Design Principles for Maximizing Hole Utilization of Semiconductor Quantum Wires toward Efficient Photocatalysis.

Maximizing hole-transfer kinetics-usually a rate-determining step in semiconductor-based artificial photosynthesis-is pivotal for simultaneously enabling high-efficiency solar hydrogen production and hole utilization. However, this remains elusive yet as efforts are largely focused on optimizing the electron-involved half-reactions only by empirically employing sacrificial electron donors (SEDs) to consume the wasted holes. Using high-quality ZnSe quantum wires as models, we show that how hole-transfer processes in different SEDs affect their photocatalytic performances. We found that larger driving forces of SEDs monotonically enhance hole-transfer rates and photocatalytic performances by almost three orders of magnitude, a result conforming well with the Auger-assisted hole-transfer model in quantum-confined systems. Intriguingly, further loading Pt cocatalyts can yield either an Auger-assisted model or a Marcus inverted region for electron transfer, depending on the competing hole-transfer kinetics in SEDs.

Proposal for the momentum-resolved and time-resolved optical measurement of the current distribution in semiconductors.

The two-color optical coherence absorption spectrum (QUIC-AB) of semiconductors in the presence of a charge current is investigated. We find that the QUIC-AB depends strongly not only on the amplitude of the electron current but also on the direction of the electron current. Thus, the amplitude and the angular distribution of current in semiconductors can be detected directly in real time with the QUIC-AB.

Determination of Nine Fentanyl Drugs in Hair Samples by GC-MS/MS and LC-MS/MS.

We established GC-MS/MS and LC-MS/MS analysis methods for nine fentanyl drugs in hair samples. Human hairs were prepared by soaking in a solution of water-dimethyl sulfoxide with target analytes. The drugs were norfentanyl, acetyl fentanyl, para-fluorofentanyl, isobutyryl fentanyl, fentanyl, thiofentanyl, 4-fluoroisobutyr fentanyl, ocfentanil, and tetrahydrofuran fentanyl. For a single-factor experiment, a Box-Behnken design-response surface was used to optimize the pretreatment conditions of samples. The prepared samples were quantitatively analyzed by GC-MS/MS and LC-MS/MS. The working curve method was used for quantitative analysis with fentanyl-D5 as the internal standard. The concentrations of the nine fentanyl drugs in the samples were 1.488-6.494 ng mg-1, RSDs < 5.0%. For GC-MS/MS, the linear range of the nine fentanyl drugs was 0.5-5.0 ng mg-1, r 2 > 0.999. The detection limits were 0.02-0.05 ng mg-1, and the recovery rates were >86%. For LC-MS/MS, the nine fentanyl drugs had an excellent linear relationship within the concentration range of 3.0-220.0 pg mg-1, r 2 > 0.999. The detection limits were 0.05 pg mg-1 and the recovery rates were >84%. The established methods were used for the detection of fentanyl drugs in human hairs, with high sensitivity, accuracy, and specificity. These two methods can be used for the certification of fentanyl certified reference substances (CRMs). In the experiment, the developed hair CRMs, which will continue to be studied in the future, are expected to be used in forensic drug abuse detection.

Selective and efficient cycloisomerization of alkynols catalyzed by a new ruthenium complex with a tetradentate nitrogen-phosphorus mixed ligand.

The new ruthenium complex [Ru(N(3)P)(OAc)][BPh(4)] (4), in which N(3)P is the N,P mixed tetradentate ligand N,N-bis[(pyridin-2-yl)methyl]-[2-(diphenylphosphino)phenyl]methanamine was synthesized. The complex was found to be catalytically active for the endo cycloisomerization of alkynols. The catalytic reactions can be used to synthesize five-, six-, and seven-membered endo-cyclic enol ethers in good to excellent yields. A catalytic cycle involving a vinylidene intermediate was proposed for the catalytic reactions. Treatment of complex 4 with PhC[triple bond]CH and H(2)O gave the alkyl complex [Ru(CH(2)Ph)(CO)(N(3)P)][BPh(4)] (30), which supports the assumption that the catalytic reactions involve addition of a hydroxyl group to the C=C bond of vinylidene ligands.

New observations on the pressure dependence of luminescence from Eu2+-doped MF2 (M = Ca, Sr, Ba) fluorides.

The luminescence from Eu(2+) ions in MF2 (M = Ca, Sr, Ba) fluorides has been investigated under the pressure range of 0-8 GPa. The emission band originating from the 4f(6)5d(1) --> 4f(7) transition of Eu(2+) ions in CaF2 and SrF2 shows the red-shift as increasing pressure with pressure coefficients of -17 meV/GPa for CaF2 and -18 meV/GPa for SrF2. At atmospheric pressure, the emission spectrum of BaF2:Eu(2+) comprises two peaks at 2.20 and 2.75 eV from the impurity trapped exciton (ITE) and the self-trapped exciton (STE), respectively. As the pressure is increased, both emission peaks shift to higher energies, and the shifting rate is slowed by the phase transition from the cubic to orthorhombic phase at 4 GPa. Due to the phase transition at 4-5 GPa pressure, the ITE emission disappears gradually, and the STE emission is gradually replaced by the 4f(6)5d(1) --> 4f(7) transition of Eu(2+). Above 5 GPa, the pressure behavior of the 4f(6)5d(1) --> 4f(7) transition of Eu(2+) in BaF2:Eu(2+) is the same as the normal emission of Eu(2+) in CaF2 and SrF2 phosphors.

Synthesis, characterization, and electrochemical properties of mono-, di-, and trinuclear transition Metal [60]fullerene complexes containing diphosphine cis-Ph2PCH=CHPPh2 ligand.

New transition metal fullerene complexes containing cis-Ph2PCH=CHPPh2 (dppet) ligand have been investigated. The mononuclear complexes (etau2-C60)M(cis-dppet) (1, 2; M = Pd, Pt) were prepared by reaction of C60 with M(dba)2 (dba = dibenzylideneacetone) followed by treatment with cis-dppet, while the in situ prepared 1 and 2 reacted with M1(PPh3)4 to afford dinuclear complexes (eta2 : eta2-C60)M(cis-dppet)M1 (PPh3)2 (3-6; M, M1 = Pd, Pt). Similarly, trinuclear complexes (eta2 : eta2-C60) M(cis-dppet)M1 (dppr) (7-10; M, M1 = Pd, Pt; dppr = (eta5-Ph2PC5H4)2Ru) could be synthesized by reaction of the in situ prepared 3-6 with dppr. 1-10 were characterized by elemental analysis and spectroscopy. Cyclic voltammetric studies on 2 (M = Pt), 3 (M = Pd, M1 = Pd) and 9 (M = Pt, M1 = Pd) provided further evidence for the eta2-coordination of C60 to one metal fragment or two metal fragments in these complexes.