Increasing the Reactivity of Amides towards Organometallic Reagents: An Overview

The nucleophilic addition of carbon nucleophiles to amides has traditionally been a difficult task, both due to reactivity and selectivity problems. When successful, these processes would represent straightforward routes towards carbonyl‐type or amine compounds, depending on the fate of the generated tetrahedral intermediate. The direct addition of nucleophiles to amides for the preparation of ketones has been studied and applied to the syntheses of several natural products. On the other hand, the addition of nucleophiles to amides to obtain substituted amines represented a major challenge, and only scattered applications on particular substrates have appeared. Initial improvements were based on the activation of amides by introduction of particular substituents, such as in N‐methoxy amides (Weinreb amides) or electron‐withdrawing groups able to increase the carbon nucleophilicity. Although these strategies facilitate the introduction of nucleophiles, chemoselectivity issues arise when additional electrophilic moieties (i.e., carbonyls) are present, thus decreasing the versatility of the methods. In recent years, important advancements towards fully chemoselective methods have been realized. The capture of tetrahedral intermediates with acids generates highly electrophilic iminium species able to undergo chemoselective additions of various nucleophiles, thus accessing substituted amines. Alternatively, the in situ generation of an iminium triflate ion allows highly chemoselective additions of nucleophiles, yielding amines, ketones or ketimines. Also thioamides can be used as precursors of ketones or α‐substituted amines. The success of the above methodologies is further showcased by the application in various syntheses of natural products or biologically active molecules.

     

Measurement of two social competence aspects in middle childhood.

[Correction Notice: An erratum for this article was reported in Vol 34(1) of Developmental Psychology (see record 2009-22882-001). On page 825, Method section, 4th paragraph, line 2, the sentence incorrectly reads, "The county sample consisted of 423 children (M =8 years 5 months, SD =3 years 3 months), constituting 71% of a randomly selected sample of children born in 1986 and living in a county in the middle of Sweden." The correct standard deviation in age in the county sample is 3 months.] The psychometric properties of a rating measure for parents and teachers for social competence, conceptualized as social skills and behaviors, were studied. The rating measure was constructed from factor analyses on 4 samples of school-age children. Factor analyses identified 2 moderately correlated competence aspects, valid for both sexes and for children from varying socioeconomic backgrounds. The first factor, Prosocial Orientation, captured a style promoting positive social interactions; the second factor, Social Initiative, described initiative as opposed to withdrawal in social situations. Scales based on the 2 factors showed reliability in internal consistency and stability across 1 year, validity in interrater agreement concurrently and across 1 year, correspondence with observed peer behavior, and the capacity to discriminate between children of different peer status. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Wafer-Scale Fabrication of Hierarchically Porous Silicon and Silica by Active Nanoparticle-Assisted Chemical Etching and Pseudomorphic Thermal Oxidation (Small 22/2023)

Many biological materials exhibit a multiscale porosity with small, mostly nanoscale pores as well as large, macroscopic capillaries to simultaneously achieve optimized mass transport capabilities and lightweight structures with large inner surfaces. Realizing such a hierarchical porosity in artificial materials necessitates often sophisticated and expensive top-down processing that limits scalability. Here, an approach that combines self-organized porosity based on metal-assisted chemical etching (MACE) with photolithographically induced macroporosity for the synthesis of single-crystalline silicon with a bimodal pore-size distribution is presented, i.e., hexagonally arranged cylindrical macropores with 1 µm diameter separated by walls that are traversed by pores 60 nm across. The MACE process is mainly guided by a metal-catalyzed reduction–oxidation reaction, where silver nanoparticles (AgNPs) serve as the catalyst. In this process, the AgNPs act as self-propelled particles that are constantly removing silicon along their trajectories. High-resolution X-ray imaging and electron tomography reveal a resulting large open porosity and inner surface for potential applications in high-performance energy storage, harvesting and conversion or for on-chip sensorics and actuorics. Finally, the hierarchically porous silicon membranes can be transformed structure-conserving by thermal oxidation into hierarchically porous amorphous silica, a material that could be of particular interest for opto-fluidic and (bio-)photonic applications due to its multiscale artificial vascularization.     

Food selection associated with sense of coherence in adults

Background  

Favorable dietary habits promote health, whereas unfavorable habits link to various chronic diseases. An individual's "sense of coherence" (SOC) is reported to correlate with prevalence of some diseases to which dietary habits are linked. However, understanding what determines an individual's dietary preferences and how to change his/her behavior remains limited. The aim of the present study was to evaluate associations between dietary intake and SOC in adults.     

Effects of orally administered yeast‐derived beta‐glucans: A review

Yeast‐derived beta‐glucans (Y‐BG) are considered immunomodulatory compounds suggested to enhance the defense against infections and exert anticarcinogenic effects. Specific preparations have received Generally Recognized as Safe status and acceptance as novel food ingredients by European Food Safety Authority. In human trials, orally administered Y‐BG significantly reduced the incidence of upper respiratory tract infections in individuals susceptible to upper respiratory tract infections, whereas significant differences were not seen in healthy individuals. Increased salivary IgA in healthy individuals, increased IL‐10 levels in obese subjects, beneficial changes in immunological parameters in allergic patients, and activated monocytes in cancer patients have been reported following Y‐BG intake. The studies were conducted with different doses (7.5–1500 mg/day), using different preparations that vary in their primary structure, molecular weight, and solubility. In animal models, oral Y‐BG have reduced the incidence of bacterial infections and levels of stress‐induced cytokines and enhanced antineoplastic effects of cytotoxic agents. Protective effects toward drug intoxication and ischemia/reperfusion injury have also been reported. In conclusion, additional studies following good clinical practice principles are needed in which well‐defined Y‐BG preparations are used and immune markers and disease endpoints are assessed. Since optimal dosing may depend on preparation characteristics, dose‐response curves might be assessed to find the optimal dose for a specific preparation.     

Estimation of the daily global solar radiation; Nepal experience

This work focuses on estimation of global solar radiation and, in particular, it explores the effect of precipitation and temperature on solar radiation profile of Kathmandu (Nepal). An accurate knowledge of solar radiation distribution in each particular geographical location is crucial for the promotion of solar energy technology. The best way of knowing the amount of global solar radiation is to install quality instruments at many locations in the given region. This requires their day to day maintenance, recording and calibration, which is very costly in developing countries like Nepal. Thus, the alternative approach is to correlate meteorological measurements with appropriate models and investigate the key parameters. For the research activities the RadEst program has been used. It includes, for evaluating the daily global solar radiation values at a given latitudes, four models which estimate the atmospheric transmissivity by measurements of daily temperature range and precipitations. The model parameters are fitted in 2 years data by iterative procedures. The values obtained by these models are, then, compared with measured radiation data. The paper reports graphical and statistical evaluations suggesting that among the four models, the Modular DCBB is the best model for Kathmandu area. This result is useful for designing solar panels able to maximize the harvesting of solar energy and to reduce the chronic shortage of hydrocarbon fuel that Nepal imports in a significant amount each year.     

Cognitive processing and posttraumatic growth after stroke.

Objective: To examine whether posttraumatic growth (PTG) after stroke is associated with cognitive processing and psychological distress and whether time since stroke moderates relationships between these variables. Method: A sample of stroke survivors (N = 60) completed the Posttraumatic Growth Inventory, the Cognitive Processing of Trauma Scale and the Hospital Anxiety and Depression Scale. Results: PTG correlated positively with four indicators of cognitive processing (i.e., positive cognitive restructuring, downward comparison, resolution, and denial) and negatively with depression. Time since stroke moderated a number of these relationships. As length of time since stroke increased, the relationships between PTG and anxiety and depression became more negative and significant, and the relationships between PTG and downward comparisons and resolution became more positive and significant. Discussion: The findings indicate the possibility of PTG after stroke and suggest that cognitive processing is an important process for engendering such growth. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Detection of Pinosylvins in Solid Wood of Scots Pine Using Fourier Transform Raman and Infrared Spectroscopy

Abstract

Diffuse reflectance Fourier transform infrared (DRIFT) and near infrared (NIR) FT-Raman spectroscopy were used to detect pinosylvins in the wood of Pinus sylvestris L. trees. NIR FT-Raman spectroscopy offered the possibility of revealing pinosylvins simply by visual inspection of Raman spectra whereas DRIFT spectra needed a more complicated evaluation. Pinosylvin and resin acids from Scots pine were examined as to the possibility of their being the cause of observed spectral differences between sapwood and heartwood. Since pinosylvins are important compounds for the decay resistance of Scots pine wood, the detection of pinosylvins with Raman spectroscopy might be used to assess durability of wood products.