Maternal Cardiovascular Impairment in Pregnancies Complicated by Severe Fetal Growth Restriction

Abstract—Fetal growth restriction and preeclampsia are both conditions of placental etiology and associated to increased risk for the long-term development of cardiovascular disease in the mother. At presentation, preeclampsia is associated with maternal global diastolic dysfunction, which is determined, at least in part, by increased afterload and myocardial stiffness. The aim of this study is to test the hypothesis that women with normotensive fetal growth-restricted pregnancies also exhibit global diastolic dysfunction. This was a prospective case-control study conducted over a 3-year period involving 29 preterm fetal growth-restricted pregnancies, 25 preeclamptic with fetal growth restriction pregnancies, and 58 matched control pregnancies. Women were assessed by conventional echocardiography and tissue Doppler imaging at diagnosis of the complication and followed-up at 12 weeks postpartum. Fetal growth-restricted pregnancies are characterized by a lower cardiac index and higher total vascular resistance index than expected for gestation. Compared with controls, fetal growth-restricted pregnancy was associated with significantly increased prevalence (P�0.001) of asymptomatic left ventricular diastolic dysfunction (28% versus 4%) and widespread impaired myocardial relaxation (59% versus 21%). Unlike preeclampsia, cardiac geometry and intrinsic myocardial contractility were preserved in fetal growth-restricted pregnancy. Fetal growth-restricted pregnancies are characterized by a low output, high resistance circulatory state, as well as a higher prevalence of asymptomatic global diastolic dysfunction and poor cardiac reserve. These findings may explain the increased long-term cardiovascular risk in these women who have had fetal growth-restricted pregnancies. Further studies are needed to clarify the postnatal natural history of cardiac dysfunction in these women

‘THE DOWNWARD PATH’: THE SEDUCTION OF THE SPECTATOR IN AMERICAN SILENT FILM HISTORIOGRAPHY

In an attempt to approach the persistent gravity of the classical Hollywood film spectator as an indicator o f its hegemonic populism, the dissertation conceives o f the historiography o f the silent era as a melodramatic seduction plot. Seeking to rise to the methodological challenge posed by early cinema, Freud’s seduction theory (as it has been elaborated by Jean Laplanche) is proposed as an alternative psychoanalytic model of cultural incorporation, to provide the frame to consider the constitution o f the film populism of classical Hollywood spectatorship as a series of decisive historical encounters with the alterity of film’s monstrative address. In an exploration of the bodies of work of film scholars including Linda Williams, Tom Gunning, Ben Brewster, Miriam Hansen and Mary Ann Doane, this project posits a dialectical itinerary to reimagine the transition from attractions to (narrative) seduction, and to rethink the way that the monstration o f cinema (and its cultural hypostases) comes to invade the intimacy o f the spectatorial interior. It reconsiders the decisive conflicts o f Américan silent film ’s infancy against the screen of analyses of early American Mutoscope and Biograph Company peepshows and the silent films of Cecil B. DeMille, Rudolph Valentino, and Louise Brooks

Photochemical Organocatalytic Regio- and Enantioselective Conjugate Addition of Allyl Groups to Enals

We report the first catalytic enantioselective conjugate addition of allyl groups to α,β-unsaturated aldehydes. The chemistry exploits the visible-light-excitation of chiral iminium ions to activate allyl silanes towards the formation of allylic radicals, which are then intercepted stereoselectively. The underlying radical mechanism of this process overcomes the poor regio- and chemoselectivity that traditionally affects the conjugate allylation of enals proceeding via polar pathways. We also demonstrate how this organocatalytic strategy could selectively install a valuable prenyl fragment at the β-carbon of enals

Synthetic Methods Driven by the Photoactivity of Electron Donor-Acceptor Complexes

The association of an electron-rich substrate with an electron-accepting molecule can generate a new molecular aggregate in the ground state, called an electron donor-acceptor (EDA) complex. Even when the two precursors do not absorb visible light, the resulting EDA complex often does. In 1952, Mulliken proposed a quantum-mechanical theory to rationalize the formation of such colored EDA complexes. However, and besides a few pioneering studies in the 20th century, it is only in the past few years that the EDA complex photochemistry has been recognized as a powerful strategy for expanding the potential of visible-light-driven radical synthetic chemistry. Here, we explain why this photochemical synthetic approach was overlooked for so long. We critically discuss the historical context, scientific reasons, serendipitous observations, and landmark discoveries that were essential for progress in the field. We also outline future directions and identify the key advances that are needed to fully exploit the potential of the EDA complex photochemistry

Green solvents and restoration: Application of biomass-derived solvents in cleaning procedures

Blends of solvents from non-renewable sources, often polluting and toxic to humans, are routinely used in the restoration of painted artifacts. Here we present the application of three different green solvents (and their mixtures) as a viable alternative to the standard triad of solvents (acetone, ethanol, and isooctane) used in the solubility test for cleaning polychromic artworks. Solketal (SOLK), γ-valerolactone (GVL), and 2-ethylhexyl pelargonate (ARGO) were selected among the solvents achievable from bio-based synthons such as glycerol, levulinic acid, and pelargonic acid, which are mainly produced from biomass and renewable feedstocks as exhausted vegetable oils, carbohydrates, and lignocellulose. Specifically, ARGO solvent was prepared by esterification reaction and characterized by nuclear magnetic resonance (NMR) and mass spectroscopy coupled to gas chromatography (GC–MS). Hansen solubility parameters for each solvent were determined by a group contribution method, thus enabling their placement in the Teas graph. Their penetration ability in wooden specimens was investigated by evaluating the volume retention of each solvent with different coated specimens. The solvent ability of the selected compounds was tested by visible and UV observations on specimens prepared with film-forming substances (Dammar, Mastic, Shellac, Paraloid® B72 and linseed oil) brushed onto glass plates. Our results pointed out the suitability of this solvent triad for application to panel painting surfaces. The effectiveness of mixtures made with the above green solvent was successfully tested to remove a terpenic varnish from a 16th century oil painting on a wooden panel

A Photochemical Organocatalytic Strategy for the α-Alkylation of Ketones by using Radicals

Reported herein is a visible-light-mediated radical approach to the α-alkylation of ketones. This method exploits the ability of a nucleophilic organocatalyst to generate radicals upon SN2-based activation of alkyl halides and blue light irradiation. The resulting open-shell intermediates are then intercepted by weakly nucleophilic silyl enol ethers, which would be unable to directly attack the alkyl halides through a traditional two-electron path. The mild reaction conditions allowed functionalization of the α position of ketones with functional groups that are not compatible with classical anionic strategies. In addition, the redox-neutral nature of this process makes it compatible with a cinchona-based primary amine catalyst, which was used to develop a rare example of enantioselective organocatalytic radical α-alkylation of ketones

Human Arm Motion Tracking by Kinect Sensor Using Kalman Filter for Collaborative Robotics

The rising interest in collaborative robotics leads to research solutions in order to increase robot interaction with the environment. The development of methods that permit robots to recognize and track human motion is relevant for safety and collaboration matters. A large quantity of data can be measured in real time by Microsoft Kinect®, a well-known low-cost depth sensor, able to recognize human presence and to provide postural information by extrapolating a skeleton. However, the Kinect sensor tracks motion with relatively low accuracy and jerky behavior. For this reason, the effective use in industrial applications in which the measurement of arm velocity is required can be unsuitable. The present work proposes a filtering method that allows the measurement of more accurate velocity values of human arm, based on row data provided by the Kinect sensor. The estimation of arm motion is achieved by a Kalman filter based on a kinematic model and by the imposition of fixed lengths for the skeleton links detected by the sensor. The development of the method is supported by experimental tests. The achieved results suggest the practical applicability of the developed algorithms

Catalytic asymmetric C–C cross-couplings enabled by photoexcitation

Enantioselective catalytic processes are promoted by chiral catalysts that can execute a specific mode of catalytic reactivity, channeling the chemical reaction through a certain mechanistic pathway. Here, we show how by simply using visible light we can divert the established ionic reactivity of a chiral allyl–iridium(iii) complex to switch on completely new catalytic functions, enabling mechanistically unrelated radical-based enantioselective pathways. Photoexcitation provides the chiral organometallic intermediate with the ability to activate substrates via an electron-transfer manifold. This redox event unlocks an otherwise inaccessible cross-coupling mechanism, since the resulting iridium(ii) centre can intercept the generated radicals and undergo a reductive elimination to forge a stereogenic centre with high stereoselectivity. This photochemical strategy enables difficult-to-realize enantioselective alkyl–alkyl cross-coupling reactions between allylic alcohols and readily available radical precursors, which are not achievable under thermal activation. [Figure not available: see fulltext.