes [Ru(H₂)(PR₃)(‘N₂Me₂S₂’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH₃)(PR₃)(‘N₂Me₂S₂’)] [ 3 a (R=iPr), 3 b (R=Cy)], and [Ru(H)(PR₃)(‘N₂Me₂S₂’)]^? [ 4 a (R=iPr), 4 b (R=Cy)]. The BH₃ and hydride complexes 3 a , 3 b , 4 a , and 4 b were obtained subsequently by rational synthesis from 1 a or 1 b and BH₃?THF or LiBEt₃H. The primary step in all reactions probably is the dissociation of N₂ from the N₂ complexes to give coordinatively unsaturated [Ru(PR₃)(‘N₂Me₂S₂’)] fragments that add H₂, BH₄^?, BH₃, or H^?. All complexes were completely characterized by elemental analysis and common spectroscopic methods. The molecular structures of [Ru(H₂)(PR₃)(‘N₂Me₂S₂’)] [ 2 a (R=iPr), 2 b (R=Cy)], [Ru(BH₃)(PiPr₃)(‘N₂Me₂S₂’)] ( 3 a ), [Li(THF)₂][Ru(H)(PiPr₃)(‘N₂Me₂S₂’)] ([Li(THF)₂]‐ 4 a ), and NBu₄[Ru(H)(PCy₃)(‘N₂Me₂S₂’)] (NBu₄‐ 4 b ) were determined by X‐ray crystal structure analysis. Measurements of the NMR relaxation time T₁ corroborated the η² bonding mode of the H₂ ligands in 2 a (T₁=35 ms) and 2 b (T₁=21 ms). The H,D coupling constants of the analogous HD complexes HD‐ 2 a (¹J(H,D)=26.0 Hz) and HD‐ 2 b (¹J(H,D)=25.9 Hz) enabled calculation of the H? D distances, which agreed with the values found by X‐ray crystal structure analysis ( 2 a : 92 pm (X‐ray) versus 98 pm (calculated), 2 b : 99 versus 98 pm). The BH₃ entities in 3 a and 3 b bind to one thiolate donor of the [Ru(PR₃)(‘N₂Me₂S₂’)] fragment and through a B‐H‐Ru bond to the Ru center. The hydride complex anions 4 a and 4 b are extremely Brønsted basic and are instantanously protonated to give the η²‐H₂ complexes 2 a and 2 b .     

Binding N2, N2H2, N2H4, and NH3 to transition-metal sulfur sites: modeling potential intermediates of biological N2 fixation

In the quest for low-molecular-weight metal sulfur complexes that bind nitrogenase-relevant small molecules and can serve as model complexes for nitrogenase, compounds with the [Ru(PiPr(3))('N(2)Me(2)S(2)')] fragment were found ('N(2)Me(2)S(2)'(2-)=1,2-ethanediamine-N,N'-dimethyl-N,N'-bis(2-benzenethiolate)(2-)). This fragment enabled the synthesis of a first series of chiral metal sulfur complexes, [Ru(L)(PiPr(3))('N(2)Me(2)S(2)')] with L=N(2), N(2)H(2), N(2)H(4), and NH(3), that meet the biological constraint of forming under mild conditions. The reaction of [Ru(NCCH(3))(PiPr(3))('N(2)Me(2)S(2)')] (1) with NH(3) gave the ammonia complex [Ru(NH(3))(PiPr(3))('N(2)Me(2)S(2)')] (4), which readily exchanged NH(3) for N(2) to yield the mononuclear dinitrogen complex [Ru(N(2))(PiPr(3))('N(2)Me(2)S(2)')] (2) in almost quantitative yield. Complex 2, obtained by this new efficient synthesis, was the starting material for the synthesis of dinuclear (R,R)- and (S,S)-[micro-N(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] ((R,R)-/(S,S)-3). (Both 2 and 3 have been reported previously.) The as-yet inexplicable behavior of complex 3 to form also the R,S isomer in solution has been revealed by DFT calculations and (2)D NMR spectroscopy studies. The reaction of 1 or 2 with anhydrous hydrazine yielded the hydrazine complex [Ru(N(2)H(4))(PiPr(3))('N(2)Me(2)S(2)')] (6), which is a highly reactive intermediate. Disproportionation of 6 resulted in the formation of mononuclear diazene complexes, the ammonia complex 4, and finally the dinuclear diazene complex [micro-N(2)H(2)[Ru(PiPr(3))('N(2)Me(2)S(2)')](2)] (5). Dinuclear complex 5 could also be obtained directly in an independent synthesis from 1 and N(2)H(2), which was generated in situ by acidolysis of K(2)N(2)(CO(2))(2). Treatment of 6 with CH(2)Cl(2), however, formed a chloromethylated diazene species [[Ru(PiPr(3))('N(2)Me(2)S(2)')]-micro-N(2)H(2)[Ru(Cl)('N(2)Me(2)S(2)CH(2)Cl')]] (9) ('N(2)Me(2)S(2)CH(2)Cl'(2-) =1,2-ethanediamine-N,N'-dimethyl-N-(2-benzenethiolate)(1-)-N'-(2-benzenechloromethylthioether)(1-)]. The molecular structures of 4, 5, and 9 were determined by X-ray crystal structure analysis, and the labile N(2)H(4) complex 6 was characterized by NMR spectroscopy.     

Orbits of parabolic subgroups on metabelian ideals

Let k be an algebraically closed field, t∈Z?1, and let B be the Borel subgroup of GLt(k) consisting of upper-triangular matrices. Let Q be a parabolic subgroup of GLt(k) that contains B and such that the Lie algebra qu of the unipotent radical of Q is metabelian, i.e. the derived subalgebra of qu is abelian. For a dimension vector with , we obtain a parabolic subgroup P(d) of GLn(k) from B by taking upper-triangular block matrices with (i,j) block of size di×dj. In a similar manner we obtain a parabolic subgroup Q(d) of GLn(k) from Q. We determine all instances when P(d) acts on qu(d) with a finite number of orbits for all dimension vectors d. Our methods use a translation of the problem into the representation theory of certain quasi-hereditary algebras. In the finite cases, we use Auslander-Reiten theory to explicitly determine the P(d)-orbits; this also allows us to determine the degenerations of P(d)-orbits.     

On the volume of a tilting module

We consider a finite dimensional k-algebraA and associate to each tilting module a cone in the Grothendieck groupK ₀ of finitely generated A-modules. We prove that the set of cones associated to tilting modules of projective dimension at most one defines a, not necessarily finite, fan Σ(A). IfA is of finite global dimension, the fan Σ(A) is smooth. Moreover, using the cone of a tilting module, we can associate a volume to each tilting module. Using the fan and the volume, we obtain new proofs for several classical results; we obtain certain convergent sums naturally associated to the algebraA and obtain criteria for the completeness of a list of tilting modules. Finally, we consider several examples. Dedicated to O. Riemenschneider on the occasion of his 65th birthday     

Continuity of the Restriction of C 0-Semigroups to Invariant Banach Subspaces

A linear semigroup in a Banach space induces a linear semigroup on a Banach space that can be continuously embedded in the former such that its image is invariant. This restriction need not be strongly continuous, although the original semigroup is strongly continuous. We show that norm or weak compactness of partial orbits is a necessary and sufficient condition for strong continuity of the restriction of a C₀-semigroup. We then show that if the embedded Banach space is reflexive and the norms of the restricted semigroup operators are bounded near the initial time, then the restricted semigroup is strongly continuous.