Brightening of triplet dark excitons by atomic hydrogen adsorption in single-walled carbon nanotubes observed by photoluminescence spectroscopy

Adsorption and desorption of atomic hydrogen on single-walled carbon nanotubes were observed by photoluminescence spectroscopy. A satellite peak appeared at the lower energy side of the E11 photoluminescence emission peak after exposure to atomic hydrogen and then disappeared after annealing at 300?°C in vacuum. The energy difference between the satellite peak and E11 peak was 40-80 meV, depending on the tube diameter. The satellite peak was attributed to the triplet dark exciton that became optically active because of the effectively enhanced spin-orbit interaction induced by adsorbed hydrogen atoms.     

Differences in dual-task performance and prefrontal cortex activation between younger and older adults

Background

The purpose of this study was to examine task-related changes in prefrontal cortex (PFC) activity during a dual-task in both healthy young and older adults and compare patterns of activation between the age groups. We also sought to determine whether brain activation during a dual-task relates to executive/attentional function and how measured factors associated with both of these functions vary between older and younger adults.

Results

Thirty-five healthy volunteers (20 young and 15 elderly) participated in this study. Near-infrared spectroscopy (NIRS) was employed to measure PFC activation during a single-task (performing calculations or stepping) and dual-task (performing both single-tasks at once). Cognitive function was assessed in the older patients with the Trail-making test part B (TMT-B). Major outcomes were task performance, brain activation during task (oxygenated haemoglobin: Oxy-Hb) measured by NIRS, and TMT-B score. Mixed ANOVAs were used to compare task factors and age groups in task performance. Mixed ANOVAs also compared task factors, age group and time factors in task-induced changes in measured Oxy-Hb. Among the older participants, correlations between the TMT-B score and Oxy-Hb values measured in each single-task and in the dual-task were examined using a Pearson correlation coefficient. Oxy-Hb values were significantly increased in both the calculation task and the dual-task within patients in both age groups. However, the Oxy-Hb values associated with there were higher in the older group during the post-task period for the dual-task. Also, there were significant negative correlations between both task-performance accuracy and Oxy-Hb values during the dual-task and participant TMT-B scores.

Conclusions

Older adults demonstrated age-specific PFC activation in response to dual-task challenge. There was also a significant negative correlation between PFC activation during dual-task and executive/attentional function. These findings suggest that the high cognitive load induced by dual-task activity generates increased PFC activity in older adults. However, this relationship appeared to be strongest in participants with better baseline attention and executive functions.     

Can Anti-Aufbau DFT Calculations Estimate Singlet Excited State Aromaticity? Correspondence on “Dibenzoarsepins: Planarization of 8π-Electron System in the Lowest Singlet Excited State”

The simple anti-aufbau DFT approach for estimating singlet excited state aromaticity suggested in a recent Communication published in this journal is shown to produce incorrect results because it targets a linear combination of the singlet and triplet configurations involving the HOMO and LUMO rather than the first singlet excited state. If the S₁ state of a molecule is dominated by the HOMO→LUMO excitation, a comparably simple but theoretically consistent and qualitatively correct approximation to the S₁ wavefunction can be achieved by performing a small “two electrons in two orbitals” CASSCF(2,2) calculation which can be followed by the evaluation of magnetic aromaticity criteria such as NICS.     

Overexpression of DnaJ-Like Chaperone Enhances Carotenoid Synthesis in <Emphasis Type="Italic">Chlamydomonas reinhardtii</Emphasis>

Production of functional carotenoids using microalgae may facilitate the commercialization of anti-aging nutritional supplements. The green alga Chlamydomonas reinhardtii uses a non-mevalonate (MEP) pathway for isopentenyl diphosphate (IPP) synthesis. Two enzymes thought to play important roles in this MEP pathway to IPP synthesis are 1-deoxy-d-xylulose 5-phosphate synthase (DXS) and reductase (DXR). DnaJ-like chaperone (Orange protein) is thought to support phytoene synthase, a key enzyme in plant carotenoid synthesis. Genes for Orange (OR), DXS, and DXR were overexpressed via nuclear transformation into C. reinhardtii. CDS of OR, DXS, and DXR were amplified and connected with dual promoters of heat-shock protein 70A and ribulose bisphosphate carboxylase small chain 2. Compared with the parental strain, transformant CrOR#2 produced increased lutein and β-carotene (1.9-fold and 1.7-fold per cell, respectively). Transformant CrDXS#1 produced lutein and β-carotene at lower per-cell abundances than those for the parental strain. CrDXR#2 transformant produced lutein and β-carotene at higher per-cell abundances than their parental counterpart; however, these transformants produced lutein and β-carotene at lower per-medium abundances than their parental counterparts. These results suggest that OR protein supports phytoene synthase in C. reinhardtii and that the phytoene synthesis step is rate-limiting in carotenoid synthesis.     

Stellatolide H,a cytotoxic peptide lactone from a deep-sea sponge Discodermia sp.

Stellatolide H (1) was isolated from a deep-sea sponge Discodermia sp. as the cytotoxic constituent. The planar structure of 1 was elucidated on the basis of the NMR spectroscopic and mass spectrometric data. The absolute configurations of the constituent amino acid residues were determined by the Marfey’s method. Stellatolide H (1) is a peptide lactone of the callipeltin class with its N-terminus blocked by 3-hydroxy-6,8-dimethyldeca-(4Z,6E)-dienoic acid (Hdda).     

DNA Origami Scaffolds as Templates for Functional Tetrameric Kir3 K+ Channels

In native systems, scaffolding proteins play important roles in assembling proteins into complexes to transduce signals. This concept is yet to be applied to the assembly of functional transmembrane protein complexes in artificial systems. To address this issue, DNA origami has the potential to serve as scaffolds that arrange proteins at specific positions in complexes. Herein, we report that Kir3 K⁺ channel proteins are assembled through zinc‐finger protein (ZFP)‐adaptors at specific locations on DNA origami scaffolds. Specific binding of the ZFP‐fused Kir3 channels and ZFP‐based adaptors on DNA origami were confirmed by atomic force microscopy and gel electrophoresis. Furthermore, the DNA origami with ZFP binding sites nearly tripled the K⁺ channel current activity elicited by heterotetrameric Kir3 channels in HEK293T cells. Thus, our method provides a useful template to control the oligomerization states of membrane protein complexes in vitro and in living cells.     

Direct construction of bicyclic heterocycles by palladium-catalyzed domino cyclization of propargyl bromides

The palladium-catalyzed domino cyclization of propargyl bromides having two nucleophilic functional groups is described. Treatment of 1,7-diamino-5-bromohept-3-yne derivatives with catalytic Pd(PPh3)4 in the presence of NaH in MeOH gives the 2,7-diazabicyclo[4.3.0]non-5-enes in good yields. Interestingly, the regioselectivity of the reaction is completely controlled by the relative reactivity of the amine functional groups, irrespective of the position of the nucleophiles. The malonate derivative also undergoes domino cyclization to produce a hexahydroindole derivative.