176 research outputs found
Attempted Diastereoselective Preparation and Chiroptical Properties of (2S)-1-(3-Mercapto-2-Methyl-1-Oxopropyl)-L-Proline (Captopril) and Some Congeners
CD and 13C-NMRstudy of the eonformational properties of (2S)-1-(3-mercapto-2-methyl-1-oxopropyl)-L-proline (captopril, 1), and its congeners 2-5, 8, 9 is reported. 13C-NMRdata (in DMSO-d6) reveal an E/Z (cis/trans) ratio of ea. (15-30) : (70-85) for the N-acetyl-prolines 1, 5, 10, and for N-acetyl-L-proline. CD data indicate practically identical conformations for the ring systems of 8 and 9. Attempted diastereoselective cyclization of the sodium salt of 7 or the free thioacid into 8 and 9 resulted in low chemical yields (-30%) and low diastereoselectivity, favouring formation of the »wrong- diastereomer 9 in small excess (-20%)
VITO combineert sensorplatformen met aardobservatie voor een betere monitoring van water
De huidige systemen om de toestand van het water op te volgen, voldoen vaak niet aan de noden van waterbeheerders, baggeraars, waterbedrijven, havenbeheerders, enzovoort. De data schieten tekort in kwaliteit en kwantiteit. Daarom ontwikkelt VITO een monitoringssysteem dat geautomatiseerde sensoren op onbemande vaartuigen combineert met aardobservatie: SAVEWATER. Ook het beschikbaar stellen van de data maakt deel uit van dit systeem. Het project wordt samen met de Europese ruimtevaartorganisatie ESA uitgewerkt
Kinetics of Cyclization of 2-(N-B-Bromoethyl)-amino-5-substituted Benzophenones into 1,4-Benzodiazepines
The overall pseudo-first order cyclization rates of 2-N-/J-bro
moethylamino-5-substituted benzophenones 1-3 into 1,4-benzodiazepines
7-9, determined in 60/o ethanolic ammonia at 100 °c, 115 °c,
and 125 °c respectively, were found to range between 1.0 X 10-• and
8.33 X 10-• s-1 for 1, between 1.6 X 10-4 and 5.83 X 10-• s·1 for 2 and
between 6.66 X 10-5 and 3.16 X 10-• s-1 for 3. Rate values calculated
from the rising concentrations of cyclization products 7-9 were
lower indicating the formation of stable intermediates. It is assumed
that these are protonated aziridine derivatives 4-6, since compounds
4 and 5 were identified as intermediates by TLC and GLC.
The formation rate for the model compound 2-amino-5-chlorobenzophenone
imine was found to be only 5.8 x 10-7 s-1 at 125 °C, which
eliminates imine (C=NH) derivatives of 1-3 as possible intermediates.
The ammonolysis rates of 3-phenylpropylbromide between
110 °c and 125 °c, were found to range from 1.5 X 10-4 to 4.16 X 10-•
s·1• These values revealed that the ~-participation of the N(2)-atom,
being a relatively rapid equilibrium, does not enhance the overall
cyclization rate. The following parameters characterize the overall
cyclization process; l\u27i H=I= = 50.0 ± 4.0 kJ mo1-1 and l\u27i S=I= = -156
± 5 J mo1-1 K-1 for 1, /\u27i H=I= = 89.9 ±.4.0 kJ moP K 1 for 2, l\u27i H=I= =
= 75.3 ± 4.0 kJ moi-1 and l\u27i S=I= = -89 ± 4 J moi-1 K\u27 for 3
Combining norms to prove termination
Automatic termination analyzers typically measure the size of terms applying norms which are mappings from terms to the natural numbers. This paper illustrates how to enable the use of size functions defined as tuples of these simpler norm functions. This approach enables us to simplify the problem of deriving automatically a candidate norm with which to prove termination. Instead of deriving a single, complex norm function, it is sufficient to determine a collection of simpler norms, some combination of which, leads to a proof of termination. We propose that a collection of simple norms, one for each of the recursive data-types in the program, is often a suitable choice. We first demonstrate the power of combining norm functions and then the adequacy of combining norms based on regular-types
The Dutch Y-chromosomal landscape
Previous studies indicated existing, albeit limited, genetic-geographic population substructure in the Dutch population based on genome-wide data and a lack of this for mitochondrial SNP based data. Despite the aforementioned studies, Y-chromosomal SNP data from the Netherlands remain scarce and do not cover the territory of the Netherlands well enough to allow a reliable investigation of genetic-geographic population substructure. Here we provide the first substantial dataset of detailed spatial Y-chromosomal haplogroup information in 2085 males collected across the Netherlands and supplemented with previously published data from northern Belgium. We found Y-chromosomal evidence for genetic-geographic population substructure, and several Y-haplogroups demonstrating significant clinal frequency distributions in different directions. By means of prediction surface maps we could visualize (complex) distribution patterns of individual Y-haplogroups in detail. These results highlight the value of a micro-geographic approach and are of great use for forensic and epidemiological investigations and our understanding of the Dutch population history. Moreover, the previously noted absence of genetic-geographic population substructure in the Netherlands based on mitochondrial DNA in contrast to our Y-chromosome results, hints at different population histories for women and men in the Netherlands.Molecular Technology and Informatics for Personalised Medicine and Healt
The assessment of neuromuscular fatigue during 120 min of simulated soccer exercise
Purpose
This investigation examined the development of neuromuscular fatigue during a simulated soccer match incorporating a period of extra time (ET) and the reliability of these responses on repeated test occasions.
Methods
Ten male amateur football players completed a 120 min soccer match simulation (SMS). Before, at half time (HT), full time (FT), and following a period of ET, twitch responses to supramaximal femoral nerve and transcranial magnetic stimulation (TMS) were obtained from the knee-extensors to measure neuromuscular fatigue. Within 7 days of the first SMS, a second 120 min SMS was performed by eight of the original ten participants to assess the reliability of the fatigue response.
Results
At HT, FT, and ET, reductions in maximal voluntary force (MVC; −11, −20 and −27%, respectively, P ≤ 0.01), potentiated twitch force (−15, −23 and −23%, respectively, P < 0.05), voluntary activation (FT, −15 and ET, −18%, P ≤ 0.01), and voluntary activation measured with TMS (−11, −15 and −17%, respectively, P ≤ 0.01) were evident. The fatigue response was robust across both trials; the change in MVC at each time point demonstrated a good level of reliability (CV range 6–11%; ICC2,1 0.83–0.94), whilst the responses identified with motor nerve stimulation showed a moderate level of reliability (CV range 5–18%; ICC2,1 0.63–0.89) and the data obtained with motor cortex stimulation showed an excellent level of reliability (CV range 3–6%; ICC2,1 0.90–0.98).
Conclusion
Simulated soccer exercise induces a significant level of fatigue, which is consistent on repeat tests, and involves both central and peripheral mechanisms
- …