Contra-thermodynamic hydrogen atom abstraction in the selective C−H functionalization of trialkylamine N‑CH3 groups

We report a simple one-pot protocol that affords functionalization of N-CH3 groups in N-methyl-N,N-dialkylamines with high selectivity over N-CH2R or N-CHR2 groups. The radical cation DABCO+•, prepared in situ by oxidation of DABCO with a triarylaminium salt, effects highly selective and contra-thermodynamic C−H abstraction from N-CH3 groups. The intermediates that result react in situ with organometallic nucleophiles in a single pot, affording novel and highly selective homologation of N-CH3 groups. Chemoselectivity, scalability, and recyclability of reagents are demonstrated, and a mechanistic proposal is corroborated by computational and experimental results. The utility of the transformation is demonstrated in the late-stage site-selective functionalization of natural products and pharmaceuticals, allowing rapid derivatization for investigation of structure−activity relationships

InterCloud: Utility-Oriented Federation of Cloud Computing Environments for Scaling of Application Services

Cloud computing providers have setup several data centers at different geographical locations over the Internet in order to optimally serve needs of their customers around the world. However, existing systems do not support mechanisms and policies for dynamically coordinating load distribution among different Cloud-based data centers in order to determine optimal location for hosting application services to achieve reasonable QoS levels. Further, the Cloud computing providers are unable to predict geographic distribution of users consuming their services, hence the load coordination must happen automatically, and distribution of services must change in response to changes in the load. To counter this problem, we advocate creation of federated Cloud computing environment (InterCloud) that facilitates just-in-time, opportunistic, and scalable provisioning of application services, consistently achieving QoS targets under variable workload, resource and network conditions. The overall goal is to create a computing environment that supports dynamic expansion or contraction of capabilities (VMs, services, storage, and database) for handling sudden variations in service demands. This paper presents vision, challenges, and architectural elements of InterCloud for utility-oriented federation of Cloud computing environments. The proposed InterCloud environment supports scaling of applications across multiple vendor clouds. We have validated our approach by conducting a set of rigorous performance evaluation study using the CloudSim toolkit. The results demonstrate that federated Cloud computing model has immense potential as it offers significant performance gains as regards to response time and cost saving under dynamic workload scenarios.Comment: 20 pages, 4 figures, 3 tables, conference pape

Cerebrospinal Fluid Leaks and Encephaloceles

Encephaloceles and cereberospinal fluid (CSF) leaks of the ventral skull base resulting from trauma (surgical and non-surgical), neoplasm, congenital, and spontaneous are a complex problem typically managed by rhinologists/skull base surgeons. Conservative management is often the first step in managing these complex problems. Endoscopic repair of CSF leaks and encephaloceles has greatly evolved with the evolution of endoscopic visualization and instrumentation. Endoscopic repairs of CSF leaks are effective and offer decreased morbidity compared to open approaches with comparative success rates. Meticulous technique is key to success in repair of skull base defects. Materials used are often less important than quality of repair

Evaluation of a Spyware Detection System Using Thin Client Computing

In previous work, we introduced a bait injection system designed to delude and detect crimeware by forcing it to reveal itself during the exploitation of monitored information. Although effective as a technique, our original system was practically limited, as it was implemented in a personal VM environment. In this paper, we extend our system by applying it to thin-clien to demonstrate how the approach can be used in a large-scale deployment. Adapting our system to such an environment revealed a number of challenging issues, such as scalability, portability, and choice of physical communication means. We provide implementation details, as well as experimental results that demonstrate the scalability and effectiveness of our system

Bound-State Variational Wave Equation For Fermion Systems In QED

We present a formulation of the Hamiltonian variational method for QED which enables the derivation of relativistic few-fermion wave equation that can account, at least in principle, for interactions to any order of the coupling constant. We derive a relativistic two-fermion wave equation using this approach. The interaction kernel of the equation is shown to be the generalized invariant M-matrix including all orders of Feynman diagrams. The result is obtained rigorously from the underlying QFT for arbitrary mass ratio of the two fermions. Our approach is based on three key points: a reformulation of QED, the variational method, and adiabatic hypothesis. As an application we calculate the one-loop contribution of radiative corrections to the two-fermion binding energy for singlet states with arbitrary principal quantum number $n$, and $l =J=0$. Our calculations are carried out in the explicitly covariant Feynman gauge.Comment: 26 page

Quaternary fossil fauna from the Luangwa Valley, Zambia

This paper describes a large collection of Quaternary fossil fauna from the Luangwa rift valley, Zambia. Stone Age artefacts have been recovered from stratified fluvial contexts, but no in situ fossil fauna have yet been recovered. We report on 500 fossil specimens collected from the surface of point bars exposed seasonally along the banks of the main Luangwa river channel. We used non-destructive x-ray fluorescence analysis of the fossils' chemical signatures to determine whether they derive from one or many primary contexts, and the relation between chemical signature and state of preservation. Specimens are identified to taxon (genus) to reconstruct palaeoenvironments and biochronology. A relatively wide range of taxa is identified, including a fossil hominin talus, described here. None of the fossils are positively attributable to extinct species, except a femur of an extinct Theropithecus reported in 2003 (Elton et al., 2003). Although no additional extinct taxa were identified, some of the remains were attributable to genera which are not currently found in this region. The results suggest that the majority of the assemblage derives from sediments which are Middle Pleistocene or later, and that past environments in the Luangwa Valley may have differed from the habitat availability found today

Cloudbus Toolkit for Market-Oriented Cloud Computing

This keynote paper: (1) presents the 21st century vision of computing and identifies various IT paradigms promising to deliver computing as a utility; (2) defines the architecture for creating market-oriented Clouds and computing atmosphere by leveraging technologies such as virtual machines; (3) provides thoughts on market-based resource management strategies that encompass both customer-driven service management and computational risk management to sustain SLA-oriented resource allocation; (4) presents the work carried out as part of our new Cloud Computing initiative, called Cloudbus: (i) Aneka, a Platform as a Service software system containing SDK (Software Development Kit) for construction of Cloud applications and deployment on private or public Clouds, in addition to supporting market-oriented resource management; (ii) internetworking of Clouds for dynamic creation of federated computing environments for scaling of elastic applications; (iii) creation of 3rd party Cloud brokering services for building content delivery networks and e-Science applications and their deployment on capabilities of IaaS providers such as Amazon along with Grid mashups; (iv) CloudSim supporting modelling and simulation of Clouds for performance studies; (v) Energy Efficient Resource Allocation Mechanisms and Techniques for creation and management of Green Clouds; and (vi) pathways for future research.Comment: 21 pages, 6 figures, 2 tables, Conference pape

Comparing open and minimally invasive surgical procedures for oesophagectomy in the treatment of cancer: the ROMIO (Randomised Oesophagectomy: Minimally Invasive or Open) feasibility study and pilot trial

Localised oesophageal cancer can be curatively treated with surgery (oesophagectomy) but the procedure is complex with a risk of complications, negative effects on quality of life and a recovery period of 6-9 months. Minimal-access surgery may accelerate recovery.The ROMIO (Randomised Oesophagectomy: Minimally Invasive or Open) study aimed to establish the feasibility of, and methodology for, a definitive trial comparing minimally invasive and open surgery for oesophagectomy. Objectives were to quantify the number of eligible patients in a pilot trial; develop surgical manuals as the basis for quality assurance; standardise pathological processing; establish a method to blind patients to their allocation in the first week post surgery; identify measures of postsurgical outcome of importance to patients and clinicians; and establish the main cost differences between the surgical approaches.Pilot parallel three-arm randomised controlled trial nested within feasibility work.Two UK NHS departments of upper gastrointestinal surgery.Patients aged ≥ 18 years with histopathological evidence of oesophageal or oesophagogastric junctional adenocarcinoma, squamous cell cancer or high-grade dysplasia, referred for oesophagectomy or oesophagectomy following neoadjuvant chemo(radio)therapy.Oesophagectomy, with patients randomised to open surgery, a hybrid open chest and minimally invasive abdomen or totally minimally invasive access.The primary outcome measure for the pilot trial was the number of patients recruited per month, with the main trial considered feasible if at least 2.5 patients per month were recruited.During 21 months of recruitment, 263 patients were assessed for eligibility; of these, 135 (51%) were found to be eligible and 104 (77%) agreed to participate, an average of five patients per month. In total, 41 patients were allocated to open surgery, 43 to the hybrid procedure and 20 to totally minimally invasive surgery. Recruitment is continuing, allowing a seamless transition into the definitive trial. Consequently, the database is unlocked at the time of writing and data presented here are for patients recruited by 31 August 2014. Random allocation achieved a good balance between the arms of the study, which, as a high proportion of patients underwent their allocated surgery (69/79, 87%), ensured a fair comparison between the interventions. Dressing patients with large bandages, covering all possible incisions, was successful in keeping patients blind while pain was assessed during the first week post surgery. Postsurgical length of stay and risk of adverse events were within the typical range for this group of patients, with one death occurring within 30 days among 76 patients. There were good completion rates for the assessment of pain at 6 days post surgery (88%) and of the patient-reported outcomes at 6 weeks post randomisation (74%).Rapid recruitment to the pilot trial and the successful refinement of methodology indicated the feasibility of a definitive trial comparing different approaches to oesophagectomy. Although we have shown a full trial of open compared with minimally invasive oesophagectomy to be feasible, this is necessarily based on our findings from the two clinical centres that we could include in this small preliminary study.Current Controlled Trials ISRCTN59036820.This project was funded by the NIHR Health Technology Assessment programme and will be published in full in Health Technology Assessment; Vol. 20, No. 48. See the NIHR Journals Library website for further project information

Impact of flipper-banding on breeding success of African penguins Spheniscus demersus at Robben Island: comparisons among silicone rubber bands, stainless-steel bands and no bands

From 2001 to 2006, two new designs of flipper bands made from silicone rubbers were tested on African penguins Spheniscus demersus at 365 nests on Robben Island, South Africa. We compared, over six years, the breeding success, from hatching to fledging, of three different groups of penguins: those with rubber bands (117 nests), with conventional stainless-steel bands (103 nests) and without bands (145 nests). There were no significant differences in breeding success between the three groups, suggesting that neither the currently used steel bands, nor either of the new rubber-band designs, were harmful during the seasons investigated. The rubber bands caused less wear of feathers and less drag on a model penguin than the steel bands. In captivity, the behaviours of African penguins fitted with rubber bands were not noticeably different to those of unbanded birds

An affordable, programmable and interactive continuous flow Photoreactor setup for undergraduate organic synthetic teaching labs

Photochemistry and continuous flow chemistry are synthetic technology platforms that have witnessed an increasing uptake by chemical industries interested in complex organic molecule synthesis. Simultaneously, automation and data science are prominent targets in organic synthesis and in chemical industries for streamlined workflows, meaning hardware-software interaction between operators and devices is crucial. Since undergraduate teaching labs at public-funded research Universities typically (i) lack budget for commercial, user-friendly continuous flow reactors and (ii) do not teach synthetic chemists how to program or interact with reactors, there is a disparity between the skills undergraduates are equipped with and the skills that future industries need. We report a teaching lab project where undergraduates assemble, program and execute a continuous flow photoreactor to realize a multigram-scale photoredox catalyzed oxidation reaction. A palladium-free synthetic access to the starting material was described to further cut costs. Not only does this exercise introduce useful skills in reactor design, programming and wet chemistry (both photochemical and thermal, both batch and flow), it also accommodates both the typical budget and afternoon timeslot (2-3 h) of a teaching lab and can be followed by thin-layer chromatography/color changes without necessarily requiring access to NMR facilities