Heterogeneous asymmetric hydrogenation of ethyl pyruvate on chirally modified Pt/Al2O3 catalyst with fixed-bed reactor

The enantioselective hydrogenation of ethyl pyruvate on the cinchonidine modified Pt/Al2O3 catalyst was investigated using a high-pressure reaction system with a fixed-bed reactor for the purpose to produce the,chiral product without separating the catalyst from the reaction system. The reaction was also investigated in a batch reactor for comparison. About 60% e. e. and 90% e. e. were obtained with the fixed-bed reactor and the batch reactor respectively, demonstrating the possibility for the heterogeneous asymmetric hydrogenation in the fixed-bed reactor. Some adsorbed chiral modifier, cinchonidine, can be slowly removed from the surface of Pt/Al2O3 under the continuous flow reaction, as a result, the e, e, values drops with the reaction time in the fixed-bed reactor. The enantio-selectivity is higher in the fixed-bed reactor, but lower in the batch reactor when ethanol was used as solvent than that when acetic acid as solvent. CO was used as molecular probe to characterize the adsorption of cinchonidine an the catalyst surface by IR spectroscopy, A red shift observed in IR spectra of coadsorbed CO with cinchonidine suggests that the cinchonidine adsorption is mainly through the pi -interaction with platinum surface and donating electron to the platinum surface.

Ligand modified real heterogeneous catalysts for fixed-bed hydroformylation of propylene

A novel ligand modified heterogeneous catalyst has been developed for hydroformylation of propylene, which showed excellent activity, selectivity and stability and need not be separated from the product after reaction in a fixed-bed reactor. The coordination bonds between triphenyl phosphine (PPh3) and Rh/SiO2 were confirmed by means of thermogravimetric (TG), solid-state P-31 NMR, XPS and FT-IR. Two types of active species for hydroformylation were formed, which were proved by in situ FT-IR techniques. The problem of metal leaching was greatly reduced by directly fastening Rh particles on the support, and the active Rh species that was responsible for the outstanding performance of propylene hydroformylation was tightly bound by the very strong metal-metal bonds. No sign of deactivation was observed over a period of more than 1000 h on the condition that PPh3 was added at 300-350 h of time on stream. (c) 2005 Elsevier B.V. All rights reserved.

Performance evaluation of the RPL Protocol in fixed and mobile sinks low-power and lossy networks.

Low-Power and Lossy-Network (LLN) are usually composed of static nodes, but the increase demand for mobility in mobile robotic and dynamic environment raises the question how a routing protocol for low-power and lossy-networks such as (RPL) would perform if a mobile sink is deployed. In this paper we investigate and evaluate the behaviour of the RPL protocol in fixed and mobile sink environments with respect to different network metrics such as latency, packet delivery ratio (PDR) and energy consumption. Extensive simulation using instant Contiki simulator show significant performance differences between fixed and mobile sink environments. Fixed sink LLNs performed better in terms of average power consumption, latency and packet delivery ratio. The results demonstrated also that RPL protocol is sensitive to mobility and it increases the number of isolated nodes.

An Autonomous Sailing Robot for Ocean Observation

Sauze, C. and Neal, M. 'An Autonomous Sailing Robot for Ocean Observation', in proceedings of TAROS 2006, Guildford, UK, Sept 4-6th 2006, pages 190-197.

Dangers of a fixed mindset: implications of self-theories research for computer science education

Murphy, L. and Thomas, L. 2008. Dangers of a fixed mindset: implications of self-theories research for computer science education. In Proceedings of the 13th Annual Conference on innovation and Technology in Computer Science Education (Madrid, Spain, June 30 - July 02, 2008). ITiCSE '08. ACM, New York, NY, 271-275.

Workers' compensation in the United States: high costs, low benefits

Studies suggest that income replacement is low for many workers with serious occupational injuries and illnesses. This review discusses three areas that hold promise for raising benefits to workers while reducing workers' compensation costs to employers: improving safety, containing medical costs, and reducing litigation. In theory, workers' compensation increases the costs to employers of injuries and so provides incentives to improve safety. Yet, taken as a whole, research does not provide convincing evidence that workers' compensation reduces injury rates. Moreover, unlike safety and health regulation, workers' compensation focuses the attention of employers on individual workers. High costs may lead employers to discourage claims and litigate when claims are filed. Controlling medical costs can reduce workers' compensation costs. Most studies, however, have focused on costs and have not addressed the effectiveness of medical care or patient satisfaction. Research also has shown that workers' compensation systems can reduce the need for litigation. Without litigation, benefits can be delivered more quickly and at lower costs.

Fixed Point vs. First-Order Logic on Finite Ordered Structures with Unary Relations

We prove that first order logic is strictly weaker than fixed point logic over every infinite classes of finite ordered structures with unary relations: Over these classes there is always an inductive unary relation which cannot be defined by a first-order formula, even when every inductive sentence (i.e., closed formula) can be expressed in first-order over this particular class. Our proof first establishes a property valid for every unary relation definable by first-order logic over these classes which is peculiar to classes of ordered structures with unary relations. In a second step we show that this property itself can be expressed in fixed point logic and can be used to construct a non-elementary unary relation.

Implications of Selfish Neighbor Selection in Overlay Networks

In a typical overlay network for routing or content sharing, each node must select a fixed number of immediate overlay neighbors for routing traffic or content queries. A selfish node entering such a network would select neighbors so as to minimize the weighted sum of expected access costs to all its destinations. Previous work on selfish neighbor selection has built intuition with simple models where edges are undirected, access costs are modeled by hop-counts, and nodes have potentially unbounded degrees. However, in practice, important constraints not captured by these models lead to richer games with substantively and fundamentally different outcomes. Our work models neighbor selection as a game involving directed links, constraints on the number of allowed neighbors, and costs reflecting both network latency and node preference. We express a node's "best response" wiring strategy as a k-median problem on asymmetric distance, and use this formulation to obtain pure Nash equilibria. We experimentally examine the properties of such stable wirings on synthetic topologies, as well as on real topologies and maps constructed from PlanetLab and AS-level Internet measurements. Our results indicate that selfish nodes can reap substantial performance benefits when connecting to overlay networks composed of non-selfish nodes. On the other hand, in overlays that are dominated by selfish nodes, the resulting stable wirings are optimized to such great extent that even non-selfish newcomers can extract near-optimal performance through naive wiring strategies.

Effect of solder volume on joint shape with variable chip-to-board contact pad ratio

The objective of this paper is to investigate the effect of the pad size ratio between the chip and board end of a solder joint on the shape of that solder joint in combination with the solder volume available. The shape of the solder joint is correlated to its reliability and thus of importance. For low density chip bond pad applications Flip Chip (FC) manufacturing costs can be kept down by using larger size board pads suitable for solder application. By using “Surface Evolver” software package the solder joint shapes associated with different size/shape solder preforms and chip/board pad ratios are predicted. In this case a so called Flip-Chip Over Hole (FCOH) assembly format has been used. Assembly trials involved the deposition of lead-free 99.3Sn0.7Cu solder on the board side, followed by reflow, an underfill process and back die encapsulation. During the assembly work pad off-sets occurred that have been taken into account for the Surface Evolver solder joint shape prediction and accurately matched the real assembly. Overall, good correlation was found between the simulated solder joint shape and the actual fabricated solder joint shapes. Solder preforms were found to exhibit better control over the solder volume. Reflow simulation of commercially available solder preform volumes suggests that for a fixed stand-off height and chip-board pad ratio, the solder volume value and the surface tension determines the shape of the joint.

An EORTC phase I study of capecitabine (Xeloda) in combination with fixed doses of cyclophosphamide and epirubicin (cex) as primary treatment for large operable or locally advanced/inflammatory breast cancer.

In breast cancer, chemotherapy regimens that include infusional 5-fluorouracil (5-FU) lead to high response rates, but require central venous access and pumps. To avoid these inconveniences, we substituted infusional 5-FU with capecitabine. The main objective of this study was to determine the maximum tolerated dose (MTD) of capecitabine when given in combination with fixed doses of epirubicin and cyclophosphamide (100 and 600 mg/m(2) day 1 every (q) 3 weeks) as primary treatment for large operable or locally advanced/inflammatory breast cancer without distant metastasis. Capecitabine was escalated from 750 mg/m(2) twice a day (bid) to 1250 mg/m(2) bid from day 1 to day 14 in four dose levels. Dose escalation was permitted if 0/3 or 1/6 patients experienced dose-limiting toxicity (DLT). A total of 23 patients were included and 117 courses were administered. At dose level 4, 2 of 2 patients presented DLTs defining the MTD. A high rate of capecitabine treatment modification was required with capecitabine 1050 mg/m(2) bid (dose level 3). 19 patients achieved an objective response (83%). In conclusion, we believe that capecitabine 900 mg/m(2) bid (dose level 2) is the recommended dose in combination with epirubicin 100 mg/m(2) and cyclophosphamide 600 mg/m(2). The acceptable toxicity profile and encouraging activity of this regimen warrant further evaluation.

An EORTC phase I study of epirubicin in combination with fixed doses of cyclophosphamide and infusional 5-fu (CEF-infu) as primary treatment of large operable or locally advanced/inflammatory breast cancer.

PURPOSE: The association of continuous infusion 5-fluorouracil, epirubicin (50 mg/m2 q 3 weeks) and a platinum compound (cisplatin or carboplatin) was found to be very active in patients with either locally advanced/inflammatory (LA/I) [1, 2] or large operable (LO) breast cancer (BC) [3]. The same rate of activity in terms of response rate (RR) and response duration was observed in LA/I BC patients when cisplatin was replaced by cyclophosphamide [4]. The dose of epirubicin was either 50 mg/m2 [ 1, 2, 3] or 60 mg/m2/cycle [4]. The main objective of this study was to determine the maximum tolerated dose (MTD) of epirubicin when given in combination with fixed doses of cyclophosphamide and infusional 5-fluorouracil (CEF-infu) as neoadjuvant therapy in patients with LO or LA/I BC for a maximum of 6 cycles. PATIENTS AND METHODS: Eligible patients had LO or LA/I BC, a performance status 0-1, adequate organ function and were <65 years old. Cyclophosphamide was administered at the dose of 400 mg/m2 day 1 and 8, q 4 weeks and infusional 5-fluorouracil 200 mg/m2/day was given day 1-28, q 4 weeks. Epirubicin was escalated from 30 to 45 and to 60 mg/m2 day 1 and 8; dose escalation was permitted if 0/3 or 1/6 patients experienced dose limiting toxicity (DLT) during the first 2 cycles of therapy. DLT for epirubicin was defined as febrile neutropenia, grade 4 neutropenia lasting for >7 days, grade 4 thrombocytopenia, or any non-haematological toxicity of CTC grade > or =3, excluding alopecia and plantar-palmar erythrodysesthesia (this toxicity was attributable to infusional 5-fluorouracil and was not considered a DLT of epirubicin). RESULTS: A total of 21 patients, median age 44 years (range 29-63) have been treated. 107 courses have been delivered, with a median number of 5 cycles per patient (range 4-6). DLTs on cycles I and 2 on level 1, 2, 3: grade 3 (G3) mucositis occurred in 1/10 patients treated at the third dose level. An interim analysis showed that G3 PPE occurred in 5/16 pts treated with the 28-day infusional 5-FU schedule at the 3 dose levels. The protocol was subsequently amended to limit the duration of infusional 5-fluorouracil infusion from 4 to 3 weeks. No G3 PPE was detected in 5 patients treated with this new schedule. CONCLUSIONS: This study establishes that epirubicin 60mg/m2 day 1 and 8, cyclophosphamide 400mg/m2 day 1 and 8 and infusional 5-fluorouracil 200 mg/m2/day day 1-21. q 4 weeks is the recommended dose level. Given the encouraging activity of this regimen (15/21 clinical responses) we have replaced infusional 5-fluorouracil by oral capecitabine in a recently activated study.

"Call for prices": Strategic implications of raising consumers' costs

Many consumer durable retailers often do not advertise their prices and instead ask consumers to call them for prices. It is easy to see that this practice increases the consumers' cost of learning the prices of products they are considering, yet firms commonly use such practices. Not advertising prices may reduce the firm's advertising costs, but the strategic effects of doing so are not clear. Our objective is to examine the strategic effects of this practice. In particular, how does making price discovery more difficult for consumers affect competing retailers' price, service decisions, and profits? We develop a model in which a manufacturer sells its product through a high-service retailer and a low-service retailer. Consumers can purchase the retail service at the high-end retailer and purchase the product at the competing low-end retailer. Therefore, the high-end retailer faces a free-riding problem. A retailer first chooses its optimal service levels. Then, it chooses its optimal price levels. Finally, a retailer decides whether to advertise its prices. The model results in four structures: (1) both retailers advertise prices, (2) only the low-service retailer advertises price, (3) only the high-service retailer advertises price, and (4) neither retailer advertises price. We find that when a retailer does not advertise its price and makes price discovery more difficult for consumers, the competition between the retailers is less intense. However, the retailer is forced to charge a lower price. In addition, if the competing retailer does advertise its prices, then the competing retailer enjoys higher profit margins. We identify conditions under which each of the above four structures is an equilibrium and show that a low-service retailer not advertising its price is a more likely outcome than a high-service retailer doing so. We then solve the manufacturer's problem and find that there are several instances when a retailer's advertising decisions are different from what the manufacturer would want. We describe the nature of this channel coordination problem and identify some solutions. © 2010 INFORMS.

Improving supply chain performance: Real-time demand information and flexible deliveries

In some supply chains, materials are ordered periodically according to local information. This paper investigates how to improve the performance of such a supply chain. Specifically, we consider a serial inventory system in which each stage implements a local reorder interval policy; i.e., each stage orders up to a local basestock level according to a fixed-interval schedule. A fixed cost is incurred for placing an order. Two improvement strategies are considered: (1) expanding the information flow by acquiring real-time demand information and (2) accelerating the material flow via flexible deliveries. The first strategy leads to a reorder interval policy with full information; the second strategy leads to a reorder point policy with local information. Both policies have been studied in the literature. Thus, to assess the benefit of these strategies, we analyze the local reorder interval policy. We develop a bottom-up recursion to evaluate the system cost and provide a method to obtain the optimal policy. A numerical study shows the following: Increasing the flexibility of deliveries lowers costs more than does expanding information flow; the fixed order costs and the system lead times are key drivers that determine the effectiveness of these improvement strategies. In addition, we find that using optimal batch sizes in the reorder point policy and demand rate to infer reorder intervals may lead to significant cost inefficiency. © 2010 INFORMS.

Early versus delayed fixed dose combination abacavir/lamivudine/zidovudine in patients with HIV and tuberculosis in Tanzania.

Fixed dose combination abacavir/lamivudine/zidovudine (ABC/3TC/ZDV) among HIV-1 and tuberculosis (TB)-coinfected patients was evaluated and outcomes between early vs. delayed initiation were compared. In a randomized, pilot study conducted in the Kilimanjaro Region of Tanzania, HIV-infected inpatients with smear-positive TB and total lymphocyte count <1200/mm(3) were randomized to initiate ABC/3TC/ZDV either 2 (early) or 8 (delayed) weeks after commencing antituberculosis therapy and were followed for 104 weeks. Of 94 patients screened, 70 enrolled (41% female, median CD4 count 103 cells/mm(3)), and 33 in each group completed 104 weeks. Two deaths and 12 serious adverse events (SAEs) were observed in the early arm vs. one death, one clinical failure, and seven SAEs in the delayed arm (p = 0.6012 for time to first grade 3/4 event, SAE, or death). CD4 cell increases were +331 and +328 cells/mm(3), respectively. TB-immune reconstitution inflammatory syndromes (TB-IRIS) were not observed in any subject. Using intent-to-treat (ITT), missing = failure analyses, 74% (26/35) vs. 89% (31/35) randomized to early vs. delayed therapy had HIV RNA levels <400 copies/ml at 104 weeks (p = 0.2182) and 66% (23/35) vs. 74% (26/35), respectively, had HIV RNA levels <50 copies/ml (p = 0.6026). In an analysis in which switches from ABC/3TC/ZDV = failure, those receiving early therapy were less likely to be suppressed to <400 copies/ml [60% (21/35) vs. 86% (30/35), p = 0.030]. TB-IRIS was not observed among the 70 coinfected subjects beginning antiretroviral treatment. ABC/3TC/ZDV was well tolerated and resulted in steady immunologic improvement. Rates of virologic suppression were similar between early and delayed treatment strategies with triple nucleoside regimens when substitutions were allowed.