Efficient light harvesting and energy transfer in organic-inorganic hybrid multichromophoric materials

Thin films of silica hybrid materials consisting of two to three covalently bound organic chromophores at different ratios were conveniently synthesized and fabricated. The photophysical properties of these materials have been studied. The fluorescence spectra reveal complete fluorescence resonance energy transfer (FRET) from donor to acceptor, and the light-harvesting ability of these hybrid materials increases with increasing the molar fraction of donor chromophore. In a three-chromophore system, the energy is transferred from 300 to 530 nm successfully. Time-resolved fluorescence experiments are employed to elucidate the average rates and efficiencies (84-97%) of energy transfer in these organic/inorganic hybrid systems. The hybrid materials have been shown to provide antenna effect to facilitate energy transfer and light harvesting.     

Synthesis and Cytotoxicity Evaluation of Metal‐Chelator‐Bearing Flavone,Carbazole, Dibenzofuran,Xanthone, and Anthraquinone

2‐(Aryloxymethyl)‐5‐benzyloxy‐1‐methyl‐1H‐pyridin‐4‐ones 8a – 8g , 2‐(aryloxymethyl)‐5‐hydroxy‐4H‐pyran‐4‐ones 9a – 9g , and 2‐(aryloxymethyl)‐5‐hydroxy‐1‐methyl‐1H‐pyridin‐4‐ones 10a – 10g were prepared from the known 5‐benzyloxy‐2‐(hydroxymethyl)pyran‐4‐one ( 3 ) in a good overall yield. These compounds were evaluated in vitro against a three‐cell lines panel consisting of MCF7 (breast), NCI‐H460 (lung), and SF‐268 (CNS), and the active compounds passed on for evaluation in the full panel of 60 human tumor cell lines derived from nine cancer cell types. The results indicated that 5‐hydroxy derivatives are more favorable than their corresponding 5‐benzyloxy precursors ( 10a – 10g vs. 8a – 8g ), and 1‐methyl‐1H‐pyridin‐4‐ones are more favorable than their corresponding pyran‐4(1H)‐ones ( 10a – 10g vs. 9a – 9g ). Among these three types of compounds, 2‐(aryloxymethyl)‐5‐hydroxy‐1‐methyl‐1H‐pyridin‐4‐ones 10a – 10g were the most cytotoxic; they inhibited the growth of almost all the cancer cells tested. On the contrary, compound 8a (a mean GI₅₀=27.8 μM ), 8b (38.5), 8d (11.0), and 8e (30.5) are especially active against the growth of SK‐MEL‐5 (a melanoma cancer cell) with a GI₅₀ of <0.01, 5.65, 0.55, and 0.03 μM , respectively (cf. Table 2).     

Semiempirical Molecular Orbital Studies of the Acylation Step in the Lipase‐Catalyzed Ester Hydrolysis

In this study, we present the results from the semiempirical molecular orbital calculations for the acylation step in the lipase‐catalyzed ester hydrolysis. The results reveal that the lowest energy path for the formation of the tetrahedral intermediate is for the serine residue of the catalytic triad to attack the substrate, followed by coupling heavy atom movement and proton transfer. The calculations of four active site models show that the cooperation of the aspartate group and the oxyanion hole is capable of lowering the activation energy by about 16 kcalmol^?1. Our results further suggest that the lipase‐catalyzed ester hydrolysis adopts the single proton transfer mechanism.     

Calculation of local insulating structure of CaCuO2 with interplanar oxygen defects

The electronic band structures of CaCuO₂ with various planar structures have been computed with the spin polarized, full potential pseudofunction method. The perfect tetragonal structure has metallic bands. If the CuO plane is puckered as proposed on the basis of pulsed neutron experiments, a semi-metallic-like behavior is found. When some of the oxygen atoms are moved from the basal plane into interplanar sites that are coplanar with Ca, an insulating ground state is obtained with antiferromagnetic moments of 0.21 _B . Around this interplanar oxygen defect site, the charge and magnetic moment distributions resemble those of a CuO chain structure with strong coupling to Cu atoms from different basal planes. Small displacements of defect oxygens at interplanar sites along the CaO planar directions produces large changes in band shape near E _F , suggesting strong electron-lattice coupling. The coupling is much weaker for displacements of O atoms within the CuO basal plane. Such interplanar defects could occur in superconducting cuprates and thus create small insulating regions for the pinning of magnetic flux lines.     

Multiple hydrogen bonds tuning guest/host excited-state proton transfer reaction: its application in molecular recognition

A molecular recognition concept exploiting multiple-hydrogen-bond fine-tuned excited-state proton-transfer (ESPT) was conveyed using 3,4,5,6-tetrahydrobis(pyrido[3,2-g]indolo)[2,3-a:3',2'-j]acridine (1a). The catalytic type 1a/carboxylic acids hydrogen-bonding (HB) complexes undergo ultrafast ESPT, resulting in an anomalously large Stokes shifted tautomer emission (lambdamax approximately 600 nm). Albeit forming a quadruple HB complex, ESPT is prohibited in the noncatalytic-type 1a/urea complexes (lambdamax approximately 430 nm). The HB configuration tuning ESPT properties lead to a feasible design for sensing multiple-HB-site analytes of biological interest.     

A Comparative Study on Analysis of Ginsenosides in American Ginseng Root Residue by HPLC-DAD-ESI-MS and UPLC-HRMS-MS/MS

Ginseng (Panax quinquefolius), a popular herbal and nutritional supplement consumed worldwide, has been demonstrated to possess vital biological activities, which can be attributed to the presence of ginsenosides. However, the presence of ginsenosides in ginseng root residue, a by-product obtained during processing of ginseng beverage, remains unexplored. The objectives of this study were to develop a high-performance liquid chromatography-photodiode array detection-mass spectrometry (HPLC-DAD-ESI-MS) and an ultra-high-performance-liquid-chromatography-tandem mass spectrometry (UPLC-HRMS-MS/MS) method for the comparison of ginsenoside analysis in ginseng root residue. Results showed that by employing a Supelco Ascentis Express C18 column (150 × 4.6 mm ID, particle size 2.7 μm) and a gradient mobile phase of deionized water and acetonitrile with a flow rate at 1 mL/min and detection at 205 nm, a total of 10 ginsenosides, including internal standard saikosaponin A, were separated within 18 min and detected by HPLC-DAD-ESI-MS. Whereas with UPLC-HRMS-MS/MS, all the 10 ginsenosides were separated within six minutes by using an Acquity UPLC BEH C18 column (50 × 2.1 mm ID, particle size 1.7 μm, 130 Å) and a gradient mobile phase of ammonium acetate and acetonitrile with column temperature at 50 °C, flow rate at 0.4 mL/min and detection by selected reaction monitoring (SRM) mode. High accuracy and precision was shown, with limit of quantitation (LOQ) ranging from 0.2–1.9 μg/g for HPLC-DAD-ESI-MS and 0.269–6.640 ng/g for UPLC-HRMS-MS/MS. The contents of nine ginsenosides in the ginseng root residue ranged from <LOQ-26.39 mg/g by HPLC-DAD-ESI-MS and <LOQ-21.25 mg/g by UPLC-HRMS-MS/MS, with a total amount of 38.37 and 34.71 mg/g, respectively.     

Hepatoprotective Activity of Nelumbo nucifera Gaertn. Seedpod Extract Attenuated Acetaminophen-Induced Hepatotoxicity

The aim is to investigate the effect of lotus (Nelumbo nucifera Gaertn.) seedpod extract (LSE) on acetaminophen (APAP)-induced hepatotoxicity. LSE is rich in polyphenols and has potent antioxidant capacity. APAP is a commonly used analgesic, while APAP overdose is the main reason for drug toxicity in the liver. Until now, there has been no in vitro test of LSE in drug-induced hepatotoxicity responses. LSEs were used to evaluate the effect on APAP-induced cytotoxicity, ROS level, apoptotic rate, and molecule mechanisms. The co-treatment of APAP and LSEs elevated the survival rate and decreased intracellular ROS levels on HepG2 cells. LSEs treatment could significantly reduce APAP-induced HepG2 apoptosis assessed by DAPI and Annexin V/PI. The further molecule mechanisms indicated that LSEs decreased Fas/FasL binding and reduced Bax and tBid to restore mitochondrial structure and subsequently suppress downstream apoptosis cascade activation. These declines in COX-2, NF-κB, and iNOS levels were observed in co-treatment APAP and LSEs, which indicated that LSEs could ameliorate APAP-induced inflammation. LSE protected APAP-induced apoptosis by preventing extrinsic, intrinsic, and JNK-mediated pathways. In addition, the restoration of mitochondria and inflammatory suppression in LSEs treatments indicated that LSEs could decrease oxidative stress induced by toxic APAP. Therefore, LSE could be a novel therapeutic option for an antidote against overdose of APAP.     

The effect of differently sized Ag catalysts on the fabrication of a silicon nanowire array using Ag-assisted electroless etching

A simple and low cost method to generate single-crystalline, well-aligned silicon nanowires (SiNWs) of large area, using Ag-assisted electroless etching, is presented and the effect of differently sized Ag catalysts on the fabrication of SiNWs arrays is investigated. The experimental results show that the size of the Ag catalysts can be controlled by adjusting the pre-deposition time in the AgNO₃/HF solution. The optimum pre-deposition time for the fabrication of a SiNWs array is 3 min (about 162.04 ± 38.53 nm Ag catalyst size). Ag catalysts with smaller sizes were formed in a shorter pre-deposition time (0.5 min), which induced the formation of silicon holes. In contrast, a large amount of Ag dendrites were formed on the silicon substrate, after a longer pre-deposition time (4 min). The existence of these Ag dendrites is disadvantageous to the fabrication of SiNWs. Therefore, a proper pre-deposition time for the Ag catalyst is beneficial to the formation of SiNWs.SiNWs were synthesized in the H₂O₂/HF solution system for different periods of time, using Ag-assisted electroless etching (pre-deposition of the Ag catalyst for 3 min). The length of the SiNWs increases linearly with immersion time. From TEM, SAED and HRTEM analysis, the axial orientation of the SiNWs is identified to be along the [001] direction, which is the same as that of the initial Si wafer. The use of HF may induce Si–H_x bonds onto the SiNW array surface. Overall, the Ag-assisted electroless etching technique has advantages, such as low temperature, operation without the need for high energy and the lack of a need for catalysts or dopants.