Phase-locked widely tunable optical single-frequency generator based on a femtosecond comb

We present an arbitrary optical single-frequency generator based on a femtosecond optical frequency comb. The functions of this device are comparable to those of a radio-frequency synthesizer. However, this device operates at hundreds of terahertz. The absolute frequency accuracy of this synthesizer is approximately 1 kHz at a 282 THz carrier frequency. The stability is approximately 2 x 10(-14) at 100 s, and the tuning speed exceeds 30 GHz/s. This source demonstrates the integration of a phase-locked optical comb into a versatile and easy-to-use system for the generation of tunable, absolute optical frequencies. By using downconversion, one could generate tunable terahertz frequencies that are phase locked to a microwave reference, such as a Cs atomic clock, and high-precision interferometry could benefit greatly from the stability and accuracy of this widely tunable source.     

Generation of sub-10-fs pulses from a Kerr-lens mode-locked Cr(3+):LiCAF laser oscillator by use of third-order dispersion-compensating double-chirped mirrors

Pulses as short as 9 fs at 220-mW average power and a 97-MHz repetition rate are generated from a cw Ti:sapphire-pumped Kerr-lens mode-locked Cr(3+)LiCAF laser oscillator employing broadband double-chirped mirrors for second- and third-order dispersion compensation. Fine adjustment of dispersion is accomplished with a fused-silica prism pair. The result demonstrates that Raman-induced self-frequency shifting of the pulse does not limit sub-10-fs pulse generation from colquiriite crystals.     

All-optical active mode locking with a nonlinear semiconductor modulator

All-optical active mode locking of a picosecond Nd:YVO(4) laser is demonstrated by use of an intracavity semiconductor nonlinear Fabry-Perot mirror. The reflectivity of the Fabry-Perot mirror is modulated by optical carrier injection. Depending on the carrier recombination time, the width of the Nd:YVO(4) laser pulses varies from 6 to 20 ps, as is typical for passively mode-locked Nd:YVO(4) lasers.     

Ultralow-threshold Kerr-lens mode-locked Ti:Al(2)O(3) laser

An ultralow-threshold Kerr-lens mode-locked Ti:Al(2)O(3) laser achieved by use of an extended cavity design is demonstrated. Mode-locking thresholds as low as 156 mW are achieved. Pulses with durations as short as 14 fs and bandwidths of >100 nm with output powers of ~15 mW at 50-MHz repetition rates are generated by only 200 mW of pump power. Reducing the pump power requirements to a factor of 10x less than required by most conventional Kerr-lens mode-locked lasers permits inexpensive, low-power pump lasers to be used. This will facilitate the development of low-cost, high-performance femtosecond Ti:Al(2)O(3) laser technology.     

"Click-to-chelate": design and incorporation of triazole-containing metal-chelating systems into biomolecules of diagnostic and therapeutic interest

The site-specific conjugation of metal chelating systems to biologically relevant molecules is an important contemporary topic in bioinorganic and bioorganometallic chemistry. In this work, we have used the CuI-catalyzed cycloaddition of azides and terminal alkynes to synthesise novel ligand systems, in which the 1,2,3-triazole is an integral part of the metal chelating system. A diverse set of bidentate alkyne building blocks with different aliphatic and aromatic backbones and various donor groups were prepared. The bidentate alkynes were reacted with benzyl azide in the presence of a catalytic amount of CuI to form tridentate model ligands. The chelators were reacted with [ReBr3(CO)3]2- to form well-defined and stable complexes with different overall charges, structures and hydrophilicities. In all cases tridentate coordination of the ligands, including through N3 of the 1,2,3-triazole ring, was observed. The ligand systems could also be quantitatively radiolabelled with the precursor [99 mTc (H2O)3(CO)3]+ at low ligand concentrations. Similarly the alkynes were reacted with an azido thymidine derivative to form a series of compounds, which could be radiolabelled in situ to form single products. Subsequent incubation of the neutral and cationic organometallic 99 mTc thymidine derivatives with human cytosolic thymidine kinase, a key enzyme in tumour proliferation, revealed that only the neutral compounds maintained substrate activity towards the enzyme. Bioconjugation, radiolabelling and enzymatic reactions were successfully performed in a matter of hours. Thus, click chemistry provides an elegant method for rapidly functionalising a biologically relevant molecule with a variety of efficient metal chelators suitable for (radio)labelling with the M(CO)3 core (M=99 mTc, Re), to offer new potential for technetium-99 m in clinical and preclinical tracer development.     

Prospects for precision measurements of atomic helium using direct frequency comb spectroscopy

We analyze several possibilities for precisely measuring electronic transitions in atomic helium by the direct use of phase-stabilized femtosecond frequency combs. Because the comb is self-calibrating and can be shifted into the ultraviolet spectral region via harmonic generation, it offers the prospect of greatly improved accuracy for UV and far-UV transitions. To take advantage of this accuracy an ultracold helium sample is needed. For measurements of the triplet spectrum a magneto-optical trap (MOT) can be used to cool and trap metastable 2³S state atoms. We analyze schemes for measuring the two-photon 2³S →4³S interval, and for resonant two-photon excitation to high Rydberg states, 2³S →3³P →n³S, D. We also analyze experiments on the singlet-state spectrum. To accomplish this we propose schemes for producing and trapping ultracold helium in the 1¹S or 2¹S state via intercombination transitions. A particularly intriguing scenario is the possibility of measuring the 1¹S →2¹S transition with extremely high accuracy by use of two-photon excitation in a magic wavelength trap that operates identically for both states. We predict a “triple magic wavelength” at 412 nm that could facilitate numerous experiments on trapped helium atoms, because here the polarizabilities of the 1¹S, 2¹S and 2³S states are all similar, small, and positive.     

Syntheses and characterization of dicarbonyl-nitrosyl complexes of technetium(I) and rhenium(I) in aqueous media: spectroscopic, structural, and DFT analyses

This work describes new synthetic routes to produce mixed carbonyl-nitrosyl complexes of technetium(I) and rhenium(I) in aqueous media. NaNO2, NOHSO4, and NO2(g) have been used to produce in situ nitrous acid as the primary source of NO+. Starting from the organometallic precursor fac-[MX3(CO)3]+, 1 (M = 99Tc, Re; X = Cl, Br), the formation of mixed dicarbonyl-mononitrosyl complexes was observed in aqueous hydrochloric and hydrobromic acid. Time-dependent analyses of the reactions by means of HATR-IR and 99Tc NMR spectroscopy in solution revealed the almost quantitative substitution of one CO ligand by NO+ and, thus, the formation of complexes with facial arrangement of the three pi-acceptor ligands. In the case of technetium, the monomeric complex (NEt4)[TcCl3(CO)2NO] (3a) and the dimeric, chloride-bridged, neutral complex [TcCl(mu-Cl)(CO)2NO]2 (4a) were produced. In the case of rhenium, the monomeric species (NEt4)[ReBr2X(CO)2NO] (X = Br (3b), NO3 (5)) was solely isolated. The X-ray structure of complexes 4a and 5 are discussed. The crystallographic analyses revealed the coordination of the NO+ group trans to the terminal chloride (4a) or the bromide (5), respectively. Crystal data: complex 4a (C4Cl4N2O(6)Tc2), monoclinic, Cc, a = 18.82(3) A, b = 6.103(6) A, c = 12.15(2) A, alpha = 90 degrees , beta = 105.8(2) degrees , gamma = 90 degrees , V = 1343(3) A(3), Z = 4; complex 5 (C10H20N3O(6)Br2Re), orthorhombic, P2(1)2(1)2(1), a = 10.2054(5) A, b = 12.5317(7) A, c = 13.9781(7) A, V = 1787.67(16) A(3), Z = 4. The isolated complexes and their potential facial isomers have been further investigated by density functional theory (DFT) calculations. The energy differences of the isomers are relatively small; however, the calculated energies are consistent with the formation of the observed and isolated compounds. The calculated bond lengths and angles of complex 5 are in good agreement with the data determined by X-ray diffraction. Experiments on the no-carrier-added level starting from fac-[99mTc(H2O)3(CO)3]+ revealed the formation of the complex fac-[99mTcCl(H2O)2(CO)2NO]+ in reasonable good yields. This aqueous-based, synthetic approach will enable the future evaluation of this novel, low-valent metal precursor for potential use in radiopharmacy.     

Derivatization of glucose and 2-deoxyglucose for transition metal complexation: substitution reactions with organometallic 99mTc and Re precursors and fundamental NMR investigations

Synthetic strategies for the bifunctionalization of glucose and 2-deoxyglucose at position C-1 for transition metal coordination are reported. In particular organometallic technetium and rhenium complexes for potential use in diagnostic nuclear medicine were synthesized and investigated. Specifically, a common iminodiacetic acid (IDA) moiety was O-glycosidically connected through an ethylene spacer group to produce the pure alpha- (in case of 2-deoxyglucose) and beta-anomer (in case of glucose). Reaction of the sugar derivatives with the organometallic precursor [M(H2O)3(CO)3]+ (M = 99mTc, Re) produced single products in high yield, which are water-soluble and water-stable. The displacement of the three water molecules of the metal precursor and thus the tridentate coordination of the metal-tricarbonyl core exclusively via the amine and the two carboxylic acid functionalities of the IDA chelate was verified by means of 1D and 2D 1H NMR spectroscopy, mass spectrometry, and IR spectroscopy. The radioactive-labeled products (99mTc) proved their excellent stability in vitro in physiological phosphate buffer (pH = 7.4) and human plasma over a period of 24 h at 37 degrees C.     

Darstellung und Strukturen von (Et4N)2[Re(CO)3(NCS)3] und (Et4N)[Re(CO)2Br4]

Syntheses and Structures of (Et₄N)₂[Re(CO)₃(NCS)₃] and (Et₄N)[Re(CO)₂Br₄] Rhenium(I) and rhenium(III) carbonyl complexes can easily be prepared by ligand exchange reactions starting from (Et₄N)₂[Re(CO)₃Br₃]. Using nonoxidizing reagents the facial Re^I(CO)₃ unit remains and only the bromo ligands are exchanged. Following this procedure, (Et₄N)₂[Re(CO)₃(NCS)₃] can be obtained in high yield and purity using trimethylsilylisothiocyanate. The compound crystallizes in the monoclinic space group P2₁/n, a = 18.442(5), b = 17.724(3), c = 18.668(5) Å, β = 92.54(1)°, Z = 8. The NCS^? ligands are coordinated via nitrogen. The reaction of [Re(CO)₃Br₃]^2? with Br₂ yields the rhenium(III) anion [Re(CO)₂Br₄]^?. The tetraethylammonium salt of this complex crystallizes in the noncentrosymmetric, orthorhombic space group Cmc2₁, a = 8.311(1), b = 25.480(6), c = 8.624(1) Å, Z = 4. The carbonyl ligands are positioned in a cis arrangement. Their strong trans influence causes a lengthening of the Re? Br bond distances by at least 0.05 Å.     

Design and fabrication of double-chirped mirrors

We present an analytic design method for the reproducible fabrication of double-chirped mirrors to achieve simultaneously a high reflectivity and dispersion compensation over an extended bandwidth compared with those of standard quarter-wave Bragg mirrors. The mirrors are fabricated by ion beam sputtering. Use of these mirrors in a Ti:sapphire laser leads to 6.5-fs pulses directly out of the laser. The method can also be applied to the design of chirped-fiber gratings and general optical filters.