Systematic study of the 87Srclock transition in an optical lattice

With ultracold 87Srconfined in a magic wavelength optical lattice, we present the most precise study (2.8 Hz statistical uncertainty) to date of the 1S0-3P0 optical clock transition with a detailed analysis of systematic shifts (19 Hz uncertainty) in the absolute frequency measurement of 429 228 004 229 869 Hz. The high resolution permits an investigation of the optical lattice motional sideband structure. The local oscillator for this optical atomic clock is a stable diode laser with its hertz-level linewidth characterized by an octave-spanning femtosecond frequency comb.     

The 2.0 angstroms crystal structure of a pocilloporin at pH 3.5: the structural basis for the linkage between color transition and halide binding

The pocilloporin Rtms5 and an engineered variant Rtms5H146S undergo distinct color transitions (from blue to red to yellow to colorless) in a pH-dependent manner. pK(a) values of 4.1 and 3.2 were determined for the blue (absorption lambda(max), 590 nm) to yellow (absorption lambda(max), approximately 453 nm) transitions of Rtms5 and Rtms5H146. The pK(a) for the blue-yellow transition of Rtms5H146S increased by 1.4 U in the presence of 0.1 M KI, whereas the pK(a) for the same transition of Rtms5 was relatively insensitive to added halides. To understand the structural basis for these observations, we have determined to 2.0 angstroms resolution the crystal structure of a yellow form of Rtms5H146S at pH 3.5 in the presence of iodide. Iodide was found occupying a pocket in the structure with a pH of 3.5, forming van der Waals contacts with the tyrosyl moiety of the chromophore. Elsewhere, it was determined that this pocket is occupied by a water molecule in the Rtms5H146S structure (pH 8.0) and by the side chain of histidine 146 in the wild-type Rtms5 structure. Collectively, our data provide an explanation for the observed linkage between color transitions for Rtms5H146S and binding to halides.     

Interaction of ionic liquid with water in ternary microemulsions (Triton X-100/water/1-butyl-3-methylimidazolium hexafluorophosphate) probed by solvent and rotational relaxation of coumarin 153 and coumarin 151

The interaction of ionic liquid with water in 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6])/Triton X-100 (TX-100)/H2O ternary microemulsions, i.e., "[bmim][PF6]-in-water" microregions of the microemulsions, has been studied by the dynamics of solvent and rotational relaxation of coumarin 153 (C-153) and coumarin 151 (C-151). The variation of the time constants of solvent relaxation of C-153 is very small with an increase in the [bmim][PF6]/TX-100 ratio (R). The rotational relaxation time of C-153 also remains unchanged in all micremulsions of different R values. The invariance of solvation and rotational relaxation times of C-153 indicates that the position of C-153 remains unaltered with an increase in R and probably the probe is located at the interfacial region of [bmim][PF6] and TX-100 in the microemulsions. On the other hand, in the case of C-151, with an increase in R the fast component of the solvation time gradually increases and the slow component gradually decreases, although the change in solvation time is small in comparison to that of microemulsions containing common polar solvents such as water, methanol, acetonitrile, etc. The rotational relaxation time of C-151 increases with an increase in R. This indicates that with an increase in the [bmim][PF6] content the number of C-151 molecules in the core of the microemulsions gradually increases. In general, the solvent relaxation time is retarded in this room temperature ionic liquid/water-containing microemulsion compared to that of a neat solvent, although retardation is very small compared to that of the solvent relaxation time of the conventional solvent in the core of the microemulsions.     

Stereoselective cascade reactions that incorporate a 7-exo acyl radical cyclization

[reaction: see text] Radical cascades that feature a 7-exo acyl radical cyclization followed by a 6-exo or 5-exo alkyl radical cyclization proceed with very good yields and diastereoselectivities. Two stereocenters are created by the reaction, and a single isomeric product was obtained from each of the five substrates examined. The relative configurations of the products are consistent with cyclizations occurring via chairlike or pseudochairlike transition states.     

Mononucleating bis(beta-diketonate) ligands and their titanium(IV) complexes

Novel bis(beta-diketones) linked by 2,2'-biphenyldiyl, 2,2'-tolandiyl, and 2,2'-bis(methylene)biphenyl moieties have been prepared. All are metalated readily by titanium(IV) isopropoxide, but the nature of the complexes formed depends on the linker structure. The biphenyl-bridged ligand gives only traces of a mononuclear complex, which is thermodynamically unstable with respect to oligomerization. The tolan-bridged ligand does form mononuclear complexes, but only as a mixture of geometric isomers. In contrast, the substituted 2,2'-bis-(2,4-dioxobutyl)biphenyl ligands, R2BobH2 (R = tBu, p-Tol), react with Ti(OiPr)4 to give, initially, a mixture of monomer and oligomers, which is converted quantitatively to monomer upon heating in the presence of excess Ti(OiPr)4. Only a single relative configuration of the biphenyl and bis(chelate) titanium moieties, established by crystallography of (tBu2Bob)Ti(O-2,6-iPr2C6H3)2 to be the (R)-/(S)- diastereomer, is observed. The kinetic and thermodynamic robustness of the (R2Bob)Ti framework is confirmed by reactions with Lewis acids. For example, (Tol2Bob)Ti(OiPr)2 reacts with trimethylsilyl triflate or triflic acid to substitute one or both of the isopropoxide groups with triflates without any redistribution or loss of the diketonate ligands. Cationic complexes can be prepared by abstraction of triflate from (Tol2Bob)Ti(OiPr)(OTf) with Na[B(C6H3(CF3)2)4]. For example, in the presence of diethyl ether, the crystallographically characterized [(Tol2Bob)Ti(OiPr)(OEt2)][B(C6H3(CF3)2)4], containing a rapidly dissociating ether ligand, is formed.     

Organic nonlinear optical materials: where we have been and where we are going

Nonlinear optical (NLO) materials can be useful for a variety of applications varying from modulation of optical signals facilitated by the electro-optic effect-the effect whereby the refractive index of a material changes in response to an applied electric field-to microfabrication, sensing, imaging, and cancer therapy facilitated by multiphoton absorption, wherein molecules simultaneously absorb two or more photons of light. This short Focus article is a brief personal perspective of some of the key advances in second-order NLO materials and in multiphoton-absorbing materials, and of how and why these advances have led to renewed interest in organic NLO materials.     

Flavothionato metal complexes: implications for the use of hydroxyflavothiones as green pesticides

Transition-metal complexes of 3-hydroxyflavothiones have been prepared and structurally characterized; the photochemical properties of these complexes have been examined and are discussed in the context of the use of these compounds as photodegradable pesticides.     

Photoinduced intermolecular electron transfer from dimethyl aniline to 7-amino coumarin dyes in the surface of beta-cyclodextrin

The photoinduced electron-transfer reaction between Coumarin dyes and N,N-dimethylaniline has been investigated using steady-state and Time-resolved fluorescence spectroscopy in the surface of beta-cyclodextrin in dimethyl formamide (DMF) solvent. The electron-transfer rate constant has been correlated with the free-energy change during the process. We have observed a diffusion-controlled ET process in pure DMF by showing a normal Marcus region. However, the picture is different in presence of cyclodextrin. Here the ET is retarded at higher free-energy region. This unusual feature in bimolecular electron-transfer reaction is assumed to be arising from the different binding possibility of the Coumarin molecules to the cyclodextrin moity.     

Ultrafast energy migration in chromophore shell-metal nanoparticle assemblies

A multifunctional ligand-coated nanoparticle system containing approximately 2000 highly two-photon absorptive chromophores has been investigated by means of steady-state and femtosecond time-resolved spectroscopy. This system with a high local concentration of chromophores showed remarkably low self-quenching and a high fluorescence quantum yield, which is important for a variety of two-photon sensing and imaging applications. We have observed evidence for ultrafast energy migration in these chromophore shell-metal nanoparticle systems. Time-resolved experiments also showed non-zero residual anisotropy after the initial fast decay, which can be interpreted as due to the formation of the specific domains on the metal surfaces. This investigation opens new avenues toward the development of multi-chromophoric efficient TPA fluorescence sensing/imaging systems with large numbers of chromophores per one metal particle nanoparticle.     

Stoichiometric aerobic PtII-Me bond cleavage in aqueous solutions to produce methanol and a PtII(OH) complex

Di(2-pyridyl)methanesulfonate ligand allows for facile aerobic oxidation of a PtIIMe complex into PtIVMe(OH)2 species and clean C-O reductive elimination of methanol from the latter in either acidic or basic aqueous solutions.