Electronic transitions and bonding properties in a series of five-coordinate “16-electron” complexes [Mn(CO)3(L2)]− (L2=chelating redox-active π-donor ligand)

In this article we present for the first time accurate density functional theory (DFT) and time-dependent (TD) DFT data for a series of electronically unsaturated five-coordinate complexes [Mn(CO)(3)(L-2)](-), where L-2 stands for a chelating strong pi-donor ligand represented by catecholate, dithiolate, amidothiolate, reduced alpha-diimine (1,4-dialkyl-1,4-diazabutadiene (R-DAB), 2,2'-bipyridine) and reduced 2,2'-biphosphinine types. The single-crystal X-ray structure of the unusual compound [Na(BPY)][Mn(CO)(3)(BPY)]center dot Et2O and the electronic absorption spectrum of the anion [Mn(CO)(3)(BPY)](-) are new in the literature. The nature of the bidentate ligand determines the bonding in the complexes, which varies between two limiting forms: from completely pi-delocalized diamagnetic {(CO)(3)Mn-L-2}(-) for L-2 = alpha-diimine or biphosphinine, to largely valence-trapped {(CO)(3)Mn-1-L-2(2-)}(-) for L-2(2-) = catecholate, where the formal oxidation states of Mn and L-2 can be assigned. The variable degree of the pi-delocalization in the Mn(L-2) chelate ring is indicated by experimental resonance Raman spectra of [Mn(CO)(3)(L-2)](-) (L-2=3,5-di-tBu-catecholate and iPr-DAB), where accurate assignments of the diagnostically important Raman bands have been aided by vibrational analysis. The L-2 = catecholate type of complexes is known to react with Lewis bases (CO substitution, formation of six-coordinate adducts) while the strongly pi-delocalized complexes are inert. The five-coordinate complexes adopt usually a distorted square pyramidal geometry in the solid state, even though transitions to a trigonal bipyramid are also not rare. The experimental structural data and the corresponding DFT-computed values of bond lengths and angles are in a very good agreement. TD-DFT calculations of electronic absorption spectra of the studied Mn complexes and the strongly pi-delocalized reference compound [Fe(CO)(3)(Me-DAB)] have reproduced qualitatively well the experimental spectra. Analyses of the computed electronic transitions in the visible spectroscopic region show that the lowest-energy absorption band always contains a dominant (in some cases almost exclusive) contribution from a pi(HOMO) -> pi*(LUMO) transition within the MnL2 metallacycle. The character of this optical excitation depends strongly on the composition of the frontier orbitals, varying from a partial L-2 -> Mn charge transfer (LMCT) through a fully delocalized pi(MnL2) -> pi*(MnL2) situation to a mixed (CO)Mn -> L-2 charge transfer (LLCT/MLCT). The latter character is most apparent in the case of the reference complex [Fe(CO)(3)(Me-DAB)]. The higher-lying, usually strongly mixed electronic transitions in the visible absorption region originate in the three lower-lying occupied orbitals, HOMO - 1 to HOMO - 3, with significant metal-d contributions. Assignment of these optical excitations to electronic transitions of a specific type is difficult. A partial LLCT/MLCT character is encountered most frequently. The electronic absorption spectra become more complex when the chelating ligand L-2, such as 2,2'-bipyridine, features two or more closely spaced low-lying empty pi* orbitals.

Effect of low-level laser therapy (GaAs 904 nm) in skeletal muscle fatigue and biochemical markers of muscle damage in rats

We wanted to test if pre-exercise muscle irradiation with 904 nm laser affects the development of fatigue, blood lactate levels and creatine kinase (CK) activity in a rat model with tetanic contractions. Thirty male Wistar rats were divided into five groups receiving either one of four different laser doses (0.1, 0.3, 1.0 and 3.0 J) or a no-treatment control group. Laser irradiation was performed immediately before the first contraction for treated groups. Electrical stimulation was used to induce six tetanic tibial anterior muscle contractions with 10 min intervals between them. Contractions were stopped when the muscle force fell to 50% of the peak value for each contraction; blood samples were taken before the first and immediately after the sixth contraction. The relative peak forces for the sixth contraction were significantly better (P < 0.05) in the two laser groups irradiated with highest doses [151.27% (SD +/- A 18.82) for 1.0 J, 144.84% (SD +/- A 34.47) for 3.0 J and 82.25% (SD +/- A 11.69) for the control group]. Similar significant (P < 0.05) increases in mean performed work during the sixth contraction for the 1.0 and 3.0 J groups were also observed. Blood lactate levels were significantly lower (P < 0.05) than the control group in all irradiated groups. All irradiated groups except the 3.0 J group had significantly lower post-exercise CK activity than the control group. We conclude that pre-exercise irradiation with a laser dose of 1.0 J and 904 nm wavelength significantly delays muscle fatigue and decreases post-exercise blood lactate and CK in this rat model.

Effect of 830 nm low-level laser therapy applied before high-intensity exercises on skeletal muscle recovery in athletes

Our aim was to investigate the immediate effects of bilateral, 830 nm, low-level laser therapy (LLLT) on high-intensity exercise and biochemical markers of skeletal muscle recovery, in a randomised, double-blind, placebo-controlled, crossover trial set in a sports physiotherapy clinic. Twenty male athletes (nine professional volleyball players and eleven adolescent soccer players) participated. Active LLLT (830 nm wavelength, 100 mW, spot size 0.0028 cm(2), 3-4 J per point) or an identical placebo LLLT was delivered to five points in the rectus femoris muscle (bilaterally). The main outcome measures were the work performed in the Wingate test: 30 s of maximum cycling with a load of 7.5% of body weight, and the measurement of blood lactate (BL) and creatine kinase (CK) levels before and after exercise. There was no significant difference in the work performed during the Wingate test (P > 0.05) between subjects given active LLLT and those given placebo LLLT. For volleyball athletes, the change in CK levels from before to after the exercise test was significantly lower (P = 0.0133) for those given active LLLT (2.52 U l(-1) +/- 7.04 U l(-1)) than for those given placebo LLLT (28.49 U l(-1) +/- 22.62 U l(-1)). For the soccer athletes, the change in blood lactate levels from before exercise to 15 min after exercise was significantly lower (P < 0.01) in the group subjected to active LLLT (8.55 mmol l(-1) +/- 2.14 mmol l(-1)) than in the group subjected to placebo LLLT (10.52 mmol l(-1) +/- 1.82 mmol l(-1)). LLLT irradiation before the Wingate test seemed to inhibit an expected post-exercise increase in CK level and to accelerate post-exercise lactate removal without affecting test performance. These findings suggest that LLLT may be of benefit in accelerating post-exercise recovery.

CMOS-based active pixel for low-light-level detection: Analysis and measurements

An analysis of the active pixel sensor (APS), considering the doping profiles of the photodiode in an APS fabricated in a 0.18 μm standard CMOS technology, is presented. A simple and accurate model for the junction capacitance of the photodiode is proposed. An analytic expression for the output voltage of the APS obtained with this capacitance model is in good agreement with measurements and is more accurate than the models used previously. A different mode of operation for the APS based on the dc level of the output is suggested. This new mode has better low-light-level sensitivity than the conventional APS operating mode, and it has a slower temporal response to the change of the incident light power. At 1μW/cm2 and lower levels of light, the measured signal-to-noise ratio (SNR) of this new mode is more than 10 dB higher than the SNR of previously reported APS circuits. Also, with an output SNR of about 10 dB, the proposed dc level is capable of detecting light powers as low as 20 nW/cm2, which is about 30 times lower than the light power detected in recent reports by other groups. © 2007 IEEE.

Effects of Low-Level Laser Therapy on Biceps Braquialis Muscle Fatigue in Young Women

Objective: This study aims to investigate the effects of low-level laser therapy (LLLT) on biceps brachi muscular fatigue in 20 young females. Background data: Exhausting physical activity leads to muscular fatigue, which could decrease muscular strength, and may cause impairment in motor control and muscle pain. Several biochemical and biophysical resources have been studied in an attempt to accelerate the recovery of muscle fatigue. Among these, LLLT is emphasized. Methods: Twenty subjects were randomized in one laser group and one placebo group in two sessions of a crossover design experimental procedure; the second session taking place within 7 days of the first. In the first session, subjects underwent a collection of surface electromyographic (SEMG) data of the biceps brachii muscle, followed by active or placebo LLLT at the same muscle, followed then by another EMG sample of biceps brachii. Blood samples were collected five times during the experimental procedure. Second session procedures were identical to the first, with exception of LLLT, which was the opposite of the first session. The fatigue protocol consisted of 60sec of elbow flexion-extension movement performed with 75% of one maximum repetition. Blood lactate, EMG fatigue, and the number of elbow flexion-extension repetitions during the fatigue protocol were used to evaluate the effects of laser therapy (808nm wavelength, 100mW output power, power density of 35.7 W/cm(2), 70sec each point and 7J/point on eight points). Results: No statistical differences were found for eletromyographic fatigue and blood lactate values between groups. Mean numbers of elbow flexion-extension repetitions were 22.6 +/- 7.58 after placebo, and 25.1 +/- 9.89 after active LLLT group, but these differences were not statistically significant (p=0.342). Conclusions: LLLT had limited effects on delaying muscle fatigue in a young female sample, although a tendency was observed in the active laser group toward showing lower electromyography fatigue of biceps brachii muscle. No intergroup differences were found in the number of muscle contractions and lactate concentration.

Low-level laser therapy (LLLT) in human progressive-intensity running: effects on exercise performance, skeletal muscle status, and oxidative stress

The aim of this work was to evaluate the effects of low-level laser therapy (LLLT) on exercise performance, oxidative stress, and muscle status in humans. A randomized double-blind placebo-controlled crossover trial was performed with 22 untrained male volunteers. LLLT (810 nm, 200 mW, 30 J in each site, 30 s of irradiation in each site) using a multi-diode cluster (with five spots - 6 J from each spot) at 12 sites of each lower limb (six in quadriceps, four in hamstrings, and two in gastrocnemius) was performed 5 min before a standardized progressive-intensity running protocol on a motor-drive treadmill until exhaustion. We analyzed exercise performance (VO(2 max), time to exhaustion, aerobic threshold and anaerobic threshold), levels of oxidative damage to lipids and proteins, the activities of the antioxidant enzymes superoxide dismutase (SOD) and catalase (CAT), and the markers of muscle damage creatine kinase (CK) and lactate dehydrogenase (LDH). Compared to placebo, active LLLT significantly increased exercise performance (VO(2 max) p = 0.01; time to exhaustion, p = 0.04) without changing the aerobic and anaerobic thresholds. LLLT also decreased post-exercise lipid (p = 0.0001) and protein (p = 0.0230) damages, as well as the activities of SOD (p = 0.0034), CK (p = 0.0001) and LDH (p = 0.0001) enzymes. LLLT application was not able to modulate CAT activity. The use of LLLT before progressive-intensity running exercise increases exercise performance, decreases exercise-induced oxidative stress and muscle damage, suggesting that the modulation of the redox system by LLLT could be related to the delay in skeletal muscle fatigue observed after the use of LLLT.

The Active Subjects of Welfare Reform: a Street-Level Comparison of Employment Services in Australia and Denmark

This paper explores the similarities and differences between Denmark and Australia in adopting welfare reform activation measures in the field of employment services. In Australia and Denmark the discourse of welfare reform centres the 'activation' of citizens through 'mutual obligation' type requirements. Through various forms of case management, unemployed individuals are encouraged to act upon themselves in creating the right set of ethical dispositions congruent with 'active citizenship'. At the same time any resistance to heightened conditionality on the part of the unemployed person is dealt with through a range of coercive and disciplinary techniques. A comparative case study between these two countries allows us to consider how similar ideas, discourse and principles are shaping policy implementation in countries that have very different welfare state trajectories and institutional arrangements for the delivery of social welfare generally and employment services specifically. And in research terms, a comparison between a Nordic welfare state and an Anglo-Saxon welfare state provides an opportunity to critically examine the utility of 'welfare regime' type analyses and the neo-liberal convergence thesis in comparative welfare research. On the basis of empirical analysis, the article concludes that a single focus on abstract typologies or political ideologies is not very helpful in getting the measure of welfare reform (or any other major policy development for that matter). At the 'street-level' of policy practice there is considerably more ambiguity, incoherence and contradiction than is suggested by linear accounts of welfare reform.

Lake-level rise in the late Pleistocene and active subaquatic volcanism since the Holocene in Lake Kivu; East African Rift

The history of Lake Kivu is strongly linked to the activity of the Virunga volcanoes. Subaerial and subaquatic volcanoes, in addition to lake-level changes, shape the subaquatic morphologic and structural features in Lake Kivu's Main Basin. Previous studies revealed that volcanic eruptions blocked the former outlet of the lake to the north in the late Pleistocene, leading to a substantial rise in the lake level and subsequently the present- day thermohaline stratification. Additional studies have speculated that volcanic and seismic activities threaten to trigger a catastrophic release of the large amount of gases dissolved in the lake. The current study presents a bathymetric mapping and seismic profiling survey that covers the volcanically active area of the Main Basin at a resolution that is unprecedented for Lake Kivu. New geomorphologic features identified on the lake floor can accurately describe related lake-floor processes for the first time. The late Pleistocene lowstand is observed at 425 m depth, and volcanic cones, tuff rings, and lava flows observed above this level indicate both subaerial and subaquatic volcanic activities during the Holocene. The geomorphologic analysis yields new implications on the geologic processes that have shaped Lake Kivu's basin, and the presence of young volcanic features can be linked to the possibility of a lake overturn.

Discharge data derived from five water level gauges and discharge measurements in the Aguima and Niaou catchment, Benin, West Africa

This paper analyzes the hydrological processes and the impact of soil properties and land use on these processes in tropical headwater catchment in the sub-humid part of Benin (West-Africa), the Aguima catchment. The presented study is integrated in the GLOWA IMPETUS project, which investigates the effects of global change on the water cycle and water availability on a regional scale in Morocco and Benin. The lack of field investigations concerning soil and surface hydrology in the Benin research area necessitates detailed field measurements including measurements of discharge, soil water dynamics, soil physical properties etc. on the local scale in order to understand the dominant runoff generation processes and its influencing factors. This is a pre-requisite to be able to forecast the effects which global change has on hydrological processes and water availability in the region. The paper gives an overview over the hydrologic measuring concept of the IMPETUS-Benin project focusing on measurements concerning the soil saturated conductivity ksat and discharge behaviour of two different sub-catchment of the Aguima catchment. The results of ksat measurements revealed that interflow is the dominant runoff process on the hillslopes of the investigated catchment. Concerning the impact of land use on the hydrological processes infiltration experiments showed that infiltration rates were reduced on cultivated land compared to natural land cover. This results in significant differences in runoff behaviour and runoff ratios while comparing natural and agricultural used catchments.

Synthesis and screening of small molecule libraries active in binding to DNA

Five synthetic combinatorial libraries of 2,080 components each were screened as mixtures for inhibition of DNA binding to two transcription factors. Rapid, solution-phase synthesis coupled to a gel-shift assay led to the identification of two compounds active at a 5- to 10-μM concentration level. The likely mode of inhibition is intercalation between DNA base pairs. The efficient deconvolution through sublibrary synthesis augurs well for the use of large mixtures of small, nonpeptide molecules in biological screens.