Choice of Optimal Shift Parameter for the Intruder State Removal Techniques in Multireference Perturbation Theory

An extensive critical evaluation of intruder state removal techniques (aka shift techniques) applicable to multireference perturbation theory (MRPT) shows that the magnitude of the shift parameter σ does not influence the spectroscopic parameters of diatomics to a significant degree, provided that the shift is chosen to be sufficiently large. In such case, typical variation of spectroscopic parameters over a wide range of shift parameters is smaller than 0.005 Å for equilibrium distances, 30 cm^–1 for harmonic vibrational frequencies, and 0.1 eV for dissociation energies. It is found that large values of σ not only remove intruder states but they also bring the MRPT energies and properties closer to experimental values. The presented analysis allows us to determine optimal values of the shift parameters to be used in conjunction with various versions of MRPT; these values are recommended to replace the <i>ad hoc</i> values of σ suggested in MRPT manuals in calculations for diatomics. Transferability of the optimal shift parameters to larger molecular systems and to other basis sets than aug-cc-pVTZ is anticipated but remains to be formally established

Structural Insights into the Glycine Pair Motifs in Type III Collagen

Human type III collagen has been suggested to play vital roles in a series of pathophysiological conditions. Sequence analysis among major fibril-forming collagens (types I, II, and III) revealed that Gly-Gly pairs are a distinct sequence feature in type III collagen. This motif occurs more than five times as often in type III compared to type I and II collagens. We used an integrated computational modeling and biophysical approach to analyze the glycine pair motifs to understand how they govern the structure of type III collagen at the molecular level. Triple helical peptides to model the regions of type III collagen containing GG motifs were used to analyze structural and thermodynamic effects of GG incorporation into the collagen sequence. We found that when amino acids adjacent to a GG motif are charged, the collagen adopts a more flexible, random conformation. The GG motif led to altered hydrogen bond patterns and decreased global melting temperatures of the triple helical peptides. The local entropic destabilization effect of the glycine pair helps explain the difference in the flexibility between types I and III collagen fibrils. This finding reveals potential physiological roles of type III collagen in regulating the mechanical properties of collagen fibrils and may enable the design of future collagen-like materials with tunable mechanical properties

Carnosic Acid Prevents 6‑Hydroxydopamine-Induced Cell Death in SH-SY5Y Cells via Mediation of Glutathione Synthesis

Understanding the neuroprotective effects of the rosemary phenolic diterpene carnosic acid (CA) has attracted increasing attention. We explored the mechanism by which CA modulates the neurotoxic effects of 6-hydroxydopamine (6-OHDA) in SH-SY5Y cells. Cells were pretreated with CA for 12 h followed by treatment with 100 μM 6-OHDA for 12 or 24 h. Cell viability determined by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolim bromide (MTT) assay indicated that 0.1 to 1 μM CA dose-dependently attenuated the cell death induced by 6-OHDA, whereas the effect of 3–5 μM CA was weaker. CA at 1 μM suppressed the 6-OHDA-induced nuclear condensation, reactive oxygen species generation, and cleavage of caspase 3 and PARP. Immunoblots showed that the phosphorylation of c-Jun NH₂-terminal kinase (JNK) and p38 by 6-OHDA was reduced in the presence of CA. Incubation of cells with CA resulted in significant increases in the total glutathione (GSH) level and the protein expression of the γ-glutamylcysteine ligase catalytic subunit and modifier subunit. l-Buthionine-sulfoximine, an inhibitor of GSH synthesis, attenuated the effect of CA on cell death and apoptosis. Treatment with CA also led to an increase in nuclear factor erythroid-2 related factor 2 (Nrf2) activation, antioxidant response element (ARE)-luciferase reporter activity, and DNA binding to the ARE. Silencing of Nrf2 expression alleviated the reversal of p38 and JNK1/2 activation by CA. These results suggest that the attenuation of 6-OHDA-induced apoptosis by CA is associated with the Nrf2-driven synthesis of GSH, which in turn down-regulates the JNK and p38 signaling pathways. The CA compound may be a promising candidate for neuroprotection in Parkinson’s disease

Circular Dichroism Control of Tungsten Diselenide (WSe₂) Atomic Layers with Plasmonic Metamolecules

Controlling circularly polarized (CP) states of light is critical to the development of functional devices for key and emerging applications such as display technology and quantum communication, and the compact circular polarization-tunable photon source is one critical element to realize the applications in the chip-scale integrated system. The atomic layers of transition metal dichalcogenides (TMDCs) exhibit intrinsic CP emissions and are potential chiroptical materials for ultrathin CP photon sources. In this work, we demonstrated CP photon sources of TMDCs with device thicknesses approximately 50 nm. CP photoluminescence from the atomic layers of tungsten diselenide (WSe₂) was precisely controlled with chiral metamolecules (MMs), and the optical chirality of WSe₂ was enhanced more than 4 times by integrating with the MMs. Both the enhanced and reversed circular dichroisms had been achieved. Through integrations of the novel gain material and plasmonic structure which are both low-dimensional, a compact device capable of efficiently manipulating emissions of CP photon was realized. These ultrathin devices are suitable for important applications such as the optical information technology and chip-scale biosensing

Plasmonic Carbon-Dot-Decorated Nanostructured Semiconductors for Efficient and Tunable Random Laser Action

Carbon dots have emerged as popular materials in various research fields, including biological and photovoltaic areas, while significant reports are lacking related to their applications in laser devices, which play a significant role in our daily life. In this work, we demonstrate the first controllable random laser assisted by the surface plasmon effect of carbon dots. Briefly, carbon dots derived from candle soot are randomly deposited on the surface of gallium nitride (GaN) nanorods to enhance the ultraviolet fluorescence of GaN and generate plasmonically enhanced random laser action with coherent feedback. Furthermore, potentially useful functionalities of tunable lasing threshold and controllable optical modes are achieved by adjusting the numbers of carbon dots, enabling applications in optical communication and identification technologies. In addition to providing an efficient alternative for plasmonically enhanced random laser devices with simple fabrication and low cost, our work also paves a useful route for the application of environmentally friendly carbon dots in optoelectronic devices