Electronic structures and nonlinear optical properties of macrocycles in model compounds and in photosynthetic systems

Ultrafast energy and electron transfer processes are carried out in natural photosynthetic systems via chlorophyll molecules attached to proteins. The chlorophyll molecules are held by the protein matrices with different relative distances and orientations. The environment around each chlorophyll determines its energetics and function in initial photochemical reactions. One of the most important factors that modify the energetics of the chlorophylls is the electronic interactions between the chlorophylls. This has been demonstrated by the structural details of the two chlorophyll arrays, B800 and B850 in photosynthetic bacterial antenna LHII, as well as the special pair chlorophylls in the bacterial photosynthetic reaction center. The former conducts the energy transfer to LFI, then to the reaction center, the latter, the electron transfer. The electronic interactions between chlorophylls in model systems and natural photosynthetic systems have been studied extensively with various techniques, e.g., linear optical absorption, but the nonlinear optical properties, such as high order nonlinear optical susceptibilities, are not well characterized. In this study, we intend to characterize the nonlinear optical susceptibility {Chi} in various molecular systems consisting of chlorophyll, porphyrin and phthalocyanine with different configurations and aggregation states. The goal of this research is twofold, (1) to establish the correlation between the electronic couplings in macrocycles and {Chi} with experimental measurements (e.g., degenerated four wave mixing, DFWM) and theoretical modeling, and (2) to explore the potential applications of biophotonics device based on the {Chi} measurements of various chlorophyll arrays which perform ultrafast energy and electron transfer similar to those desirable functions in photonic devices

Synergistic therapeutic effect of arsenic trioxide and radiotherapy in BALB/C nude mice bearing nasopharyngeal carcinoma xenografts

It has been shown that arsenic trioxide (ATO) induced apoptosis in human nasopharyngeal carcinoma cells and inhibited the growth of nasopharyngeal carcinoma xenografts (NPCX) in nude mice. Aim: The present study was designed to determine whether ATO at the non-toxic dose level could potentiate the therapeutic effectiveness of radiation therapy in nasopharyngeal carcinoma, using a BALB/C nude mouse xenograft model. Methods: The mice bearing NPCX were treated with radiation alone (2, 4, and 6 Gy), ATO alone (4 mg/kg/day x 6 days), and ATO plus radiation at the same dosage levels. Time of tumor growth delay (defined as the time necessary for the tumor to grow four-fold of its initial volume after, compared with untreated tumors) and toxic effects were determined. Results: The low dose ATO alone has no pronounced effects on tumor growth delay compared to untreated control. However, compared with radiation alone, the combined regimen delayed the tumor growth by 2–10 days and had no significant toxic effects such as the liver function damage. Conclusions: Combination of ATO at non-toxic dose level and radiation has synergistic effects on tumor growth inhibition in vivo and is well tolerated.Установлено, что триоксид мышьяка (ТОМ) индуцирует апоптоз в клетках карциномы носоглотки человека и ингибирует рост ксенографта карциномы носоглотки у атимических мышей. Цель работы — установить терапевтическую эффективность радиотерапии в комбинации ТОМ в нетоксичной дозе мышам линии BALB/ с ксенографтом карциномы носоглотки. Методы: животные с ксенографтом карциномы носоглотки получали либо только радиотерапию (2, 4 и 6 Гр) или ТОМ (4 мг/кг/день в течение 6 дней), или их комбинацию в тех же режимах и дозах. Задержку роста опухоли определяли как различие во времени, необходимом для достижения опухолью 4-кратного объема по сравнению с начальным объемом в опытной группе versus такового в контрольной группе. Результаты: введение ТОМ в низкой дозе не оказывало выраженного влияния на рост опухоли по сравнению с показателями в конт­рольной группе, а в комбинации с облучением приводило к задержке роста опухоли на 2–12 сут по сравнению с показателями у животных, получавших только лучевую терапию при отсутствии выраженных побочных эффектов. Выводы: комбинация ТОМ в нетоксической дозе и лучевой терапии приводит к ингибированию роста опухоли in vivo и не вызывает побочных эффектов. Ключевые слова: триоксид мышьяка, радиотерапия, ксенографт карциномы носоглотки

Molecular structure determination for photogenerated intermediates in photoinduced electron transfer reactions using steady-state and transient XAFS

Many photoinduced electron transfer reactions are accompanied by nuclear rearrangements of the molecules involved. In order to understand the reactivities of the molecules and the reaction mechanisms, precise information on the molecular structural changes accompanying the electron transfer is often required. We present here conventional XAFS and transient energy dispersive XAFS studies on structures of excited and photoinduced charge separated state of porphyrin and porphyrin based supermolecules, and structures of TiO{sub 2} colloid and the heavymetal ions that bind to the colloid surfaces during photocatalytic reductions

Preparation, characterization and anti-ageing activity of Gastrodia elata blume polysaccharide

Gastrodia elata Blume polysaccharide (GEP) was extracted and then chemically characterised. Its antioxidant activity was evaluated in vitro and in vivo. The results of the in vitro investigation show that GEP consists of glucose with molecular weight of 875 185 Da and exhibits high hydroxyl radical scavenging, as well as 2,2-diphenyl-1- picrylhydrazyl activity and reducing capacity. For antioxidant activity in vivo, D-galactose-induced-aged mice were orally administered with three different doses of GEP over a period of 6 weeks. The administration of GEP dosedependently increased the body weight gain rates, liver and brain indices, superoxide dismutase and glutathione peroxidase activities, and malondialdehyde levels in the sera and brains of ageing mice. These results suggest that GEP exhibits high antioxidant activity and can retard human ageing associated with free radicals

Crystal Structure, Infrared Spectra, and Microwave Dielectric Properties of Temperature-Stable Zircon-Type (Y,Bi)VO<inf>4</inf> Solid-Solution Ceramics

A series of (Bi 1-x Y x )VO 4 (0.4 ≤ x ≤ 1.0) ceramics were synthesized using the traditional solid-state reaction method. In the composition range of 0.4 ≤ x ≤ 1.0, a zircon-type solid solution was formed between 900 and 1550 °C. Combined with our previous work (scheelite monoclinic and zircon-type phases coexist in the range of x < 0.40), a pseudobinary phase diagram of BiVO 4 -YVO 4 is presented. As x decreased from 1.0 to 0.40, the microwave permittivity (ϵ r ) of (Bi 1-x Y x )VO 4 ceramics increased linearly from 11.03 to 30.9, coincident with an increase in the temperature coefficient of resonant frequency (TCF) from -61.3 to +103 ppm/°C. Excellent microwave dielectric properties were obtained for (Bi 0.3 Y 0.7 )VO 4 sintered at 1025 °C and (Bi 0.2 Y 0.8 )VO 4 sintered at 1075 °C with ϵ r ∼ 19.35, microwave quality factor (Qf) ∼ 25 760 GHz, and TCF ∼ +17.8 ppm/°C and ϵ r ∼ 16.3, Qf ∼ 31 100 GHz, and TCF ∼ -11.9 ppm/°C, respectively. Raman spectra, Shannon's additive rule, a classical oscillator model, and far-infrared spectra were employed to study the structure-property relations in detail. All evidence supported the premise that Bi-based vibrations dominate the dielectric permittivity in the microwave region

A strong steric hindrance effect on ground state, excited state, and charge separated state properties of a CuI-diimine complex captured by X-ray transient absorption spectroscopy

Steady-state and transient structures of a copper diimine dye sensitizer on TiO2 nanoparticles undergoing photoinduced interfacial electron transfer are determined.</p

Rotating day and night disturb growth hormone secretion profiles, body energy metabolism, and insulin levels in mice

Background: Insulin and growth hormone (GH) - 2 vital metabolic regulatory hormones - regulate glucose, lipid, and energy metabolism. These 2 hormones determine substrate and energy metabolism under different living conditions. Shift of day and night affects the clock system and metabolism probably through altered insulin and GH secretion. Methods: Five-week-old male mice were randomly assigned to a rotating light (RL) group (3-day normal light/dark cycle followed by 4-day reversed light/dark cycle per week) and normal light (NL) group. Body weight and food intake were recorded every week. Series of blood samples were collected for pulsatile GH analysis, glucose tolerance test, and insulin tolerance test at 9, 10, and 11 weeks from the start of intervention, respectively. Indirect calorimetric measurement was performed, and body composition was tested at 12 weeks. Expressions of energy and substrate metabolism-related genes were evaluated in pituitary and liver tissues at the end of 12-week intervention. Results: The RL group had an increased number of GH pulsatile bursts and reduced GH mass/burst. RL also disturbed the GH secretion regularity and mode. It suppressed insulin secretion, which led to a disturbed insulin/GH balance. It was accompanied by the reduced metabolic flexibility and modified gene expression involved in energy balance and substrate metabolism. Indirect calorimeter recording revealed that RL decreased the respiratory exchange ratio (RER) and oxygen consumption at the dark phase, which resulted in an increase in fat mass and free fatty acid levels in circulation. Conclusion: RL disturbed pulsatile GH secretion and decreased insulin secretion in male mice with significant impairment in energy, substrate metabolism, and body composition.Diabetes mellitus: pathophysiological changes and therap

The superconductivity at 18 K in LiFeAs system

A new iron arsenide superconducting system LiFeAs was found that crystallizes into a tetragonal structure with space group P4/nmm. The superconductivity with Tc up to 18 K was observed in the compounds. This simple 111 type layered iron arsenide superconductor can be viewed as an analogue of the infinite layer structure of copper oxides.Comment: 11 pages 3 Figure

Carbon nanotubes adhesion and nanomechanical behavior from peeling force spectroscopy

Applications based on Single Walled Carbon Nanotube (SWNT) are good example of the great need to continuously develop metrology methods in the field of nanotechnology. Contact and interface properties are key parameters that determine the efficiency of SWNT functionalized nanomaterials and nanodevices. In this work we have taken advantage of a good control of the SWNT growth processes at an atomic force microscope (AFM) tip apex and the use of a low noise (1E-13 m/rtHz) AFM to investigate the mechanical behavior of a SWNT touching a surface. By simultaneously recording static and dynamic properties of SWNT, we show that the contact corresponds to a peeling geometry, and extract quantities such as adhesion energy per unit length, curvature and bending rigidity of the nanotube. A complete picture of the local shape of the SWNT and its mechanical behavior is provided