Widely tunable THz synthesizer

The generation of cw-THz radiation by photomixing is particularly suited to the high resolution spectroscopy of gases; nevertheless, until recently, it has suffered from a lack of frequency metrology. Frequency combs are a powerful tool that can transfer microwave frequency standards to optical frequencies and a single comb has permitted accurate (10⁻⁸) THz frequency synthesis with a limited tuning range. A THz synthesizer composed of three extended cavity laser diodes phase locked to a frequency comb has been constructed and its utility for high resolution gas phase spectroscopy demonstrated. The third laser diode allows a larger tuning range of up to 300 MHz to be achieved without the need for large frequency excursions, while the frequency comb provides a versatile link to be established from any traceable microwave frequency standard. The use of a single frequency comb as a reference for all of the cw-lasers eliminates the dependency of synthesized frequency on the carrier envelope offset frequency. This greatly simplifies the frequency comb stabilization requirements and leads to a reduced instrument complexity.     

Improved measurement of the hydrogen 1S-2S transition frequency

We have measured the 1S-2S transition frequency in atomic hydrogen via two-photon spectroscopy on a 5.8 K atomic beam. We obtain f(1S-2S) = 2,466,061,413,187,035 (10) Hz for the hyperfine centroid, in agreement with, but 3.3 times better than the previous result [M. Fischer et al., Phys. Rev. Lett. 92, 230802 (2004)]. The improvement to a fractional frequency uncertainty of 4.2 × 10(-15) arises mainly from an improved stability of the spectroscopy laser, and a better determination of the main systematic uncertainties, namely, the second order Doppler and ac and dc Stark shifts. The probe laser frequency was phase coherently linked to the mobile cesium fountain clock FOM via a frequency comb.     

Accurate spectroscopy of Sr atoms

We report the frequency measurement with an accuracy in the 100 kHz range of several optical transitions of atomic Sr: 1S0-3P1 at 689 nm, 3P1-3S1 at 688 nm and 3P0-3S1 at 679 nm. Measurements are performed with a frequency chain based on a femtosecond laser referenced to primary frequency standards. They allowed the indirect determination with a 70 kHz uncertainty of the frequency of the doubly forbidden transition of 87Sr at 698 nm and in a second step its direct observation. Frequency measurements are performed for 88Sr and 87Sr, allowing the determination of 3P0, 3P1 and 3S1 isotope shifts, as well as the 3S1 hyperfine constants.     

Synthesis of new pyridine intermediates as precursors for the elaboration of streptonigrin analogues by the metalation-cross-coupling strategy

Starting from available 2-amino-6-chloro-3-nitropyridine, synthesis of 3-amino-6-pyridinecarboxylic acid derivatives precursor for pyridine ring C of streptonigrin analogues is described.     

Preparation of polymer-anchored dinuclear rhodium(I) catalysts attached by the bridging groups

We describe a method to anchor dinuclear rhodium(I) complexes by substitution of the chlorine bridge in Rh₂(μ-Cl)₂L₄ with LiSR where R represents a polymeric chain. The catalytic activity of such complexes compares well with that observed in homogeneous phase.     

Photodynamic studies and photoinactivation of Escherichia coli using meso-substituted cationic porphyrin derivatives with asymmetric charge distribution

The photodynamic activities of novel asymmetrically meso-substituted cationic porphyrins, 5,10-di(4-methylphenyl)-15,20-di(4-trimethylammoniumphenyl)porphyrin iodide 1 and 5-(4-trifluorophenyl)-10,15,20-tris(4-trimethylammoniumphenyl)porphyrin iodide 2 and its metal complex with Pd(II) 3, have been investigated in both homogeneous medium bearing photooxidizable substrates and in vitro on a typical gram-negative bacterium Escherichia coli. The amphiphilic character of porphyrin 2 was increased by the presence of a high-lipophilic trifluoromethyl group and its photophysical properties changed by forming a complex with Pd(II). Absorption and fluorescence spectroscopic studies were compared in different media. Fluorescence quantum yields (phi(F)) of 0.16 for 1 in tetrahydrofuran and 0.08 for 2 in N, N-dimethylformamide (DMF) were calculated, whereas no significant emission was detected for Pd(II) porphyrin 3. The singlet molecular oxygen, O(2)((1)Delta(g)), production was evaluated using 9,10-dimethylanthracene in DMF yielding relative values of 1, 0.55 and 0.47 for porphyrins 3, 2 and 1, respectively. A faster decomposition of l-tryptophan was obtained using Pd(II) porphyrin 3 as sensitizer with respect to the free-base porphyrins 1 and 2. In biological medium, the behavior of cationic porphyrins 1-3 were compared with that of 5-(4-carboxyphenyl)-10,15,20-tris(4-methylphenyl)porphyrin 4, which was used as a noncationic sensitizer. These porphyrins are rapidly bound to E. coli cells in 5 min and the amount of cell-bound sensitizer is not appreciably changed incubating the cultures for longer times. The recovered porphyrin 2 after one washing step reaches a value of approximately 2.9 nmol/10(6) cells and this amount remains high even after three washes, indicating that this sensitizer is tightly bound to cells. Photosensitized inactivation of E. coli was analyzed using cells without and with one washing step. In both cases, a higher photoinactivation of cells was found for tricationic porphyrin 2 and 3, causing a approximately 5.5 log (99.999%) decrease of cell survival, when treated with 10 microM of sensitizer. Under these conditions, a lower effect was found for porphyrin 1 (approximately 4 log) whereas sensitizer 4 did not produce appreciable photodamage. The results were also confirmed by growth delay experiments. These studies show that the amphiphilic tricationic porphyrin 2 and 3 bearing a trifluoromethyl group can be a promising model for phototherapeutic agents with potential applications in inactivation of bacteria by photodynamic therapy.     

Isotopic shift measurement of the 3P1-3P0 fine structure transition of 24Mg and 26Mg

The isotopic frequency shift for the ³P₁-³P₀Δm_j=0 fine structure transition in the first metastable triplet of ²⁴Mg and ²⁶Mg is reported. The transitions corresponding to the two even isotopes of Mg have been observed via the fluorescence emission at 4571 Å of the intercombination line ³P₁-¹P₀ in a metastable atomic beam. The center frequencies have been measured with an uncertainty of 7×10^-9; the isotopic shift turned out to be 1706 ± 2 kHz.     

Buffer gas pressure shift in the mF = 0 → mF = 0 ground state hyperfine line in Cs

The pressure shift of the m_F:0 → 0 microwave transition of the cesium ground state has been measured for seven buffer gases (He, Ne, N₂, CH₄, C₂H₆, C₃H₈, C₄H₁₀). The high resolution of the experimental apparatus (about one part in 10¹¹ also allows an accurate measurement of the temperature dependence of the shift.     

An optical lattice clock with spin-polarized 87Sr atoms

We present a new evaluation of an ⁸⁷Sr optical lattice clock using spin polarized atoms. The frequency of the ¹S₀→³P₀ clock transition is found to be 429 228 004 229 873.6 Hz with a fractional uncertainty of 2.6×10^-15, a value that is comparable to the frequency difference between the various primary standards throughout the world. This measurement is in excellent agreement with a previous one of similar accuracy [Phys. Rev. Lett. 98, 083002 (2007)].