Constraints of nutrient availability on primary production in two alpine tundra communities

A nutrient amendment experiment was conducted for two growing seasons in two alpine tundra communities to test the hypotheses that: (1) primary production is limited by nutrient availability, and (2) physiological and developmental constraints act to limit the responses of plants from a nutrient-poor community more than plants from a more nutrient-rich community to increases in nutrient availability. Experimental treatments consisted of N, P, and N+P amendments applied to plots in two physiognomically similar communities, dry and wet meadows. Extractable N and P from soils in nonfertilized control plots indicated that the wet meadow had higher N and P availability. Photosynthetic, nutrient uptake, and growth responses of the dominants in the two communities showed little difference in the relative capacity of these plants to respond to the nutrient additions. Aboveground production responses of the communities to the treatments indicated N availability was limiting to production in the dry meadow community while N and P availability colimited production in the wet meadow community. There was a greater production response to the N and N+P amendments in the dry meadow relative to the wet meadow, despite equivalent functional responses of the dominant species of both communities. The greater production response in the dry meadow was in part related to changes in community structure, with an increase in the proportion of graminoid and forb biomass, and a decrease in the proportion of community biomass made up by the dominant sedge Kobresia myosuroides. Species richness increased significantly in response to the N+P treatment in the dry meadow. Graminoid biomass increased significantly in the wet meadow N and N+P plots, while forb biomass decreased significantly, suggesting a competitive interaction for light. Thus, the difference in community response to nutrient amendments was not the result of functional changes at the leaf level of the dominant species, but rather was related to changes in community structure in the dry meadow, and to a shift from a nutrient to a light limitation of production in the wet meadow.

Organometallic macrocyclic chemistry. 8.(1) : an unusual metallacycle derived from phosphine−alkynyl thioether coupling

The α,ω-diyne 4,7,10-trithiatrideca-2,11-diyne reacts with [RuCl2(PPh3)3] and KPF6 to form the phosphonio-substituted metallatricyclic salt [RuCl(PPh3){κ4C,S,S′,S′′-S(C≡CMe)C2H4SC2H4SC(PPh3)CMe}]PF6 arising from the activation of one alkynyl group toward nucleophilic attack by extraneous phosphine.

From reader to writer : citizen journalism as news produsage

Today, participatory or citizen journalism – journalism which enables readers to become writers – exists online and offline in a variety of forms and formats, operates under a number of editorial schemes, and focusses on a wide range of topics from the specialist to the generic, and the micro-local to the global. Key models in this phenomenon include veteran sites Slashdot and Indymedia, as well as news-related Weblogs; more recent additions into the mix have been the South Korean OhmyNews, which in 2003 was “the most influential online news site in that country, attracting an estimated 2 million readers a day” (Gillmor, 2003a, p. 7), with its new Japanese and international offshoots, as well as the Wikipedia with its highly up-to-date news and current events section and its more recent offshoot Wikinews, and even citizen-produced video news as it is found in sites such as YouTube and Current.tv.

Construction safety in the repair and maintenance sector

Statistics indicate that the percentage of fatal industrial accidents arising from repair, maintenance, minor alteration and addition (RMAA) works in Hong Kong was disturbingly high and was over 56% in 2006. This paper provides an initial report of a research project funded by the Research Grants Council (RGC) of the HKSAR to address this safety issue. The aim of this study is to scrutinize the causal relationship between safety climate and safety performance in the RMAA sector. It aims to evaluate the safety climate in the RMAA sector; examine its impacts on safety performance, and recommend measures to improve safety performance in the RMAA sector. This paper firstly reports on the statistics of construction accidents arising from RMAA works. Qualitative and quantitative research methods applied in conducting the research are dis-cussed. The study will critically review these related problems and provide recommendations for improving safety performance in the RMAA sector.

Property Agents and Motor Dealers Act : strike three

The Tourism, Racing and Fair Trading (Miscellaneous Provisions) Act 2002 (“the Act”) which was passed on 18 April 2002 contains a number of significant amendments relevant to the operation of the Property Agents and Motor Dealers Act 2000. The main changes relevant to property transactions are: (i) Changes to the process for appointment of a real estate agent and consolidation of the appointment forms; (ii) Additions to the disclosure obligation of agents and property developers; (iii) Simplification of the process for commencing the cooling off period; (iv) Alteration of the common law position concerning when the parties are bound by a contract; (v) Removal of the requirement for a seller’s signature on the warning statement to be witnessed; (vi) Retrospective amendment of s 170 of the Body Corporate and Community Management Act 1997; (vii) Inclusion of a new power to allow inspectors to enter the place of business of a licensee or a marketeer without consent and without a warrant; and (viii) Inclusion of a new power for inspectors to require documents to be produced by marketeers. The majority of the amendments are effective from the date of assent, 24 April 2002, however, some of the amendments do not commence until a date fixed by proclamation. No proclamation has been made at the time of writing (2 May 2002). Where the amendments have not commenced this will be noted in the article. Before providing clients with advice, practitioners should carefully check proclamation details.

The contribution of maize cropping in the Midwest USA to global warming: A regional estimate

Agricultural soils emit about 50% of the global flux of N2O attributable to human influence, mostly in response to nitrogen fertilizer use. Recent evidence that the relationship between N2O fluxes and N-fertilizer additions to cereal maize are non-linear provides an opportunity to estimate regional N2O fluxes based on estimates of N application rates rather than as a simple percentage of N inputs as used by the Intergovernmental Panel on Climate Change (IPCC). We combined a simple empirical model of N2O production with the SOCRATES soil carbon dynamics model to estimate N2O and other sources of Global Warming Potential (GWP) from cereal maize across 19,000 cropland polygons in the North Central Region (NCR) of the US over the period 1964–2005. Results indicate that the loading of greenhouse gases to the atmosphere from cereal maize production in the NCR was 1.7 Gt CO2e, with an average 268 t CO2e produced per tonne of grain. From 1970 until 2005, GHG emissions per unit product declined on average by 2.8 t CO2e ha−1 annum−1, coinciding with a stabilisation in N application rate and consistent increases in grain yield from the mid-1970’s. Nitrous oxide production from N fertilizer inputs represented 59% of these emissions, soil C decline (0–30 cm) represented 11% of total emissions, with the remaining 30% (517 Mt) from the combustion of fuel associated with farm operations. Of the 126 Mt of N fertilizer applied to cereal maize from 1964 to 2005, we estimate that 2.2 Mt N was emitted as N2O when using a non-linear response model, equivalent to 1.75% of the applied N.

Use of a zeolite synthesised from alkali treated kaolin as a K fertiliser : glasshouse experiments on leaching and uptake of K by wheat plants in sandy soil

Zeolite N, a zeolite referred to in earlier publications as MesoLite, is made by caustic reaction of kaolin at temperatures between 80 °C and 95 °C. This material has a very high cation exchange capacity (CEC ≈ 500 meq/100 g). Soil column leaching experiments have shown that K-zeolite N additions greatly reduce leaching of NH4+ fertilisers but the agronomic effectiveness of the retained K+ and NH4+ is unknown. To measure the bioavailability of K in this zeolite, wheat was grown in a glasshouse with K-zeolite N as the K fertiliser in highly-leached and non-leached pots for four weeks and compared with a soluble K fertiliser (KCl). The plants grown in non-leached pots and fertilised with K-zeolite N were slightly larger than those grown with KCl. The elemental compositions in the plants were similar except for Si being significantly more concentrated in the plants supplied with K-zeolite N. Thus K-zeolite N may be an effective K-fertiliser. Plants grown in highly-leached pots were significantly smaller than those grown in non-leached pots. Plants grown in highly-leached pots were severely K deficient as half of the K from both KCl and K-zeolite N was leached from the pots within three days.

A context sensitive model for querying linked scientific data

This thesis provides a query model suitable for context sensitive access to a wide range of distributed linked datasets which are available to scientists using the Internet. The model is designed based on scientific research standards which require scientists to provide replicable methods in their publications. Although there are query models available that provide limited replicability, they do not contextualise the process whereby different scientists select dataset locations based on their trust and physical location. In different contexts, scientists need to perform different data cleaning actions, independent of the overall query, and the model was designed to accommodate this function. The query model was implemented as a prototype web application and its features were verified through its use as the engine behind a major scientific data access site, Bio2RDF.org. The prototype showed that it was possible to have context sensitive behaviour for each of the three mirrors of Bio2RDF.org using a single set of configuration settings. The prototype provided executable query provenance that could be attached to scientific publications to fulfil replicability requirements. The model was designed to make it simple to independently interpret and execute the query provenance documents using context specific profiles, without modifying the original provenance documents. Experiments using the prototype as the data access tool in workflow management systems confirmed that the design of the model made it possible to replicate results in different contexts with minimal additions, and no deletions, to query provenance documents.

Tangible cultural heritage and adaptive reuse: the Old Government House, Brisbane, Australia

The Old Government House, a former residence of the Queen’s representatives in Brisbane, Australia, symbolises British cultural heritage of Colonial Queensland. Located on the campus of the Queensland University of Technology, it is one of the oldest surviving examples of a stately residence in Queensland. Built in 1860s, the Old Government House was originally intended as a temporary residence for the first governor of the newly independent colony of Queensland. However, it remained the vice-regal residence until 1909, serving eleven succeeding governors. Nearly seven decades later, it became the first building in Queensland to be protected under heritage legislation. Thus its importance, as an excellent exemplar that demonstrates the significance of cultural heritage, was established. The Old Government House has survived 150 years of restoration work, refurbishments, and additions. Through these years, it has served the people of Queensland in a multitude of roles. This paper aims to investigate the survival of heritage listed buildings through their adaptive re-use. Its focus will be on the adaptive reuse of the Old Government House through its refurbishments and additions over a period of 150 years. Through a qualitative research process this paper will endeavour to establish the significance of restoration work on the Old Government house; the new opportunities that has opened up as a result of the restoration work; the continued maintenance and management of the building through adaptive re-use; the economic benefits of restoration work; and its contribution to the on-going interest in the preservation of the Tangible Cultural Heritage.

Joint Ventures Law in Australia (3rd ed.)

Following on from the 2nd edition published in 2005, this new edition updates its predecessor and adds considerable new material as a result of changes in the law generally and commercial approaches to financing joint ventures in particular. Of special note, Financing of Joint Ventures has been completely re-written with considerable additions to take account of the new legislative regimes such as the Personal Property Securities. The impact of climate change legislation has been covered, specifically carbon pricing with additional material on structuring generally and particularly in relation to large joint ventures with governments through Public Private Partnerships. A new Chapter has been added called Resources Joint Ventures and undertakes a thorough analysis of a typical resources joint venture and is heavily cross referenced into the chapter on Default which has also been updated. In addition, International Joint Ventures now includes additional material on structuring and dispute resolution and Joint Ventures and the Competition and Consumer Act has been substantially re-written to take account of 2009 legislative amendments on cartel conduct, and the impact of changes wrought by the Competition and Consumer Act 2010. All other chapters and material has been updated to accommodate other legislative changes and new case law over the seven years since the last edition.

Intellectual Property and Joint Ventures

Following upon the success of the 2nd edition published in 2005, this new edition not only updates its predecessor but also adds considerable new material in consequences of changes in the law generally and commercial approaches to financing joint ventures in particular. Of special note are the following: Financing of Joint Ventures has been completely re-written with considerable additions to take account of the new legislative regimes such as the Personal Property Securities, the impact of climate change legislation, specifically carbon pricing with additional material on structuring generally and particularly in relation to large joint ventures with governments through Public Private Partnerships. A new Chapter called Resources Joint Ventures undertakes a thorough analysis of a typical resources joint venture and is heavily cross referenced into the chapter on Default which has also been updated. International Joint Ventures now includes additional material on structuring and dispute resolution. Joint Ventures and the Competition and Consumer Act has been substantially re-written to take account of 2009 legislative amendments on cartel conduct, and the impact of changes wrought by the Competition and Consumer Act 2010. All other chapters and material has been updated to accommodate other legislative changes and new case law over the seven years since the last edition.

A comprehensive investigation of the risky driving behaviour of young novice drivers

Young novice drivers - that is, drivers aged 16-25 years who are relatively inexperienced in driving on the road and have a novice (Learner, Provisional) driver's licence - have been overrepresented in car crash, injury and fatality statistics around the world for decades. There are numerous persistent characteristics evident in young novice driver crashes, fatalities and offences, including variables relating to the young driver themselves, broader social influences which include their passengers, the car they drive, and when and how they drive, and their risky driving behaviour in particular. Moreover, there are a range of psychosocial factors influencing the behaviour of young novice drivers, including the social influences of parents and peers, and person-related factors such as age-related factors, attitudes, and sensation seeking. Historically, a range of approaches have been developed to manage the risky driving behaviour of young novice drivers. Traditional measures predominantly relying upon education have had limited success in regulating the risky driving behaviour of the young novice driver. In contrast, interventions such as graduated driver licensing (GDL) which acknowledges young novice drivers' limitations - principally pertaining to their chronological and developmental age, and their driving inexperience - have shown to be effective in ameliorating this pervasive public health problem. In practice, GDL is a risk management tool that is designed to reduce driving at risky times (e.g., at night) or in risky driving conditions (e.g., with passengers), while still enabling novice drivers to obtain experience. In this regard, the GDL program in Queensland, Australia, was considerably enhanced in July 2007, and major additions to the program include mandated Learner practice of 100 hours recorded in a logbook, and passenger limits during night driving in the Provisional phase. Road safety researchers have also continued to consider the influential role played by the young driver's psychosocial characteristics, including psychological traits and states. In addition, whilst the majority of road safety user research is epidemiological in nature, contemporary road safety research is increasingly applying psychological and criminological theories. Importantly, such theories not only can guide young novice driver research, they can also inform the development and evaluation of countermeasures targeting their risky driving behaviour. The research is thus designed to explore the self-reported behaviours - and the personal, psychosocial, and structural influences upon the behaviours - of young novice drivers This thesis incorporates three stages of predominantly quantitative research to undertake a comprehensive investigation of the risky driving behaviour of young novices. Risky driving behaviour increases the likelihood of the young novice driver being involved in a crash which may harm themselves or other road users, and deliberate risky driving such as driving in excess of the posted speed limits is the focus of the program of research. The extant literature examining the nature of the risky behaviour of the young novice driver - and the contributing factors for this behaviour - while comprehensive, has not led to the development of a reliable instrument designed specifically to measure the risky behaviour of the young novice driver. Therefore the development and application of such a tool (the Behaviour of Young Novice Drivers Scale, or BYNDS) was foremost in the program of research. In addition to describing the driving behaviours of the young novice, a central theme of this program of research was identifying, describing, and quantifying personal, behavioural, and environmental influences upon young novice driver risky behaviour. Accordingly the 11 papers developed from the three stages of research which comprise this thesis are framed within Bandura's reciprocal determinism model which explicitly considers the reciprocal relationship between the environment, the person, and their behaviour. Stage One comprised the foundation research and operationalised quantitative and qualitative methodologies to finalise the instrument used in Stages Two and Three. The first part of Stage One involved an online survey which was completed by 761 young novice drivers who attended tertiary education institutions across Queensland. A reliable instrument for measuring the risky driving behaviour of young novices was developed (the BYNDS) and is currently being operationalised in young novice driver research in progress at the Centre for Injury Research and Prevention in Philadelphia, USA. In addition, regression analyses revealed that psychological distress influenced risky driving behaviour, and the differential influence of depression, anxiety, sensitivity to punishments and rewards, and sensation seeking propensity were explored. Path model analyses revealed that punishment sensitivity was mediated by anxiety and depression; and the influence of depression, anxiety, reward sensitivity and sensation seeking propensity were moderated by the gender of the driver. Specifically, for males, sensation seeking propensity, depression, and reward sensitivity were predictive of self-reported risky driving, whilst for females anxiety was also influential. In the second part of Stage One, 21 young novice drivers participated in individual and small group interviews. The normative influences of parents, peers, and the Police were explicated. Content analysis supported four themes of influence through punishments, rewards, and the behaviours and attitudes of parents and friends. The Police were also influential upon the risky driving behaviour of young novices. The findings of both parts of Stage One informed the research of Stage Two. Stage Two was a comprehensive investigation of the pre-Licence and Learner experiences, attitudes, and behaviours, of young novice drivers. In this stage, 1170 young novice drivers from across Queensland completed an online or paper survey exploring their experiences, behaviours and attitudes as a pre- and Learner driver. The majority of novices did not drive before they were licensed (pre-Licence driving) or as an unsupervised Learner, submitted accurate logbooks, intended to follow the road rules as a Provisional driver, and reported practicing predominantly at the end of the Learner period. The experience of Learners in the enhanced-GDL program were also examined and compared to those of Learner drivers who progressed through the former-GDL program (data collected previously by Bates, Watson, & King, 2009a). Importantly, current-GDL Learners reported significantly more driving practice and a longer Learner period, less difficulty obtaining practice, and less offence detection and crash involvement than Learners in the former-GDL program. The findings of Stage Two informed the research of Stage Three. Stage Three was a comprehensive exploration of the driving experiences, attitudes and behaviours of young novice drivers during their first six months of Provisional 1 licensure. In this stage, 390 of the 1170 young novice drivers from Stage Two completed another survey, and data collected during Stages Two and Three allowed a longitudinal investigation of self-reported risky driving behaviours, such as GDL-specific and general road rule compliance; risky behaviour such as pre-Licence driving, crash involvement and offence detection; and vehicle ownership, paying attention to Police presence, and punishment avoidance. Whilst the majority of Learner and Provisional drivers reported compliance with GDL-specific and general road rules, 33% of Learners and 50% of Provisional drivers reported speeding by 10-20 km/hr at least occasionally. Twelve percent of Learner drivers reported pre-Licence driving, and these drivers were significantly more risky as Learner and Provisional drivers. Ten percent of males and females reported being involved in a crash, and 10% of females and 18% of males had been detected for an offence, within the first six months of independent driving. Additionally, 75% of young novice drivers reported owning their own car within six months of gaining their Provisional driver's licence. Vehicle owners reported significantly shorter Learner periods and more risky driving exposure as a Provisional driver. Paying attention to Police presence on the roads appeared normative for young novice drivers: 91% of Learners and 72% of Provisional drivers reported paying attention. Provisional drivers also reported they actively avoided the Police: 25% of males and 13% of females; 23% of rural drivers and 15% of urban drivers. Stage Three also allowed the refinement of the risky behaviour measurement tool (BYNDS) created in Stage One; the original reliable 44-item instrument was refined to a similarly reliable 36-item instrument. A longitudinal exploration of the influence of anxiety, depression, sensation seeking propensity and reward sensitivity upon the risky behaviour of the Provisional driver was also undertaken using data collected in Stages Two and Three. Consistent with the research of Stage One, structural equation modeling revealed anxiety, reward sensitivity and sensation seeking propensity predicted self-reported risky driving behaviour. Again, gender was a moderator, with only reward sensitivity predicting risky driving for males. A measurement model of Akers' social learning theory (SLT) was developed containing six subscales operationalising the four constructs of differential association, imitation, personal attitudes, and differential reinforcement, and the influence of parents and peers was captured within the items in a number of these constructs. Analyses exploring the nature and extent of the psychosocial influences of personal characteristics (step 1), Akers' SLT (step 2), and elements of the prototype/willingness model (PWM) (step 3) upon self-reported speeding by the Provisional driver in a hierarchical multiple regression model found the following significant predictors: gender (male), car ownership (own car), reward sensitivity (greater sensitivity), depression (greater depression), personal attitudes (more risky attitudes), and speeding (more speeding) as a Learner. The research findings have considerable implications for road safety researchers, policy-makers, mental health professionals and medical practitioners alike. A broad range of issues need to be considered when developing, implementing and evaluating interventions for both the intentional and unintentional risky driving behaviours of interest. While a variety of interventions have been historically utilised, including education, enforcement, rehabilitation and incentives, caution is warranted. A multi-faceted approach to improving novice road safety is more likely to be effective, and new and existing countermeasures should capitalise on the potential of parents, peers and Police to be a positive influence upon the risky behaviour of young novice drivers. However, the efficacy of some interventions remains undetermined at this time. Notwithstanding this caveat, countermeasures such as augmenting and strengthening Queensland's GDL program and targeting parents and adolescents particularly warrant further attention. The findings of the research program suggest that Queensland's current-GDL can be strengthened by increasing compliance of young novice drivers with existing conditions and restrictions. The rates of speeding reported by the young Learner driver are particularly alarming for a number of reasons. The Learner is inexperienced in driving, and travelling in excess of speed limits places them at greater risk as they are also inexperienced in detecting and responding appropriately to driving hazards. In addition, the Learner period should provide the foundation for a safe lifetime driving career, enabling the development and reinforcement of non-risky driving habits. Learners who sped reported speeding by greater margins, and at greater frequencies, when they were able to drive independently. Other strategies could also be considered to enhance Queensland's GDL program, addressing both the pre-Licence adolescent and their parents. Options that warrant further investigation to determine their likely effectiveness include screening and treatment of novice drivers by mental health professionals and/or medical practitioners; and general social skills training. Considering the self-reported pre-licence driving of the young novice driver, targeted education of parents may need to occur before their child obtains a Learner licence. It is noteworthy that those participants who reported risky driving during the Learner phase also were more likely to report risky driving behaviour during the Provisional phase; therefore it appears vital that the development of safe driving habits is encouraged from the beginning of the novice period. General education of parents and young novice drivers should inform them of the considerably-increased likelihood of risky driving behaviour, crashes and offences associated with having unlimited access to a vehicle in the early stages of intermediate licensure. Importantly, parents frequently purchase the car that is used by the Provisional driver, who typically lives at home with their parents, and therefore parents are ideally positioned to monitor the journeys of their young novice driver during this early stage of independent driving. Parents are pivotal in the development of their driving child: they are models who are imitated and are sources of attitudes, expectancies, rewards and punishments; and they provide the most driving instruction for the Learner. High rates of self-reported speeding by Learners suggests that GDL programs specifically consider the nature of supervision during the Learner period, encouraging supervisors to be vigilant to compliance with general and GDL-specific road rules, and especially driving in excess of speed limit. Attitudes towards driving are formed before the adolescent reaches the age when they can be legally licensed. Young novice drivers with risky personal attitudes towards driving reported more risky driving behaviour, suggesting that countermeasures should target such attitudes and that such interventions might be implemented before the adolescent is licensed. The risky behaviours and attitudes of friends were also found to be influential, and given that young novice drivers tend to carry their friends as their passengers, a group intervention such as provided in a school class context may prove more effective. Social skills interventions that encourage the novice to resist the negative influences of their friends and their peer passengers, and to not imitate the risky driving behaviour of their friends, may also be effective. The punishments and rewards anticipated from and administered by friends were also found to influence the self-reported risky behaviour of the young novice driver; therefore young persons could be encouraged to sanction the risky, and to reward the non-risky, driving of their novice friends. Adolescent health programs and related initiatives need to more specifically consider the risks associated with driving. Young novice drivers are also adolescents, a developmental period associated with depression and anxiety. Depression, anxiety, and sensation seeking propensity were found to be predictive of risky driving; therefore interventions targeting psychological distress, whilst discouraging the expression of sensation seeking propensity whilst driving, warrant development and trialing. In addition, given that reward sensitivity was also predictive, a scheme which rewards novice drivers for safe driving behaviour - rather than rewarding the novice through emotional and instrumental rewards for risky driving behaviour - requires further investigation. The Police were also influential in the risky driving behaviour of young novices. Young novice drivers who had been detected for an offence, and then avoided punishment, reacted differentially, with some drivers appearing to become less risky after the encounter, whilst for others their risky behaviour appeared to be reinforced and therefore was more likely to be performed again. Such drivers saw t

Development of lightweight aggregate concrete with high resistance to water and chloride-ion penetration

This paper presents an experimental study to evaluate the effect of coarse and fine LWA in concrete on its water absorption and permeability, and resistance to chloride-ion penetration. In additions, LWC with lower unit weight of about 1300 kg/m3 but high resistance to water and chloride-ion penetration was developed and evaluated. The results indicate that the incorporation of coarse LWA in concrete increases water sorptivity and permeability slightly compared to NWC of similar w/c. The resistance of the sand-LWC to chloride-ion penetration depends on porosity of the coarse LWA. Fine LWA has more influence on the transport proper-ties of concrete than coarse LWA. Use of lightweight crushed sand <1.18 mm reduced the resistance of the LWC to water and chloride-ion penetration to some extent. With low w/cm and silica fume, low unit weight LWC (~1300 kg/m3) was produced with higher resistance to water and chloride ion penetration compared with concretes of higher unit weights.

Addition of diazomethane to armchair single-walled carbon nanotubes and their reaction sequences : A computational study

The sidewall additions of diazomethane to (n, n), n = 3–10 armchair single-walled carbon nanotubes (SWCNTs) on two different orientations of C–C bonds have been studied using the ONIOM(B3LYP/6-31G(d):PM3) approach. The binding energies of SWCNTs complexes with CH2N2, CH2 and their transition-state structures were computed at the B3LYP/6-31G(d) level. The effects of diameters of armchair SWCNTs on their binding energies were studied. Relative reactivities of all the SWCNTs and their complexes based on their frontier orbital energies gaps are reported.

Insights into the mechanism of the reaction between ttrachloro-p-bnzoquinone and hydrogen peroxide and their implications in the catalytic role of water molecules in producing the hydroxyl radial

Detailed mechanisms for the formation of hydroxyl or alkoxyl radicals in the reactions between tetrachloro-p-benzoquinone (TCBQ) and organic hydroperoxides are crucial for better understanding the potential carcinogenicity of polyhalogenated quinones. Herein, the mechanism of the reaction between TCBQ and H2O2 has been systematically investigated at the B3LYP/6-311++G** level of theory in the presence of different numbers of water molecules. We report that the whole reaction can easily take place with the assistance of explicit water molecules. Namely, an initial intermediate is formed first. After that, a nucleophilic attack of H2O2 onto TCBQ occurs, which results in the formation of a second intermediate that contains an OOH group. Subsequently, this second intermediate decomposes homolytically through cleavage of the O-O bond to produce a hydroxyl radical. Energy analyses suggest that the nucleophilic attack is the rate-determining step in the whole reaction. The participation of explicit water molecules promotes the reaction significantly, which can be used to explain the experimental phenomena. In addition, the effects of F, Br, and CH3 substituents on this reaction have also been studied.