Hesseltin A, a novel antiviral metabolite from Penicillium hesseltinei

[structure: see text] Hesseltin A 1, a novel compound of mixed polyketide-terpenoid origins was isolated from the filamentous fungus Penicillium hesseltinei. The structure and stereochemistry were determined from extensive one- and two-dimensional NMR and mass spectral data.     

Optical waveguide sensor for on-line monitoring of bacteria

A grating-coupled planar optical waveguide sensor is presented for sensing of bacteria by evanescent waves. The waveguide design results in increased depth of penetration into the sample volume, which makes it suitable for detecting micrometer-sized biological objects. We tested the sensor's performance by monitoring the adhesion of Escherichia coli K12 cells to the sensor surface.     

High-power intracavity frequency doubling of a Ti:sapphire femtosecond oscillator

We demonstrate intracavity frequency doubling of a standard femtosecond Ti:sapphire oscillator. The cavity is extended with a pair of focusing mirrors and a 0.5-mm-thick BBO crystal. We achieve a repetition rate of 50 MHz and simultaneously generate 22 mW of 55-fs pulses at 810 nm and 200 mW of 73-fs pulses at 405 nm, which corresponds to 4 nJ per pulse. We create a total of 330-mW, 405-nm light when pumping the Ti:sapphire crystal with 5.7 W from an Ar-ion laser, corresponding to a conversion efficiency of 5.7%. No saturation is found, which implies that higher outputs can be achieved with higher pump rates. Preliminary results from the use of blue pulses as pump in an optical parametric amplifier seeded by pulses from a photonic crystal fiber are presented. Received: 27 January 2003 / Revised version: 27 March 2003 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +45-861/96199, E-mail: tva@chem.au.dk     

Relations between 77Se NMR chemical shifts of (phenylseleno)-benzenes and their molecular structures derived from nine X-ray crystal structures

An extensive library of 77Se chemical shifts have been generated from the NMR measurements on substituted (phenylseleno)benzenes, including 33 new compounds. The variation in chemical shifts cover 265 ppm ranging from 446 to 181 ppm. Crystal structures have been determined for nine selected representatives of the substituted (phenylseleno)-benzenes. The analysis of the crystal structures supported that through-space interactions between selenium and the ortho-substituent observed in the crystal structures also are likely to be present in solution. The variation in the 77Se NMR chemical shifts can be rationalised from the intramolecular interactions with the substituent in the ortho-position. Furthermore it appears that these ortho-effects are roughly additive, and that it is the actual interactions and not the resulting conformational constraints that are responsible for the variations in the 77Se NMR chemical shifts.     

Three dimensional alignment of molecules using elliptically polarized laser fields

We demonstrate, theoretically and experimentally, that an intense, elliptically polarized, nonresonant laser field can simultaneously force all three axes of a molecule to align along given axes fixed in space, thus inhibiting the free rotation in all three Euler angles. Theoretically, the effect is illustrated through time dependent quantum mechanical calculations. Experimentally, 3, 4-dibromothiophene molecules are aligned with a nanosecond laser pulse. The alignment is probed by 2D ion imaging of the fragments from a 20 fs laser pulse induced Coulomb explosion.     

On The Correlation Of Binary M-sequences

We obtain the upper bound O(2^14n/15 n^−1/5) on the number of distinct values of all possible correlation functions between M-sequences of order n .     

A family of 13 tetranuclear zinc(II)-lanthanide(III) complexes of a [3+3] Schiff-base macrocycle derived from 1,4-diformyl-2,3-dihydroxybenzene

A family of thirteen tetranuclear heterometallic zinc(II)-lanthanide(III) complexes of the hexa-imine macrocycle (L(Pr))(6-), with general formula Zn(II)(3)Ln(III)(L(Pr))(NO(3))(3)·xsolvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), were prepared in a one-pot synthesis using a 3:1:3:3 reaction of zinc(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene (H(2)L(1)) and 1,3-diaminopropane. A hexanuclear homometallic zinc(II) macrocyclic complex [Zn(6)(L(Pr))(OAc)(5)(OH)(H(2)O)]·3H(2)O was obtained using a 2:0:1:1 ratio of the same reagents. A control experiment using a 1:0:1:1 ratio failed to generate the lanthanide-free [Zn(3)(L(Pr))] macrocyclic complex. The reaction of H(2)L(1) and zinc(II) acetate in a 1:1 ratio yielded the pentanuclear homometallic complex of the dialdehyde H(2)L(1), [Zn(5)(L(1))(5)(H(2)O)(6)]·3H(2)O. An X-ray crystal structure determination revealed [Zn(3)(II)Pr(III)(L(Pr))(NO(3))(2)(DMF)(3)](NO(3))·0.9DMF has the large ten-coordinate lanthanide(III) ion bound in the central O(6) site with two bidentate nitrate anions completing the O(10) coordination sphere. The three square pyramidal zinc(II) ions are in the outer N(2)O(2) sites with a fifth donor from DMF. Measurement of the magnetic properties of [Zn(II)(3)Dy(III)(L(Pr))(NO(3))(3)(MeOH)(3)]·4H(2)O with a weak external dc field showed that it has a frequency-dependent out-of-phase component of ac susceptibility, indicative of slow relaxation of the magnetization (SMM behaviour). Likewise, the Er and Yb analogues are field-induced SMMs; the latter is only the second example of a Yb-based SMM. The neodymium, ytterbium and erbium complexes are luminescent in the solid phase, but only the ytterbium and neodymium complexes show strong lanthanide-centred luminescence in DMF solution.     

Fluctuations in flow produced by competition between apparent wall slip and dilatancy

Dense suspensions can exhibit a dramatic stress-induced transition from liquid-like to solid-like behavior. In many materials, the solid-like flow state is characterized by large flow fluctuations and instabilities. Although various experiments have been performed to characterize flow fluctuations, the mechanisms that govern the flow instabilities remain poorly understood. To elucidate these mechanisms, we characterize a system that rapidly fluctuates between two flow states. One of the flow states is dominated by apparent wall slip, and the other is dominated by dilatancy. The dilatant regime occurs at elevated stresses and is associated with reduced wall slip, whereas the wall slip-dominated regime occurs at lower stresses. At stresses that are intermediate between these two regimes, the material fluctuates between the two regimes in a semi-regular fashion. Our analysis of the fluctuations at millisecond timescales shows that fluctuations occur because neither regime is capable of supporting a constant stress in a stable manner. We rationalize our results in terms of the differences in the shear-induced particle pressure between regions that are particle-rich and regions of slip that are particle-depleted.     

Crystal structure of a partly self-complementary peptide nucleic acid (PNA) oligomer showing a duplex-triplex network

The X-ray structure of a partly self-complementary peptide nucleic acid (PNA) decamer (H-GTAGATCACT-l-Lys-NH(2)) to 2.60 A resolution is reported. The structure is mainly controlled by the canonical Watson-Crick base pairs formed by the self-complementary stretch of four bases in the middle of the decamer (G(4)A(5)T(6)C(7)). One right- and one left-handed Watson-Crick duplex are formed. The two PNA units C(9)T(10) change helical handedness, so that each PNA strand contains both a right- and a left-handed section. The changed handedness in C(9)T(10) allows formation of Hoogsteen hydrogen bonding between C(9)T(10) and G(4)A(5) of a PNA strand in an adjacent Watson-Crick double helix of the same handedness. Thereby, a PNA-PNA-PNA triplex is formed. The PNA unit A(3) forms a noncanonical base pair with A(8) in a symmetry-related strand of opposite handedness; the base pair is of the A-A reverse Hoogsteen type. The structural diversity of this PNA demonstrates how the PNA backbone is able to adapt to structures governed by the stacking and hydrogen-bonding interactions between the nucleobases. The crystal structure further shows how PNA oligomers containing limited sequence complementarity may form complex hydrogen-bonding networks.