Thiophene-benzothiadiazole-thiophene (D-A-D) based polymers : Effect of donor/acceptor moieties adjacent to D-A-D segment on photophysical and photovoltaic properties

New push-pull copolymers based on thiophene (donor) and benzothiadiazole (acceptor) units, poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co- thiophene] (PT3B1) and poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] (PT2B2), are designed and synthesized via Stille and Suzuki coupling routes respectively. Gel permeation chromatography shows the number average molecular weights are 31100 and 8400 g mol-1 for the two polymers, respectively. Both polymers have shown absorption throughout a wide range of the UV-vis region, from 300 to 650 nm. A significant red shift of the absorption edge is observed in thin films compared to solution of the copolymers; the optical band gap is in the range of 1.7 to 1.8 eV. Cyclic voltammetry indicates reversible oxidation and reduction processes with HOMO energy levels calculated to be in the range of 5.2 to 5.4 eV. Upon testing both materials for organic field-effect transistors (OFETs), PT3B1 showed a hole mobility of 6.1 × 10-4 cm2 V-1 s -1, while PT2B2 did not show any field effect transport. Both copolymers displayed a photovoltaic response when combined with a methanofullerene as an electron acceptor. The best performance was achieved when the copolymer PT3B1 was blended with [70]PCBM in a 1:4 ratio, exhibiting a short-circuit current of 7.27 mA cm-2, an open circuit voltage of 0.85 V, and a fill factor of 41% yielding a power conversion efficiency of 2.54% under simulated air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm-2). Similar devices utilizing PT2B2 in place of PT3B1 demonstrated reduced performance with a short-circuit current of 4.8 mA cm -2, an open circuit voltage of 0.73 V, and a fill factor of 30% resulting in a power conversion efficiency of roughly 1.06%.

Relation between charge carrier mobility and lifetime in organic photovoltaics

The relationship between charge carrier lifetime and mobility in a bulk heterojunction based organic solar cell, utilizing diketopyrrolopyrole- naphthalene co-polymer and PC71BM in the photoactive blend layer, is investigated using the photoinduced charge extraction by linearly increasing voltage technique. Light intensity, delay time, and temperature dependent experiments are used to quantify the charge carrier mobility and density as well as the temperature dependence of both. From the saturation of photoinduced current at high laser intensities, it is shown that Langevin-type bimolecular recombination is present in the studied system. The charge carrier lifetime, especially in Langevin systems, is discussed to be an ambiguous and unreliable parameter to determine the performance of organic solar cells, because of the dependence of charge carrier lifetime on charge carrier density, mobility, and type of recombination. It is revealed that the relation between charge mobility (μ) and lifetime (τ) is inversely proportional, where the μτ product is independent of temperature. The results indicate that in photovoltaic systems with Langevin type bimolecular recombination, the strategies to increase the charge lifetime might not be beneficial because of an accompanying reduction in charge carrier mobility. Instead, the focus on non-Langevin mechanisms of recombination is crucial, because this allows an increase in the charge extraction rate by improving the carrier lifetime, density, and mobility simultaneously. © 2013 AIP Publishing LLC.

Measurement of contact voltage drop and resistance in organic solar cells

Bulk heterojunction organic solar cells based on poly[4,7-bis(3- dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] and [6,6]-phenyl C71-butyric acid methyl ester are investigated. A prominent kink is observed in the fourth quadrant of the current density-voltage (J-V) response. Annealing the active layer prior to cathode deposition eliminates the kink. The kink is attributed to an extraction barrier. The J-V response in these devices is well described by a power law. This behavior is attributed to an imbalance in charge carrier mobility. An expected photocurrent for the device displaying a kink in the J-V response is determined by fitting to a power law. The difference between the expected and measured photocurrent allows for the determination of a voltage drop within the device. Under simulated 1 sun irradiance, the peak voltage drop and contact resistance at short circuit are 0.14 V and 90 Ω, respectively. © 2012 American Institute of Physics.

A novel dc-link voltage regulation method for single source hybrid multilevel inverters

This paper presents a novel dc-link voltage regulation technique for a hybrid inverter system formed by cascading two 3-level inverters. The two inverters are named as “bulk inverter” and “conditioning inverter”. For the hybrid system to act as a nine level inverter, conditioning inverter dc link voltage should be maintained at one third of the bulk inverter dc link voltage. Since the conditioning inverter is energized by two series connected capacitors, dc-link voltage regulation should be carried out by controlling the capacitor charging/discharging times. A detailed analysis of conditioning inverter capacitor charging/discharging process and a simplified general rule, derived from the analysis, are presented in this paper. Time domain simulations were carried out to demonstrate efficacy of the proposed method on regulating the conditioning inverter dc-link voltage under various operating conditions.

Better cars or older cars?: Assessing CO2 emission reduction potential of passenger vehicle replacement programs

The primary motivation for the vehicle replacement schemes that were implemented in many countries was to encourage the purchase of new cars. The basic assumption of these schemes was that these acquisitions would benefit both the economy and the environment as older and less fuel-efficient cars were scrapped and replaced with more fuel-efficient models. In this article, we present a new environmental impact assessment method for assessing the effectiveness of scrappage schemes for reducing CO2 emissions taking into account the rebound effect, driving behavior for older versus new cars and entire lifecycle emissions for during the manufacturing processes of new cars. The assessment of the Japanese scrappage scheme shows that CO2 emissions would only decrease if users of the scheme retained their new gasoline passenger vehicles for at least 4.7 years. When vehicle replacements were restricted to hybrid cars, the reduction in CO2 achieved by the scheme would be 6-8.5 times higher than the emissions resulting from a scheme involving standard, gasoline passenger vehicles. Cost-benefit analysis, based on the emission reduction potential, showed that the scheme was very costly. Sensitivity analysis showed that the Japanese government failed to determine the optimum, or target, car age for scrapping old cars in the scheme. Specifically, scrapping cars aged 13 years and over did not maximize the environmental benefits of the scheme. Consequently, modifying this policy to include a reduction in new car subsidies, focused funding for fuel-efficient cars, and modifying the target car age, would increase environmental benefits. © 2013 Elsevier Ltd.

Catch limits, capacity utilization and cost reduction in Japanese fishery management

Japan's fishery harvest peaked in the late 1980s. To limit the race for fish, each fisherman could be provided with specific catch limits in the form of individual transferable quotas (ITQs). The market for ITQs would also help remove the most inefficient fishers. In this article we estimate the potential cost reduction associated with catch limits, and find that about 300 billion yen or about 3 billion dollars could be saved through the allocation and trading of individual-specific catch shares.

Proposed MBMs for reduction of greenhouse gas emissions from international shipping and the WTO rules

The international shipping sector is a major contributor to global greenhouse gas (GHG) emissions. The International Maritime Organisation (IMO) has adopted some technical and operational measures to reduce GHG emissions from international shipping. However, these measures may not be enough to reduce the amount of GHG emissions from international shipping to an acceptable level. Therefore, the IMO Member States are currently considering a number of proposals for the introduction of market-based measures (MBMs). During the negotiation process, some leading developing countries raised questions about the probable confl ict of the proposed MBMs with the rules of the World Trade Organisation (WTO). This article comprehensively examines this issue and argues that none of the MBM proposals currently under consideration by the IMO has any confl ict with the WTO rules.

Improving voltage profile of residential distribution systems using rooftop PVs and Battery Energy Storage systems

Large number of rooftop Photovoltaics (PVs) have turned traditional passive networks into active networks with intermittent and bidirectional power flow. A community based distribution network grid reinforcement process is proposed to address technical challenges associated with large integration of rooftop PVs. Probabilistic estimation of intermittent PV generation is considered. Depending on the network parameters such as the R/X ratio of distribution feeder, either reactive control from PVs or coordinated control of PVs and Battery Energy Storage (BES) has been proposed. Determination of BES capacity is one of the significant outcomes from the proposed method and several factors such as variation in PV installed capacity as well as participation from community members are analyzed. The proposed approach is convenient for the community members providing them flexibility of managing their integrated PV and BES systems

Biological monitoring in workers in a nitrobenzene reduction plant : Haemoglobin versus serum albumin adducts

The high priority of monitoring workers exposed to nitrobenzene is a consequence of clear findings of experimental carcinogenicity of nitrobenzene and the associated evaluations by the International Agency for Research on Cancer. Eighty male employees of a nitrobenzene reduction plant, with potential skin contact with nitrobenzene and aniline, participated in a current medical surveillance programme. Blood samples were routinely taken and analysed for aniline, 4-aminodiphenyl (4-ADP) and benzidine adducts of haemoglobin (Hb) and human serum albumin (HSA). Also, levels of methaemoglobin (Met-Hb) and of carbon monoxide haemoglobin (CO-Hb) were monitored. Effects of smoking were straightforward. Using the rank sum test of Wilcoxon, we found that very clear-cut and statistically significant smoking effects (about 3-fold increases) were apparent on CO-Hb (P = 0.00085) and on the Hb adduct of 4-ADP (P = 0.0006). The mean aniline-Hb adduct level in smokers was 1.5 times higher than in non-smokers; the significance (P = 0.05375) was close to the 5% level. The strongest correlation was evident between the Hb and HSA adducts of aniline (rs = 0.846). Less pronounced correlations (but with P values < 0.02) appeared between aniline-Hb and 4-ADP-Hb adducts (rs = 0.388), between 4-ADP and 4-ADP-HSA adducts (rs = 0.373), and between 4-ADP-Hb and aniline-HSA adducts (rs = 0.275). In view of the proposal for additional use of the aniline-HSA adduct for biological monitoring, particularly in cases of acute overexposures or poisonings, the strong correlation of the Hb and HSA conjugates is noteworthy; the ratio aniline-HSA:aniline-Hb was 1:42 for the entire cohort.

Available evidence does not support serosorting as an HIV risk reduction strategy

Recent data highlighted the association between penetration of antiretrovirals in the central nervous system (CNS) and neurocognitive impairment in HIVpositive patients. Existing antiretrovirals have been ranked according to a score of neuropenetration, which was shown to be a predictor of anti-HIVactivity in the CNS and improvement of neurocognitive disorders [1]. Main factors affecting drug penetration are known to be protein binding, lipophilicity and molecular weight [2]. Moreover, active translation by membrane transporters (such as p-glycoprotein) could be a key mechanism of passage [3]. The use of raltegravir (RGV), a novel antiretroviral drug targeted to inhibit the HIV preintegrase complex, is increasing worldwide due to its efficacy and tolerability. However, penetration of RGV in the CNS has not been yet elucidated. In fact, prediction of RGV neuropenetration according to molecular characteristics is controversial. Intermediate protein binding (83%) and large volume of distribution (273 l) could suggest a high distribution beyond extracellular spaces [4]. On the contrary, low lipophilicity (oil/water partition coefficient at pH 7.4 of 2.80) and intermediate molecular weight (482.51 Da) suggest a limited diffusion. Furthermore, in-vitro studies suggest that RGV is substrate of p-glycoprotein, although this efflux pump has not been identified to significantly affect plasma pharmacokinetics [5]. In any case, no data concerning RGV passage into cerebrospinal fluid of animals or humans have yet been published.

Implications of differences in technical efficiency of fishing boats for capacity measurement and reduction

Capacity measurement and reduction is a major international issue to emerge in the new millennium. However, there has been limited assessment of the success of capacity reduction schemes (CRS). In this paper, the success of a CRS is assessed for a European fishery characterised by differences in efficiency levels of individual boats. In such a fishery, given it is assumed that the least efficient producers are the first to exit through a CRS, the reduction in harvesting capacity is less than the nominal reduction in physical fleet capacity. Further, there is potential for harvesting capacity to increase if remaining vessels improve their efficiency.