Chemoenzymatic Asymmetric Synthesis of Pyridine-Based α-Fluorinated Secondary Alcohols

Fluoro-substituted and heteroaromatic compounds are valuable intermediates for a variety of applications in pharma- and agrochemistry and synthetic chemistry. This study investigates the chemoenzymatic preparation of chiral alcohols bearing a heteroaromatic ring with an increasing degree of fluorination in α-position. Starting from readily available picoline derivatives prochiral α-halogenated acyl moieties were introduced with excellent selectivity and 64–95 % yield. The formed carbonyl group was subsequently reduced to the corresponding alcohols using the alcohol dehydrogenase from Lactobacillus kefir, yielding an enantiomeric excess of 95–>99 % and up to 98 % yield.     

Massive transformation and absolute stability

Under carefully chosen conditions, solidification theory may be applied to solid-state transformations, and this has been done here for composition-invariant diffusion transformations. The predictions of the modeling are compared with isovelocity experiments in two iron systems, Fe-7.29 wt pct Cr and Fe-3.1 wt pct Ni. The ferrite to austenite phase transformation is used to demonstrate that stabilization of a planar transformation front at absolute stability is the natural lower velocity limit for a composition-invariant (massive) transformation. The results of the model, which includes nonequilibrium effects, clearly show that steady-state plane-front growth leading to composition invariance can be obtained at various temperatures depending on the growth velocity. In the lower velocity range, at the limit of absolute stability (of the order of 10 μm/s in the systems studied), the transformation interface moves under conditions of local equilibrium, and the temperature corresponds to the lower solvus temperature. At higher velocity (of the order of the interface diffusion rate, which in these systems is of the order of cm/s), the transformation is predicted to proceed at temperatures close to T ₀. At even higher rates, atom attachment kinetic undercooling will decrease the transformation temperature with respect to T ₀. In some cases, this temperature might even drop below the lower solvus. This article is based on a presentation made at the symposium entitled “The Mechanisms of the Massive Transformation,” a part of the Fall 2000 TMS Meeting held October 16–19, 2000, in St. Louis, Missouri, under the auspices of the ASM Phase Transformations Committee.     

The beginning of immigrant settlement in the Helsinki metropolitan area and the role of social housing

Finland has experienced a rapid increase inimmigration since the beginning of the 1990s.Almost half of the foreign population isconcentrated in the metropolitan area of thecapital, Helsinki. The development andexplanations of their settlement patterns havenot yet been thoroughly studied. It ishypothesised in this study that social housingcan explain the settlement patterns. Indices ofdissimilarity were calculated to study thelevel and development of spatial segregation ofimmigrant groups in the Helsinki metropolitanarea in 1995–99, and the association betweenthe settlement patterns of immigrants andsocial housing was studied by regressionanalysis. Neighbourhood-level data were used.The results indicate that the Helsinkimetropolitan area has avoided extreme ethnicsegregation so far and that segregation isdecreasing. Especially immigrants from poorcountries are clearly associated with socialhousing in their settlement patterns, evenafter adjustment for socio-economic anddemographic differentiation. Also newconstruction of social housing seems to haveaffected the spatial distribution of thisgroup. Despite this dependence, the group isnot extremely segregated, which is probablybecause the social housing sector is nottotally marginalised.     

Applications of the discrete element method in mechanical engineering

Compared to other fields of engineering, in mechanical engineering, the Discrete Element Method (DEM) is not yet a well known method. Nevertheless, there is a variety of simulation problems where the method has obvious advantages due to its meshless nature. For problems where several free bodies can collide and break after having been largely deformed, the DEM is the method of choice. Neighborhood search and collision detection between bodies as well as the separation of large solids into smaller particles are naturally incorporated in the method. The main DEM algorithm consists of a relatively simple loop that basically contains the three substeps contact detection, force computation and integration. However, there exists a large variety of different algorithms to choose the substeps to compose the optimal method for a given problem. In this contribution, we describe the dynamics of particle systems together with appropriate numerical integration schemes and give an overview over different types of particle interactions that can be composed to adapt the method to fit to a given simulation problem. Surface triangulations are used to model complicated, non-convex bodies in contact with particle systems. The capabilities of the method are finally demonstrated by means of application examples. Commemorative Contribution.     

Online Calculation and Prediction of the Strip Temperature in a Hot Strip Finishing Mill

The paper deals with a physical model for the calculation of the strip temperature in a hot rolling mill. Beside the heat transfer from the strip to the environment in the different mill sections a sub‐model for the material properties of steel including phase transitions is introduced. For the application in a process automation system an online adaptation of the model to the current state of the mill is indispensable. The adaptation is explained in detail.     

Finnish general contracting in the USSR

When dealing with a Soviet client, tendering, scheduling, consideration of available resources, management responsibilities, start-up and hand-over must be approached from a slightly different angle than when dealing with Western clients. Aspects of project management from feasibility analysis to hand-over are described, based on the experience of a Finnish general contractor, Finn Stroi.     

Alpha 1-adrenoceptors and calcium sources in adrenergic neurogenic contractions of rat vas deferens

1. The involvement of alpha 1-adrenoceptor subtypes in adrenergic neurogenic contractions of different type was studied in epididymal and prostatic portions of the rat vas deferens. 2. The adrenergic component of neurogenic contractions was isolated by suramin (300 microM). Twitch-like and tonic contractions were elicited by appropriate pulse patterns of electrical field stimulation, and contractions relying on intracellular calcium mobilization and calcium entry were isolated by means of nifedipine (10 microM) and ryanodine (20 microM), respectively. Increasing concentrations of 2-(2,6-dimethoxyphenoxyethyl)aminomethyl-1,4-benzodioxane (WB 4101), alpha-ethyl-3,4,5-trimethoxy-alpha-(3-((2-(2-methoxyphenoxy)ethyl)- amino)-propyl)benzeneacetonitrile (HV 723), prazosin and 5-methylurapidil progressively, monophasically and with potency decreasing in that order reduced and finally abolished all types of contraction, with one exception: concentration-effect curves of 5-methylurapidil in epididymal segments in the presence of ryanodine levelled off at about 75% inhibition. In the presence of both nifedipine (10 microM) and ryanodine (20 microM), contractions were abolished. 3. Contractions elicited by exogenous noradrenaline were also studied in the presence of either nifedipine 10 microM (prostatic segments) or ryanodine 20 microM (epididymal segments). Increasing concentrations of tamsulosin, WB 4101, benoxathian, HV 723, prazosin, 5-methylurapidil and urapidil progressively, monophasically and with potency decreasing in that order reduced and eventually abolished both kinds of contraction, with two exceptions: in epididymal segments in the presence of ryanodine, the concentration-effect curve of 5-methylurapidil was biphasic and the curve of urapidil levelled off at only partial inhibition. 4. In slices prepared from the prostatic end and preincubated with [3H]-noradrenaline, WB 4101, HV 723, prazosin and 5-methylurapidil, at the highest concentrations tested against neurogenic contractions, increased only slightly the overflow of tritium elicited by trains of 50 pulses at 5 Hz. 5. It is concluded that two alpha l-adrenoceptor subtypes mediate adrenergic neurogenic contractions of rat vas deferens. The main one, pharmacologically alpha 1A, activates both calcium mobilization and entry. In addition there is a second receptor, not previously detected in the vas deferens and not corresponding to any named alpha l subtype, characterized by high and similar affinity for tamsulosin, WB 4101, benoxathian,HV 723 and prazosin and very low affinity for 5-methylurapidil and urapidil, and linked exclusively to calcium entry. Both subtypes and their respective transduction pathways also contribute to contractions elicited by exogenous noradrenaline. An alpha 1B-adrenoceptor-mediated contraction was not found under any experimental conditions.     

The impact of agricultural management practices on nutrient losses to water: data on the effects of soil drainage characteristics.

Against the background of increasing nutrient concentrations in Irish water bodies, this study set out to gain information on the potential of agricultural grassland to lose nutrients to water. Overland flow, flow from artificial subsurface drains and stream flow were gauged and sampled during heavy rainfall events. Dissolved reactive phosphorus (DRP), potassium (K), total ammonia (TA), and total oxidised nitrogen (TON) were measured in water samples. When the nutrient concentrations in water were examined in relation to the grassland management practices of the study catchments it emerged that soil P levels, the application of organic and inorganic fertilisers before heavy rainfall and the presence of grazing animals could all influence nutrient concentrations in surface and subsurface drainage water. Overall, the drainage characteristics of soil were found to have a considerable influence on the potential of land to lose nutrients to water.     

A Graphene Field-Effect Device

In this letter, a top-gated field-effect device (FED) manufactured from monolayer graphene is investigated. Except for graphene deposition, a conventional top-down CMOS-compatible process flow is applied. Carrier mobilities in graphene pseudo-MOS structures are compared to those obtained from the top-gated Graphene-FEDs. The extracted values exceed the universal mobility of silicon and silicon-on-insulator MOSFETs