Conditions favoring the formation of monomeric Pt(III) derivatives in the electrochemical oxidation of trans-[Pt(II){(p-BrC6F4)NCH2CH2NEt2}Cl(py)]

Characterization of the anticancer active compound trans-[Pt^II{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] is described along with identification of electrochemical conditions that favor formation of a monomeric one-electron-oxidized Pt^III derivative. The square-planar organoamidoplatinum(II) compound was synthesized through a carbon dioxide elimination reaction. Structural characterization by using single-crystal X-Ray diffraction reveals a trans configuration with respect to donor atoms of like charges. As Pt^III intermediates have been implicated in the reactions of platinum anticancer agents, electrochemical conditions favoring the formation of one-electron-oxidized species were sought. Transient cyclic voltammetry at fast scan rates or steady-state rotating disc and microelectrode techniques in a range of molecular solvents and an ionic liquid confirm the existence of a well-defined, chemically and electrochemically reversible one-electron oxidation process that, under suitable conditions, generates a Pt^III complex, which is proposed to be monomeric [Pt^III{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]⁺. Electron paramagnetic resonance spectra obtained from highly non-coordinating dichloromethane/([Bu4N][B(C6F5)4]) solutions, frozen to liquid nitrogen temperature immediately after bulk electrolysis in a glove box, support the Pt^III assignment rather than formation of a Pt^II cation radical. However, the voltammetric behavior is highly dependent on the timescale of the experiments, temperature, concentration of trans-[Pt^II{(p-BrC6F4)NCH2CH2NEt2}- Cl(py)], and the solvent/electrolyte. In the low-polarity solvent CH2Cl2 containing the very weakly coordinating electrolyte [Bu4N][B(C6F5)4], a well-defined reversible one-electron oxidation process is observed on relatively long timescales, which is consistent with the stabilization of the cationic platinum(III) complex in non-coordinating media. Bulk electrolysis of low concentrations of [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] favors the formation of monomeric [Pt^III{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]⁺. Simulations allow the reversible potential of the Pt^II/Pt^III process and the diffusion coefficient of [Pt^III{(p-BrC6F4)- NCH2CH2NEt2}Cl(py)]⁺ to be calculated. Reversible electrochemical behavior, giving rise to monomeric platinum(III) derivatives, is rare in the field of platinum chemistry.

Breaking up prolonged sitting reduces resting blood pressure in overweight/obese adults

Abstract
Aim:
To compare the effect of 7 h of prolonged sitting on resting blood pressure with asimilar duration of sitting combined with intermittent brief bouts of light-intensity or moderate-intensity physical activity.
Methods and results:
Overweight/obeseadults(nZ19;aged45 e65years) were recruited for a randomized three-treatment crossover trial with a one-week washout between treatments: 1) uninterrupted sitting; 2) sitting with 2 min bouts of light-intensity walking at 3.2 km/h every 20 min;and, 3) sitting with 2 min bouts of moderate-intensity walking at between 5.8 and 6.4 km/h every 20 min. After an initial 2 h period seated, participants consumed a test meal (75 g carbohydrate,50 g fat) and completed each condition over the next 5 h. Resting blood pressure was assessed oscillometrically every hour as a single measurement, 5 min prior to each activity bout. GEE models were adjusted for sex, age, BMI, fasting blood pressure and treatment order. After adjustment for potential confounding variables, breaking up prolonged sitting with lightand moderate-intensity activity breaks was associated with lower systolic blood pressure [light:120

1 mmHg (estimated marginal mean

SEM),
P
Z
0.002; moderate: 121

1 mmHg,
P
Z
0.02], compared to uninterrupted sitting (123

1 mmHg). Diastolic blood pressure was also
signi
fi
cantly lower during both of the activity conditions (light: 76

1 mmHg,
P
Z
0.006; moder-
ate: 77

1mmHg,
P
Z
0.03) compared to uninterrupted sitting (79

1 mmHg). No significant between-condition differences were observed in mean arterial pressure or heart rate.
Conclusion:
Regularly breaking up prolonged sitting may reduce systolic and diastolic blood pressure.

Inner architecture of bonded splats under combined high pressure and shear

Micron size aluminum particles (Figure 1) are deformed into “interlocked splats” at room temperature under high pressure and shear. Sample's induced inner architecture is examined (Figure 2). Tests are carried out to characterize material's heterogeneous properties (Figure 3). Presented formulation of the test data indicates an excellent shear strength; stronger than its solid counterpart.

A new biocompatible ionic liquid as an antiwear additive for biodegradable lubricants

A new biocompatible ionic liquid P1444DPP (IL1) was investigated as an antiwear additive and compared against Amine Phosphate (AP), one of the commonly used conventional antiwear additives in various biodegradable base stocks. In general, such base stocks (vegetable oil and synthetic esters) are being used for preparing biodegradable industrial lubricants. To further check its efficacy, the results were also compared with one of the ionic liquid P66614DPP (IL2) which has better performance as a lubricant, but is less biocompatible. IL1 showed excellent antiwear performance on pin-on-disc tribometer, when blended in biodegradable base stocks. The steel balls after the pin-on-disc test were analyzed using SEM-EDS technique. The oxidation stability of IL1 was studied by Pressure Differential Scanning Calorimeter (PDSC) and compared with the behavior of AP after incorporating optimized dosage of antioxidant additives in the biodegradable base stock.

Influence of work pressure on proactive skill development in China: the role of career networking behavior and guanxi HRM

This research examines how work pressure influences proactive skill development in the contextof the Chinese workplace. Drawing from the conservation of resources theory, we developa model which argues that career networking behavior serves as the mechanism that allowsemployees to transform work pressure into proactive skill development. We further arguethat in the context of the Chinese workplace, guanxi HRM, which is a culturally-specific workplacepractice deeply-rooted in Chinese tradition, plays a contingency role in influencing theextent to which work pressure influences career networking behavior. We test our modelusing Partial Least Squares Structural Equation Modeling for a sample of employees (N =392) in China. The results show that career networking behavior positively mediates the influenceof work pressure on proactive skill development and that guanxi HRM positively and significantlymoderates the influence of work pressure on career networking behavior. The overallfindings provide empirical support for the relevance of contextual and motivational factors inexplaining employee proactive skill development. The theoretical and practical implicationsof the findings are fully discussed.