A new class of cyclometalated ruthenium sensitizers of the type ĈNN for efficient dye-sensitized solar cells

A new class of cyclometalated ruthenium sensitizers incorporating a ?NN ligand and conjugated 2,2'-bipyridine in the ancillary ligand have been designed and synthesized. The photovoltaic performance of JK-206 using an electrolyte containing 0.6 M 1,2-dimethyl-3-propylimidazolium iodide, 0.05 M I(2), 0.1 M LiI, and 0.5 M tert-butylpyridine in CH(3)CN gave a short-circuit photocurrent density of 19.63 mA cm(-2), an open-circuit voltage of 0.74 V, and a fill factor of 0.72, affording an overall conversion efficiency of 10.39%. The efficiency is the highest one reported for dye-sensitized solar cells based on the cyclometalated ruthenium sensitizer of the type ?NN. Moreover, the same device using a polymer gel electrolyte exhibited a remarkable stability under 1000 h of light soaking at 60 °C, retaining 91% of the initial efficiency of 7.14%.     

Correlation between Hepatic Fat Content Using 3-Echo 3-D Dixon Method and Intravoxel Incoherent Motion (IVIM) Perfusion MR Imaging

Fat accumulates as droplets in the hepatocyte swelling, distortion of microcirculatory anatomy and compression of sinus. This study aims to investigate the correlation between the T2*-corrected fat fraction (FF) value acquired via gradient echo with a low flip angle and parenchymal pseudorandom blood perfusion (P _fraction), microcirculation (D _fast), and slow component of diffusion (D _slow), acquired via intravoxel incoherent motion (IVIM), and to investigate the blood microcirculation and diffusion components of liver parenchyma, according to fat deposition. A total of 126 patients underwent 3-T magnetic resonance imaging, including a 3-echo three-dimensional (3-D) gradient echo sequence with T2*-corrected Dixon reconstruction and IVIM sequence. Pearson’s correlation analysis was conducted to investigate the correlation of the FF obtained via the Dixon method with the apparent diffusion coefficient (ADC), D _slow, P _fraction, and D _fast obtained via IVIM. Correlation analysis was also conducted for the IVIM mapping images. A confidence level of p < 0.05 was set. A negative correlation was found between the T2*-corrected FF acquired using the 3-echo 3-D Dixon method and D _slow acquired via IVIM (r = ?0.181, p < 0.05). It was likely due to the increased extracellular collagen deposition and increased intracellular fat droplets during the progression of liver fibrosis.     

Brain tumor diagnostic model and dietary effect based on extracellular vesicle microbiome data in serum

The human microbiome has been recently associated with human health and disease. Brain tumors (BTs) are a particularly difficult condition to directly link to the microbiome, as microorganisms cannot generally cross the blood–brain barrier (BBB). However, some nanosized extracellular vesicles (EVs) released from microorganisms can cross the BBB and enter the brain. Therefore, we conducted metagenomic analysis of microbial EVs in both serum (152 BT patients and 198 healthy controls (HC)) and brain tissue (5 BT patients and 5 HC) samples based on the V3–V4 regions of 16S rDNA. We then developed diagnostic models through logistic regression and machine learning algorithms using serum EV metagenomic data to assess the ability of various dietary supplements to reduce BT risk in vivo. Models incorporating the stepwise method and the linear discriminant analysis effect size (LEfSe) method yielded 12 and 29 significant genera as potential biomarkers, respectively. Models using the selected biomarkers yielded areas under the curves (AUCs) >0.93, and the model using machine learning resulted in an AUC of 0.99. In addition, Dialister and [Eubacterium] rectale were significantly lower in both blood and tissue samples of BT patients than in those of HCs. In vivo tests showed that BT risk was decreased through the addition of sorghum, brown rice oil, and garlic but conversely increased by the addition of bellflower and pear. In conclusion, serum EV metagenomics shows promise as a rich data source for highly accurate detection of BT risk, and several foods have potential for mitigating BT risk.Subject terms: Diagnostic markers, Machine learning     

Contrasting Effects of Axial Ligands on Electron‐Transfer Versus Proton‐Coupled Electron‐Transfer Reactions of Nonheme Oxoiron(IV) Complexes

The effects of axial ligands on electron‐transfer and proton‐coupled electron‐transfer reactions of mononuclear nonheme oxoiron(IV) complexes were investigated by using [Fe^IV(O)(tmc)(X)]ⁿ⁺ ( 1 ‐X) with various axial ligands, in which tmc is 1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane and X is CH₃CN ( 1 ‐NCCH₃), CF₃COO^? ( 1 ‐OOCCF₃), or N₃^? ( 1 ‐N₃), and ferrocene derivatives as electron donors. As the binding strength of the axial ligands increases, the one‐electron reduction potentials of 1 ‐X (E_red, V vs. saturated calomel electrode (SCE)) are more negatively shifted by the binding of the more electron‐donating axial ligands in the order of 1 ‐NCCH₃ (0.39) > 1 ‐OOCCF₃ (0.13) > 1 ‐N₃ (?0.05 V). Rate constants of electron transfer from ferrocene derivatives to 1 ‐X were analyzed in light of the Marcus theory of electron transfer to determine reorganization energies (λ) of electron transfer. The λ values decrease in the order of 1 ‐NCCH₃ (2.37) > 1 ‐OOCCF₃ (2.12) > 1 ‐N₃ (1.97 eV). Thus, the electron‐transfer reduction becomes less favorable thermodynamically but more favorable kinetically with increasing donor ability of the axial ligands. The net effect of the axial ligands is the deceleration of the electron‐transfer rate in the order of 1 ‐NCCH₃ > 1 ‐OOCCF₃ > 1 ‐N₃. In sharp contrast to this, the rates of the proton‐coupled electron‐transfer reactions of 1 ‐X are markedly accelerated in the presence of an acid in the opposite order: 1 ‐NCCH₃ < 1 ‐OOCCF₃ < 1 ‐N₃. Such contrasting effects of the axial ligands on the electron‐transfer and proton‐coupled electron‐transfer reactions of nonheme oxoiron(IV) complexes are discussed in light of the counterintuitive reactivity patterns observed in the oxo transfer and hydrogen‐atom abstraction reactions by nonheme oxoiron(IV) complexes (Sastri et al. Proc. Natl. Acad. Sci. U.S.A. 2007 , 104, 19 181–19 186).     

Lensed photonic crystal fiber obtained by use of an arc discharge

A lensed photonic crystal fiber (PCF) is proposed as an effective element for an optical free-space interconnector. By simultaneously forming a beam-expansion region and a focusing lens on a single piece of PCF, effective coupling between PCFs could be achieved. A long working distance of up to 1 mm with wide longitudinal and lateral tolerances was measured. The optical characteristics of the lensed PCFs and the connectors made from them are analyzed experimentally and theoretically.     

Resonant optical nonlinearity measurement of Yb(3+) / Al(3+) codoped optical fibers by use of a long-period fiber grating pair

A new method of measuring optical nonlinearity for resonant nonlinear optical fibers is proposed. A long-period fiber grating (LPG) pair was used to measure the nonlinear refractive index n(2) of a Yb(3+)/Al (3+) codoped optical fiber, which was spliced between the two LPGs, as the fiber was pumped with a laser diode. The nonlinear refractive index of the Yb(3+)/Al (3+) codoped fiber near 1580 nm depended on the pump power. As the pump power increased, the nonlinear refractive index decreased. At launched pump powers of 2-8 mW, the nonlinear refractive index of the Yb(3+)/Al (3+) codoped fiber near 1580 nm was ~7.5x10(-15)m (2)/W .     

Diffraction-limited dark laser spot produced by a hollow optical fiber

By using the diffracted field of the LP(11) mode of a hollow-core optical fiber, we have produced a micrometer-sized, focused dark laser spot in the near field of the fiber. The minimum half-width of the dark spot is less than 1 mum . In particular, by masking the hollow core and metal coating the cladding with a microsphere, we blocked the light propagating in the cladding and obtained a clean dark spot, which may be useful in atom-optical experiments such as with atomic lenses, atom traps, and atom switches.     

Tunable photonic crystal fiber coupler based on a side-polishing technique

A tunable photonic crystal fiber (PCF) coupler, which couples part of the optical power in one PCF with that in another PCF, has been made by side polishing. We fabricated the PCF coupler by mating two side-polished PCFs. We achieved evanescent field coupling between the core modes of the two PCFs by using side polishing to bring the cores close to each other. By adjusting the mating angle between the two side-polished PCFs we obtained as much as 90% tunability in the coupling ratio. The spectrum of the coupling ratio was almost flat, with small ripples, over a 400-nm wavelength range.     

Plastic enzyme-linked immunosorbent assays (ELISA)-on-a-chip biosensor for botulinum neurotoxin A

A plastic ELISA-on-a-chip (EOC) employing the concept of cross-flow immuno-chromatographic analysis was applied to the measurement of botulinum neurotoxin A (BoNT/A) as agent for bio-terrorism. Two monoclonal antibodies specific to the heavy chain of the toxin were raised and identified to form sandwich binding complexes as the pair with the analyte. For the construction of an immuno-strip, one was utilized as the capture antibody immobilized onto nitrocellulose membrane and the other as the detection coupled to an enzyme, horseradish peroxidase. The two plates of EOC used in this study were fabricated by injection molding of polycarbonate to improve the reproducibility of manufacture and, after inclusion of the immuno-strip, bonded using a UV-sensitive adhesive. Under optimal conditions of analysis, the chip produced a color signal in proportion to the analyte dose and the signal was quantified using a detector equipped with a digital camera. From the dose-response curve, the detection limit of BoNT/A was 2.0 ng mL⁻¹, approximately five times more sensitive than a commercial-version detection kit employing colloidal gold tracer.     

Organometallic fragments coordinated to a multiisocyanide ligand and their physical properties

Preparation of a triisocyanide ligand, 1,3,5-tris[(4-isocyano-3,5-diisoproyl-phenyl)ethynyl]benzene (5), is presented. Ligand 5 is obtained in three steps in 76% overall yield. Reaction of 5 with (eta5-Cp*)Rh(Cabs,s')(Cabs,s'= 1,2-S2C2B10H10-S,S') produced the rhodadithiolene adduct [[(eta5-Cp*)Rh(Cabs,s')(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5] (6). Ligand 5 reacts with Cr(CO)5(THF) to give the triisocyanide complex [[Cr(CO)5(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5] (8) and with [AuCl(SMe2)] to give the triisocyanide complex [[AuCl(CNC6H2iPr2-2,6-CC-3)]3C6H3-1,3,5] (9). As revealed by a single-crystal X-ray diffraction study, the C(9)-N(3)-C(61) angle of 5.9 degrees of trichromium complex 8 occurs in the plane of the bridge and the gold center has a slightly bent linear configuration with a Cl(1)-Au(1)-C(21) angle of 175.4(4) degrees . The rhenation and platination of 5 employing [Re(bpy)(CO)3(AN)]PF6 (AN= acetonitrile) and [(CwedgeNwedgeN)PtCl] ((HCwedgeNwedgeN)= 6-phenyl-2,2'-bipyridine) yielded the luminescent Re(I) and Pt(II) complexes. Full characterization includes structural study of complexes 2, 8, and 9.