Search results for "force"

ChemInform Abstract: Diastereoselective Synthesis of Spongian Diterpenes. Total Synthesis of the Furanoditerpene (-)-Spongia-13(16),14-diene.

2010

Abstract An effective diastereoselective synthesis of the marine-sponge metabolite (−)-spongia-13(16),14-diene 1 is achieved starting from S-(+)-carvone via a homochiral phenanthrenone as the key intermediate for the construction of the furan ring system. S-(+)-Carvone was transformed into the phenanthrenone 2a in six steps (53% overall yield), using an intramolecular Diels-Alder reaction as the key step. Conversion of the enone function in 2a into an epoxyaldehyde function followed by cyclisation and aromatisation in acid conditions completed the construction of ring D.

1-Methyl-4-nitraminopyridinium nitrate and 4-nitraminopyridinium methanesulfonate

2001

In the title compounds, C6H8N3O2+*NO3- and C5H6N3O2+*-CH3SO3-, respectively, the cations are almost planar; the twist of the nitramino group about the C-N and N-N bonds does not exceed 10 degrees. The deviations from coplanarity are accounted for by intermolecular N-H...O interactions. The coplanarity of the NHNO2 group and the phenyl ring leads to the deformation of the nitramino group. The C-N-N angle and one C-C-N angle at the junction of the phenyl ring and the nitramino group are increased from 120 degrees by ca 6 degrees, whereas the other junction C-C-N angle is decreased by ca 5 degrees. Within the nitro group, the O-N-O angle is increased by ca 5 degrees and one O-N-N angle is decr…

Hydrogen-bonded dimers of tetra-urea calix[4]arenes stable in THF.

2007

[structure: see text]. Whereas tetra-urea derivatives of tetra-alkoxy calix[4]arenes 1 exist as single molecules in THF, dimeric hydrogen-bonded capsules are exclusively found for the corresponding calix[4]arene derivatives 3 and 2 with two or four free hydroxyl groups. Comparison with the rigidified tetra-urea 5 suggests that this increased stability of the dimers is due to the stabilization of their four-fold symmetry by intramolecular hydrogen bonds between the phenolic hydroxyl groups.

Computational Modeling of Biological Systems: The LDH Story

2010

Lactate dehydrogenases, LDH, catalyzed reaction has been used in this chapter as a conductor wire to present the evolution and difficulties on computing methods to model chemical reactions in enzymes, since the early calculations based at semiempirical level carried out in gas phase to the recent sophisticated simulations based on hybrid Quantum Mechanical/Molecular Mechanics Dynamics (QM/MM MD) schemes. LDH catalyzes the reversible transformation of pyruvate into lactate. The chemical step consists in a hydride and a proton transfer from the cofactor (NADH) and a protonated histidine (His195), respectively. This fact has generated a lot of controversy about the timing of both transfers in …

2015

Chemical ligation has been used to alter motions in specific regions of dihydrofolate reductase from E. coli and to investigate the effects of localized motional changes on enzyme catalysis. Two isotopic hybrids were prepared; one with the mobile N-terminal segment containing heavy isotopes (2H, 13C, 15N) and the remainder of the protein with natural isotopic abundance, and the other one with only the C-terminal segment isotopically labeled. Kinetic investigations indicated that isotopic substitution of the N-terminal segment affected only a physical step of catalysis, whereas the enzyme chemistry was affected by protein motions from the C-terminal segment. QM/MM studies support the idea th…

Synthetic/ECM-inspired hybrid platform for hollow microcarriers with ROS-triggered nanoporation hallmarks

2017

Reactive oxygen species (ROS) are key pathological signals expressed in inflammatory diseases such as cancer, ischemic conditions and atherosclerosis. An ideal drug delivery system should not only be responsive to these signals but also should not elicit an unfavourable host response. This study presents an innovative platform for drug delivery where a natural/synthetic composite system composed of collagen type I and a synthesized polythioether, ensures a dual stimuli-responsive behaviour. Collagen type I is an extracellular matrix constituent protein, responsive to matrix metalloproteinases (MMP) cleavage per se. Polythioethers are stable synthetic polymers characterized by the presence o…

Smart switching in feedforward control of grip force during manipulation of elastic objects

2017

AbstractSwitching systems are common in artificial control systems. Here, we suggest that the brain adopts a switched feedforward control of grip forces during manipulation of objects. We measured how participants modulated grip force when interacting with soft and rigid virtual springs when stiffness varied nearly continuously between trials. We identified a sudden phase transition between two forms of feedforward control that differed in the timing of the synchronization between the anticipated load force and the applied grip force. The switch occurred several trials after a threshold stiffness level. These results suggest that in the control of grip force, the brain acts as a switching c…

Factors related to excessive patellofemoral loading in rearfoot running

2015

Running is recognized as one of the most popular exercise methods. Furthermore, running related injuries have been under the scope for the last few decades. Synchronous function between the segments of the lower limbs is necessary for efficient locomotion. Patellofemoral pain syndrome is a common exercise related syndrome and multifactorial in nature. The purpose of this study was to measure contact forces and frontal plane moments to detect the factors that are associated with atypically high patellofemoral joint loading in rearfoot striking (RFS) running pattern, and moreover, which could possibly contribute to development of the patellofemoral pain syndrome. 39 team sport female athletes…

A reckoning with the maintenance of the built environment, a Sisyphean task

2023

Maintenance concerns most of the artifacts, referring simultaneously to the socio-cultural, technical and managerial spheres. Contemporary scenarios impose an overall rethinking, where key-topics such as tradition, consumerism, sustainability and digitization become pivotal in the search for suitable production models, between post-industrial and neo-craftsmanship, in order to have fresher references for the maintenance activities.
 In the construction field, maintenance is not limited to the objective of prolonging the duration of quality levels that only affect direct users, but also has important implications of a social and collective nature, in the case of both public and private …

Recognition of Chip Forms by Means of Dynamic Force Spectrum Analysis

1993

In this study the ability to identify chip forms occurrs in the turning of austenitic stainless steel using dynamic force spectrum analysis has been tested. For this purpose the frequency spectra obtained from various metal cutting tests were recorded along with the static cutting forces. A dual channel analysis, based on the Fast Fourier Transform (FFT), was adopted to help identify the continuous/discontinuous (favourable/unfavourable) chip forming boundary. The results showed an acceptable correlation between the types of the frequency spectra and the types of chip forms. Finally, an original classification of the spectra obtained during turning of AISI 304 (DIN 1.4301) stainless steel i…