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.     

Long-term sensor measurements of lung deposited surface area of particulate matter emitted from local vehicular and residential wood combustion sources

Abstract

Lung deposited surface area (LDSA) is a relatively new metric that has been argued to be more accurate at predicting health effects from aerosol exposure. For typical atmospheric aerosol, the LDSA concentration depends mainly on the concentration of ultrafine particles (e.g. vehicular exhaust emissions and residential wood combustion) and therefore optical methods cannot be used to measure and quantify it. The objective of this study was to investigate and describe typical characteristics of LDSA under different urban environments and evaluate how a diffusion charging-based Pegasor AQ Urban sensor (Pegasor Ltd., Finland) can be used as an alternative to optical sensors when assessing local combustion emissions and respective LDSA concentrations. Long-term (12?months) sensor measurements of LDSA were carried out at three distinctly different measurement sites (four sensor nodes) in the Helsinki metropolitan area, Finland. The sites were affected mainly by vehicular exhaust emission (street canyon and urban background stations) and by residential wood combustion (two detached housing area stations). The results showed that the accuracy of the AQ Urban was good (R² = 0.90) for the measurement of LDSA when compared to differential mobility particle sizer. The mean concentrations of LDSA were more than twice as high at the street canyon (mean 22 µm² cm^?3) site when compared to the urban background site (mean 9.4 µm² cm^?3). In the detached housing area, the mean concentrations were 12 µm² cm^?3, and wood combustion typically caused high LDSA peaks in the evenings. High correlations and similar diurnal cycles were observed for the LDSA and black carbon at street canyon and urban background stations. The utilization of a small-scale sensor network (four nodes) showed that the cross-station variability in hourly LDSA concentrations was significant in every site, even within the same detached housing area (distance between the two sites ～670?m).     

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.     

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.     

Bio-derived fuels may ease the regeneration of diesel particulate traps

Particulate is the most problematic emission from diesel engines. To comply with environmental regulations, these engines are often equipped with particulate traps, which must be regenerated frequently for the sake of efficiency. The regeneration is commonly achieved by rising the temperature in the trap till the particulate self-ignites. However, this method implies energy losses and thermal shocks in the trap. Alternatively, catalysts and additives have been recently considered for reducing the ignition temperature of particulate, but these techniques suffer from poisoning and undesirable byproducts. The present experimental study shows that the ignition temperature of particulate from seed-derived oils (SO) and from blends of SO with diesel fuel oil (DO) can be lower than that of particulate from neat DO. If substantiated by more extensive studies, such finding could have noteworthy implications on the future of fuels and traps.     

Danckwerts’ law for mean residence time revisited

This paper shows that Danckwerts’ law for mean residence time in a vessel with continuous and steady throughflow holds for a stochastic model based on a Markov chain for the particle spatial position, under a set of three very general conditions on the transfer probabilities. These are natural conditions and represent mass balance conditions on the transfer between spatial regions in the process. It is shown that a stochastic model for particle residence time distribution with these three conditions may describe almost any physical flow configuration, and also covers published mathematical RTD models, independent of their mathematical form or the nature of the associated boundary conditions, models for which Danckwert's law has hitherto been shown to be satisfied on a case-by-case basis. Two examples, namely those birth-death Markov chains and fluidized bed models are discussed.     

Suboptimal Exposure to Facial Expressions When Viewing Video Messages From a Small Screen: Effects on Emotion, Attention, and Memory.

The authors examined the effects of suboptimally presented facial expressions on emotional and attentional responses and memory among 39 young adults viewing video (business news) messages from a small screen. Facial electromyography (EMG) and respiratory sinus arrhythmia were used as physiological measures of emotion and attention, respectively. Several congruency priming effects were found. In particular, happy facial primes prompted increased (a) pleasure ratings, (b) orbicularis oculi EMG activity, (c) perceived trustworthiness, and (d) recognition memory for video messages with a positive emotional tone. Emotional and other responses to video messages presented on a small screen can be modified with suboptimal affective primes, but even small differences in the emotional tone of the messages should be allowed for. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Is the development of adenoma and carcinoma in proximal colon related to apolipoprotein E phenotype?

BACKGROUND & AIMS: Alterations in plasma lipoprotein levels and bile acid metabolism observed in patients with colorectal adenoma and carcinoma may reflect a genetic background predisposing to altered lipid metabolism and tumors. This study was designed to determine whether the polymorphism of apolipoprotein E, one of the key regulatory proteins in cholesterol metabolism, is associated with proximal or distal colonic neoplasia. METHODS: Apolipoprotein E phenotype was determined in 135 patients with colorectal adenoma, 122 patients with colorectal carcinoma, and 199 randomly selected control subjects. RESULTS: The frequency of the epsilon 4 allele of apolipoprotein E was low (0.075 and 0.073) in patients with proximal adenoma and those with carcinoma, respectively, compared with the control subjects (0.181) (P < 0.05). In patients with distal tumors, there was no alteration in epsilon 4 frequency. In all subjects with the epsilon 4 allele compared with subjects without epsilon 4, the odds ratio for proximal adenoma was 0.36 (95% confidence interval, 0.14-0.89), and the odds ratio for proximal carcinoma was 0.35 (95% confidence interval, 0.14-0.86). CONCLUSIONS: The data suggest that the epsilon 4 allele of apolipoprotein E provides protection from the development of adenoma and carcinoma of the proximal colon. These results support the theory that there are common susceptibility genes modulating the susceptibility to external carcinogenic factors.