Proton occupation numbers for Ca

The (d, ³He) proton pickup reaction on ⁴⁴Ca has been studied at a deuteron energy of Ed = 19.0 MeV using the Minnesota MP Tandem Van de Graaff. Differential cross sections were measured at forward angles and spectroscopic factors were extracted in the usual fashion for the transitions to five states of ⁴³K. The results are compared with previous proton pickup and stripping reactions on the even Ca isotopes. Only about half of the sd hole state excitation strength observed in the stripping reactions could be found in the pickup from the fp orbitals if the data are analyzed by standard distorted wave calculations. This discrepancy can be removed by using bound state potential radii which are slightly larger for sd orbitals than for fp orbitals.     

X-ray photoelectron spectra of aryldiazo derivatives of transition metals

The X-ray photoelectron spectra of singly bent, doubly bent, and protonated doubly bent aryldiazonium complexes have been obtained and show that the RN₂ ligand is highly reduced. The correlation observed between binding energies and structure of the MN₂R moiety permit the assignment of the N(1s) photopeaks.     

Excited states of100Tc from100Mo(p,nγ)100Tc reaction and the parabolic rule

γ-spectra and excitation functions of the¹⁰⁰Mo(p, nγ)¹⁰⁰Tc reaction were measured in the 1.2–3.6 MeV proton energy range by using thick, enriched targets, Ge(Li) and low energy photon (hyperpure Ge) spectrometers. These detectors were used inγγ-coincidence experiments, too. Conversion electron spectrum measurements were performed by means of a superconducting magnet transporter Si(Li) spectrometer (SMS) atE _p =4 MeV and multipolarities of some transitions have been determined. Based on the experimental results a level scheme of¹⁰⁰Tc has been constructed. Level energies of¹⁰⁰Tc were calculated on the basis of the parabolic rule, derived from the cluster-vibration model.     

Ruthenium-catalyzed azide-alkyne cycloaddition: scope and mechanism

The catalytic activity of a series of ruthenium(II) complexes in azide-alkyne cycloadditions has been evaluated. The [Cp*RuCl] complexes, such as Cp*RuCl(PPh 3) 2, Cp*RuCl(COD), and Cp*RuCl(NBD), were among the most effective catalysts. In the presence of catalytic Cp*RuCl(PPh 3) 2 or Cp*RuCl(COD), primary and secondary azides react with a broad range of terminal alkynes containing a range of functionalities selectively producing 1,5-disubstituted 1,2,3-triazoles; tertiary azides were significantly less reactive. Both complexes also promote the cycloaddition reactions of organic azides with internal alkynes, providing access to fully-substituted 1,2,3-triazoles. The ruthenium-catalyzed azide-alkyne cycloaddition (RuAAC) appears to proceed via oxidative coupling of the azide and alkyne reactants to give a six-membered ruthenacycle intermediate, in which the first new carbon-nitrogen bond is formed between the more electronegative carbon of the alkyne and the terminal, electrophilic nitrogen of the azide. This step is followed by reductive elimination, which forms the triazole product. DFT calculations support this mechanistic proposal and indicate that the reductive elimination step is rate-determining.     

Ruthenium-catalyzed cycloaddition of aryl azides and alkynes

The formation of 1,5-disubstituted 1,2,3-triazoles from aryl azides and alkynes was readily accomplished using [Cp*RuCl]4 catalyst in dimethylformamide. It was also demonstrated that the reaction provided higher yields, cleaner product, and shorter reaction times when carried out under microwave irradiation.     

Insight into the nonlinear absorbance of two related series of two-photon absorbing chromophores

A comprehensive photophysical study of the linear and nonlinear absorption properties has been carried out on two series of two-photon absorbing dyes to gain insight into how structure-property relationships influence observed nonlinear absorption. The materials studied consist of an electron accepting benzothiazole group connected to an electron donating diphenylamine via a fluorene bridging group. Two series differ from each other by the addition of one phenyl group and for each series one-arm (dipolar, AF240 and AF270), two-arm (quadrupolar, AF287 and AF295), and three-arm (octupolar, AF350 and AF380) versions were studied. Overall the AF240 series exhibits higher intrinsic two-photon absorption (TPA) cross-sections than the AF270 series as well as enhanced nanosecond nonlinear absorption, with an increase with number of branches. The enhanced nanosecond nonlinearity is understood by taking into account the contribution from the singlet and triplet excited states and was verified by a two-photon assisted excited-state absorption model that satisfactorily predicts the nonlinear absorption of the chromophores.     

Not All Fluorescent Nanodiamonds Are Created Equal: A Comparative Study

Fluorescent nanodiamonds (FNDs) are vital to many emerging nanotechnological applications, from bioimaging and sensing to quantum nanophotonics. Yet, understanding and engineering the properties of fluorescent defects in nanodiamonds remain challenging. The most comprehensive study to date is presented, of the optical and physical properties of five different nanodiamond samples, in which fluorescent nitrogen‐vacancy (NV) centers are created using different fabrication techniques. The FNDs' fluorescence spectra, lifetime, and spin relaxation time (T₁) are investigated via single‐particle confocal fluorescence microscopy and in ensemble measurements in solution (T₁ excepted). Particle sizes and shapes are determined using scanning electron microscopy and correlated with the optical results. Statistical tests are used to explore correlations between the properties of individual particles and also analyze average results to directly compare different fabrication techniques. Spectral unmixing is used to quantify the relative NV charge‐state (NV^? and NV⁰) contributions to the overall fluorescence. A strong variation is found and quantified in the properties of individual particles within all analyzed samples and significant differences between the different particle types. This study is an important contribution toward understanding the properties of NV centers in nanodiamonds. It motivates new approaches to the improved engineering of NV‐containing nanodiamonds for future applications.     

Excited-state structural dynamics of 5-fluorouracil

5-Fluorouracil is an analogue of thymine and uracil, nucleobases found in DNA and RNA, respectively. The photochemistry of thymine is significant; UV-induced photoproducts of thymine in DNA lead to skin cancer and other diseases. In previous work, we have suggested that the differences in the excited-state structural dynamics of thymine and uracil arise from the methyl group in thymine acting as a mass barrier, localizing the vibrations at the photochemical active site. To further test this hypothesis, we have measured the resonance Raman spectra of 5-fluorouracil at wavelengths throughout its 267 nm absorption band. The spectra of 5-fluorouracil and thymine are very similar. Self-consistent analysis of the resulting resonance Raman excitation profiles and absorption spectrum using a time-dependent wave packet formalism suggests that, at most, 81% of the reorganization energy upon excitation is directed along photochemically relevant modes. This compares well with what was found for thymine, supporting the mass barrier hypothesis.