Biological responses of human bone marrow mesenchymal stem cells to Sr-M-Si (M = Zn, Mg) silicate bioceramics

Strontium (Sr), Zinc (Zn), magnesium (Mg), and silicon (Si) are reported to be essential trace elements for the growth and mineralization of bone. We speculated that the combination of these bioactive elements in bioceramics may be effective to regulate the osteogenic property of boneforming cells. In this study, two Sr-containing silicate bioceramics, Sr2ZnSi2O7 (SZS) and Sr2MgSi2O7 (SMS), were prepared. The biological response of human bone marrow mesenchymal stem cells (BMSCs) to the two bioceramics (in the forms of powders and dense ceramic bulks) was systematically studied. In powder form, the effect of powder extracts on the viability and alkaline phosphatase (ALP) activity of BMSCs was investigated. In ceramic disc form, both direct and indirect coculture of BMSCs with ceramic discs were used to investigate their biological response, including attachment, proliferation, ALP activity, and bone-related genes expression. Beta-tricalcium phosphate (b-TCP) and akermanite (Ca2MgSi2O7, CMS) were used as control materials. The results showed that the Sr, Zn, and Si (or Sr, Mg, and Si)-containing ionic products from SZS and SMS powders enhanced ALP activity of BMSCs, compared to those from b-TCP. Both SZS and SMS ceramic discs supported the growth of BMSCs, and most importantly, significantly enhanced the ALP activity and bone-related genes expression of BMSCs as compared to b-TCP. The results suggest that the specific combination of bioactive ions (Sr, Zn, Si, e.g.) in bioceramics is a viable way to improve the biological performance of biomaterials, and the form of materials and surface properties were nonnegligible factors to influence cell response.

Computational design of cyclic nitroxides as efficient redox mediators for dye-sensitized solar cells

Cyclic nitroxide radicals represent promising alternatives to the iodine-based redox mediator commonly used in dye-sensitized solar cells (DSSCs). To date DSSCs with nitroxide-based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one-electron oxidation and it must possess an oxidation potential in a range of 0.600-0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N-containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl-, methoxy-, amino-, carboxy-, etc.) to the ring. Standard oxidation potentials were calculated using high-level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired E° ox and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A small molecule that walks non-directionally along a track without external intervention

Charge of the light brigade: A molecule is able to walk back and forth upon a five-foothold pentaethylenimine track without external intervention. The 1D random walk is highly processive (mean step number 530) and exchange takes place between adjacent amine groups in a stepwise fashion. The walker performs a simple task whilst walking: quenching of the fluorescence of an anthracene group sited at one end of the track. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic covalent chemistry on surfaces employing highly reactive cyclopentadienyl moieties

Silicon substrates coated with a bromide-terminated silane are transformed into highly reactive, cyclopentadiene covered analogues. These surfaces undergo rapid cycloaddition reactions with various dienophile-capped polymers. Mild heating of the substrates causes the retro-Diels-Alder reaction to occur, thus reforming the reactive cyclopentadiene surface, generating an efficiently switchable surface.

Photoclickable surfaces for profluorescent covalent polymer coatings

The nitrile imine-mediated tetrazole-ene cycloaddition reaction (NITEC) is introduced as a powerful and versatile conjugation tool to covalently ligate macromolecules onto variable (bio)surfaces. The NITEC approach is initiated by UV irradiation and proceeds rapidly at ambient temperature yielding a highly fluorescent linkage. Initially, the formation of block copolymers by the NITEC methodology is studied to evidence its efficacy as a macromolecular conjugation tool. The grafting of polymers onto inorganic (silicon) and bioorganic (cellulose) surfaces is subsequently carried out employing the optimized reaction conditions obtained from the macromolecular ligation experiments and evidenced by surface characterization techniques, including X-ray photoelectron spectroscopy and FT-IR microscopy. In addition, the patterned immobilization of variable polymer chains onto profluorescent cellulose is achieved through a simple masking process during the irradiation. Photoinduced nitrile imine-alkene 1,3-dipolar cycloaddition (NITEC) is employed to covalently bind well-defined polymers onto silicon oxide or cellulose. A diaryl tetrazole-functionalized molecule is grafted via silanization or amidification, respectively. Under UV light, a reactive nitrile imine rapidly forms and reacts with maleimide-functionalized polymers yielding a fluorescent linkage. Via a masking method, polymeric fluorescent patterns are achieved.

Unit commitment in power systems with plug-in hybrid electric vehicles

With the continued development of renewable energy generation technologies and increasing pressure to combat the global effects of greenhouse warming, plug-in hybrid electric vehicles (PHEVs) have received worldwide attention, finding applications in North America and Europe. When a large number of PHEVs are introduced into a power system, there will be extensive impacts on power system planning and operation, as well as on electricity market development. It is therefore necessary to properly control PHEV charging and discharging behaviors. Given this background, a new unit commitment model and its solution method that takes into account the optimal PHEV charging and discharging controls is presented in this paper. A 10-unit and 24-hour unit commitment (UC) problem is employed to demonstrate the feasibility and efficiency of the developed method, and the impacts of the wide applications of PHEVs on the operating costs and the emission of the power system are studied. Case studies are also carried out to investigate the impacts of different PHEV penetration levels and different PHEV charging modes on the results of the UC problem. A 100-unit system is employed for further analysis on the impacts of PHEVs on the UC problem in a larger system application. Simulation results demonstrate that the employment of optimized PHEV charging and discharging modes is very helpful for smoothing the load curve profile and enhancing the ability of the power system to accommodate more PHEVs. Furthermore, an optimal Vehicle to Grid (V2G) discharging control provides economic and efficient backups and spinning reserves for the secure and economic operation of the power system

Effectiveness of red light cameras on the right-angle crash involvement of motorcycles

Red light cameras (RLC) have been used to reduce right-angle collisions at signalized intersections. However, the effect of RLCs on motorcycle crashes has not been well investigated. The objective of this study is to evaluate the effectiveness of RLCs on motorcycle safety in Singapore. This is done by comparing their exposure, proneness of at-fault right-angle crashes as well as the resulting right-angle collisions at RLC with those at non-RLC sites. Estimating the crash vulnerability from not-at-fault crash involvements, the study shows that with a RLC, the relative crash vulnerability or crash-involved exposure of motorcycles at right-angle crashes is reduced. Furthermore, field investigation of motorcycle maneuvers reveal that at non-RLC arms, motorcyclists usually queue beyond the stop-line, facilitating an earlier discharge and hence become more exposed to the conflicting stream. However at arms with a RLC, motorcyclists are more restrained to avoid activating the RLC and hence become less exposed to conflicting traffic during the initial period of the green. The study also shows that in right-angle collisions, the proneness of at-fault crashes of motorcycles is lowest among all vehicle types. Hence motorcycles are more likely to be victims than the responsible parties in right-angle crashes. RLCs have also been found to be very effective in reducing at-fault crash involvements of other vehicle types which may implicate exposed motorcycles in the conflicting stream. Taking all these into account, the presence of RLCs should significantly reduce the vulnerability of motorcycles at signalized intersections.

Effects of impulsive sensation seeking, aggression and risk-taking behavior on the vulnerability of motorcyclists

While extensive research efforts have been devoted to improve the motorcycle safety, the relationship between the rider behavior and the crash risk is still not well understood.The objective of this study is to evaluate how behavioral factors influence crash risk and to identify the most vulnerable group of motorcyclists. To explore the rider behavior, a questionnaire containing 61-items of impulsive sensation seeking, aggression, and risk-taking behavior was developed. By clustering the crash risk using the medoid portioning algorithm, the log-linear model relating the rider behavior to crash risk has been developed. Results show that crash-involved motorcyclists score higher in all three behavioral traits. Aggressive and high risk-taking motorcyclists are more likely to fall under the high vulnerable group while impulsive sensation seeking is not found to be significant. Defining personality types from aggression and risk-taking behavior, “Extrovert” and “Follower” personality type of motorcyclists are more prone to crashes. The findings of this study will be useful for road safety campaign planners to be more focused in the target group as well as those who employ motorcyclists for their delivery business

Road safety in Singapore

Singapore is a highly developed country that has a well connected island-wide road transport system including a network of expressways. The road standards of Singapore are generally good and road safety level is very high by international standards. This chapter discusses road safety status in Singapore and highlights the practices that have been undertaken to enhance the road safety. Statistics show that road traffic fatalities were decreasing over the years, albeit an increasing trend for total crashes. Motorcyclists and pedestrians were two vulnerable road user groups and shared significant proportions respectively about 49% and 28% of total road traffic deaths. In particular, young riders and pedestrians had a higher crash potential. To enhance safety of those vulnerable road users, Singapore has taken several initiatives including infrastructure improvements like paving better skid-resistant materials at crash-prone sites, providing more rain shelters for motorcyclists, and installation of reflective signs and markings near school zones; safety campaigns and awareness programs like ride safe programme, the road courtesy campaign, and the anti-drink drive campaign. While Land Transport Authority (LTA) looks into road safety through engineering solutions and road infrastructure developments, the Traffic Police of Singapore is responsible for law enforcements and regulations. A number of non-government organizations, private companies, and university research groups are also continuously working with the Traffic Police to study, promote, and educate the general public on road safety matters.