Serum proteome profiles revealed dysregulated proteins and mechanisms associated with fibromyalgia syndrome in women.

Fibromyalgia syndrome (FM) is a multifactorial disorder whose pathogenesis and diagnosis are poorly understood. This study investigated differential serum proteome profiles in patients with FM and healthy pain-free controls and explored the association between serum proteome and clinical profiles in patients with FM. Twenty patients with FM (according to the American College of Rheumatology criteria, 2010) and 20 healthy pain-free controls were recruited for optimized quantitative serum proteomics analysis. The levels of pain, pressure pain threshold, sleep, anxiety, depression, and functional status were evaluated for patients with FM. We identified 22 proteins differentially expressed in FM when compared with healthy pain-free controls and propose a panel of methyltransferase-like 18 (METTL18), immunoglobulin lambda variable 3-25 (IGLV3-25), interleukin-1 receptor accessory protein (IL1RAP), and IGHV1OR21-1 for differentiating FM from controls by using a decision tree model (accuracy: 0.97). In addition, we noted several proteins involved in coagulation and inflammation pathways with distinct expression patterns in patients with FM. Novel proteins were also observed to be correlated with the levels of pain, depression, and dysautonomia in patients with FM. We suggest that upregulated inflammation can play a major role in the pathomechanism of FM. The differentially expressed proteins identified may serve as useful biomarkers for diagnosis and evaluation of FM in the future.

Effects of Internal Electron-Withdrawing Moieties in D-A-π-A Organic Sensitizers on Photophysical Properties for DSSCs: A Computational Study.

D-A-π-A dyes differ from the traditional D-π-A framework having several merits in dye-sensitized solar cell (DSSC) applications. With regard to D-π-A dyes, D-A-π-A dyes red-shift absorption spectra and show particular photostability. Nevertheless, the effects of internal acceptor on the charge transfer (CT) probability are unclear. We employed density functional theory (DFT), time-dependent DFT (TD-DFT), and TD-DFT molecular dynamics (MD) simulations to investigate the effects of internal acceptor on the photophysical properties of D-A-π-A dyes on DSSCs. Our calculations show the absorption bands of D-A-π-A dyes with strong electron-withdrawing internal acceptors exhibiting significant characteristics of dual CT; the excited electron density is transferred to the internal and terminal acceptors simultaneously. Particularly, the internal acceptor traps a significant amount of electron density upon photoexcitation. The TD-DFT MD simulations at 300 K show that only a small amount of excited electron density is pushing and pulling between the internal acceptor and terminal acceptor moieties; the thermal energy is not high enough to drive the electron density from the internal acceptor to the terminal acceptor. Our study reveals the nature of CT bands of D-A-π-A dyes providing a theoretical basis for further rational engineering.

First-Principle Characterization of the Adsorption Configurations of Cyanoacrylic Dyes on TiO2 Film for Dye-Sensitized Solar Cells.

The loading of sensitizers on a semiconductor is crucial for determining the light-harvesting efficiency of dye-sensitized solar cells (DSSCs). The interfacial properties of dyes adsorbed on a TiO2 film, such as adsorption configurations and adsorption energy, can influence the total amount of dye sensitizers that loads and the stability of a DSSC device. Therefore, it is important to characterize the adsorption properties of sensitizers on TiO2 films atomically and electronically to ensure rational structure-based dye design for high-performance DSSCs. Due to the complex properties of interfacial dyes, previous works on the identification of adsorption configurations of dyes on TiO2 have sometimes been controversial, in particular, the essential IR band assignments. In this study, we employed density functional theory to investigate the adsorption energies, geometries, and vibrational frequencies of various adsorption configurations of 2-cyano-3-(thiophen-2-yl)acrylic acid adsorbed on TiO2. We performed a comparative assignment of the calculated vibrational peaks of tridentate and bidentate configurations to the experimental FT-IR spectra simultaneously. Our work backs up the coexistence of tridentate and bidentate bridging configurations, first proposed by Meng and co-workers. Moreover, our comparative IR mode assignments provide clues for further studies of the interfacial properties of dyes adsorbed on TiO2. Study of the transformation mechanisms between tridentate and bidentate modes suggests that the bidentate bridging configuration is a kinetically trapped adsorption mode and the tridentate configuration is thermodynamically the most stable one. Finally, we investigated the photophysical properties of a D-π-A dye in tridentate and bidentate adsorption configurations.