Intermolecular Gold(I)‐Catalyzed Alkyne Carboalkoxylation Reactions for the Multicomponent Assembly of β‐Alkoxy Ketones

A new gold(I)‐catalyzed multicomponent synthesis of β‐alkoxy ketones from aldehydes, alcohols, and alkynes is described. This atom economical synthesis was achieved through the use of the gold complex (SPhos)AuNTf₂ as a catalyst, and allows for the preparation of a diverse array of β‐alkoxy ketone products. Mechanistic studies illustrate that these reactions proceed via gold(I)‐catalyzed hydrolysis of the alkyne to an aryl ketone, which then undergoes an aldol reaction with an oxocarbenium ion generated in situ from the aldehyde and alcohol components.     

Silica Nanoparticle Phytotoxicity to Arabidopsis thaliana

The phytotoxicity of silica nanoparticles (SiNPs) was evaluated as a function of particle size (14, 50, and 200 nm), concentration (250 and 1000 mg L(-1)), and surface composition toward Arabidopsis thaliana plants grown hydroponically for 3 and 6 weeks. Reduced development and chlorosis were observed for plants exposed to highly negative SiNPs (-20.3 and -31.9 mV for the 50 and 200 nm SiNPs, respectively) regardless of particle concentration when not controlling pH of the hydroponic medium, which resulted in increased alkalinity (～pH 8). Particles were no longer toxic to the plants at either concentration upon calcination or removal of surface silanols from the SiNP surface, or adjusting the pH of the growth medium to pH 5.8. The phytotoxic effects observed for the negatively charged 50 and 200 nm SiNPs were attributed to pH effects and the adsorption of macro- and micro-nutrients to the silica surface. Size-dependent uptake of the nanoparticles by the plants was confirmed using transmission electron microscopy (TEM) and inductively coupled plasma-optical emission spectroscopy (ICP-OES) with plant roots containing 32.0, 1.85, and 7.00 × 10(-3) mg Si·kg tissue(-1)/nm(3) (normalized for SiNP volume) for the 14, 50, and 200 nm SiNPs respectively, after 6 weeks exposure at 1000 ppm (pH 5.8). This study demonstrates that the silica scaffolds are not phytotoxic up to 1000 ppm despite significant uptake of the SiNPs (14, 50, and 200 nm) into the root system of A. thaliana.     

Evaluation of vapor intrusion using controlled building pressure

The use of measured volatile organic chemical (VOC) concentrations in indoor air to evaluate vapor intrusion is complicated by (i) indoor sources of the same VOCs and (ii) temporal variability in vapor intrusion. This study evaluated the efficacy of utilizing induced negative and positive building pressure conditions during a vapor intrusion investigation program to provide an improved understanding of the potential for vapor intrusion. Pressure control was achieved in five of six buildings where the investigation program was tested. For these five buildings, the induced pressure differences were sufficient to control the flow of soil gas through the building foundation. A comparison of VOC concentrations in indoor air measured during the negative and positive pressure test conditions was sufficient to determine whether vapor intrusion was the primary source of VOCs in indoor air at these buildings. The study results indicate that sampling under controlled building pressure can help minimize ambiguity caused by both indoor sources of VOCs and temporal variability in vapor intrusion.     

Copper oxide nanoparticle mediated DNA damage in terrestrial plant models

Engineered nanoparticles, due to their unique electrical, mechanical, and catalytic properties, are presently found in many commercial products and will be intentionally or inadvertently released at increasing concentrations into the natural environment. Metal- and metal oxide-based nanomaterials have been shown to act as mediators of DNA damage in mammalian cells, organisms, and even in bacteria, but the molecular mechanisms through which this occurs are poorly understood. For the first time, we report that copper oxide nanoparticles induce DNA damage in agricultural and grassland plants. Significant accumulation of oxidatively modified, mutagenic DNA lesions (7,8-dihydro-8-oxoguanine; 2,6-diamino-4-hydroxy-5-formamidopyrimidine; 4,6-diamino-5-formamidopyrimidine) and strong plant growth inhibition were observed for radish (Raphanus sativus), perennial ryegrass (Lolium perenne), and annual ryegrass (Lolium rigidum) under controlled laboratory conditions. Lesion accumulation levels mediated by copper ions and macroscale copper particles were measured in tandem to clarify the mechanisms of DNA damage. To our knowledge, this is the first evidence of multiple DNA lesion formation and accumulation in plants. These findings provide impetus for future investigations on nanoparticle-mediated DNA damage and repair mechanisms in plants.     

Evaluating the effectiveness of photocatalysts based on titanium dioxide in the degradation of the dye Ponceau 4R

The performance of different titanium dioxide (TiO₂) catalysts and a composite based on the association between TiO₂ P25 and Zinc Phthalocyanine (TiO₂/ZnPc 1.6%) was evaluated in the photocatalytic degradation of the dye Ponceau 4R (C.I. 16255). The results show that the composite presents a better performance than the other, reaching about 50% mineralization of the dye in 120 min of reaction, around three times higher than that observed under the action of pure TiO₂ P25, although this catalyst presents a quantum yield of hydroxyl radical generation about three times higher than that estimated for the composite. This result seems to be a consequence of the synergism between the electronically excited ZnPc aggregates and the TiO₂ surface.A parallel study, based on methods from quantum mechanics also suggested the most feasible routes for the photodegradation of the dye in the absence of the catalyst.     

Where Were We?

This essay examines the twentieth-century water infrastructure of Phoenix, Arizona. An extensive network of canals transformed the desert into farmland, then farmland into suburban sprawl. This infrastructure can be studied as a vital force, one whose arrival so contradicted preexisting geology and ecology that it produced unexpected effects and admitted uninvited visitors. Historical documentation of the canals' transition from agricultural to suburban infrastructure reveals complex human-nature interactions mediated by engineered waters. This brief account argues for the potential of infrastructural history as a form of vibrant postnatural history, one which challenges the notion of genius loci on sites where terrestrial definitions of region have been ruptured.     

Endotracheal tube biofilm and ventilator‐associated pneumonia with mechanical ventilation

Objective: To analyze biofilm on internal and external surfaces of endotracheal tubes after their use in critical care patients, and to produce evidence of association between use of the tube, presence of biofilm, and the occurrence of pneumonia. Methods: This was a clinical study performed at the Intensive Care Unit of an emergency hospital in the interior of São Paulo state, Brazil. Data collection involved 30 endotracheal tubes used on adult patients for a period of ≥48 h of mechanical ventilation for scanning electron microscopy. Results: Analysis of the biofilm on the 30 tubes by scanning electron microscopy showed various abiotic and biotic structures, predominately on the internal surface, such as: fibrin network, erythrocytes, leukocytes, cocci, bacilli, and molds, among others. The intubation period of the endotracheal tube for ≥8 days represented one of the risk factors for ventilator‐associated pneumonia (RR 7.41, P < 0.001). Conclusions: The presence of the endotracheal tube permits microbial colonization, overall contributing to the development of biofilm and the occurrence of pneumonia. Microsc. Res. Tech. 77:305–312, 2014. © 2014 Wiley Periodicals, Inc.     

Nanomaterials for X-ray imaging: gold nanoparticle enhancement of X-ray scatter imaging of hepatocellular carcinoma

We present the development of a new imaging technique for the early diagnosis of hepatocellular carcinoma that utilizes surface-modified gold nanoparticles in combination with X-ray imaging. Tissues labeled with these electron-dense particles show enhanced X-ray scattering over normal tissues, distinguishing cells containing gold nanoparticles from cells without gold in X-ray scatter images. Our results suggest that this novel approach could enable the in vivo detection of tumors as small as a few millimeters in size.     

Cisplatin-loaded porous Si microparticles capped by electroless deposition of platinum

The loading and release of the anti-cancer drug platinum cis-dichlorodiamine (cisplatin) from mesoporous silicon (pSi) microparticles is studied. The pSi microparticles are modified with 1-dodecene or with 1,12-undecylenic acid by hydrosilylation, and each modified pSi material acts as a reducing agent, forming a deposit of Pt on its surface that nucleates further deposition, capping the mesoporous structure and trapping free (unreduced) cisplatin within. Slow oxidation and hydrolytic dissolution of the Si/SiO(2) matrix in buffer solution or in culture medium leads to the release of drugs from the microparticles. The drug-loaded particles show significantly greater toxicity toward human ovarian cancer cells (in vitro), relative to an equivalent quantity of free cisplatin. This result is consistent with the mechanism of drug release, which generates locally high concentrations of the drug in the vicinity of the degrading particles. Control assays with pSi particles loaded in a similar manner with the therapeutically inactive trans isomer of the platinum drug, and with pSi particles containing no drug, result in low cellular toxicity. A hydrophobic pro-drug, cis,trans,cis-[Pt(NH(3))(2)(O(2)C(CH(2))(8)CH(3))(2)Cl(2)], is loaded into the pSi films from chloroform without concomitant reduction of the pSi carrier.     

Evidence that gendered wording in job advertisements exists and sustains gender inequality.

Social dominance theory (Sidanius & Pratto, 1999) contends that institutional-level mechanisms exist that reinforce and perpetuate existing group-based inequalities, but very few such mechanisms have been empirically demonstrated. We propose that gendered wording (i.e., masculine- and feminine-themed words, such as those associated with gender stereotypes) may be a heretofore unacknowledged, institutional-level mechanism of inequality maintenance. Employing both archival and experimental analyses, the present research demonstrates that gendered wording commonly employed in job recruitment materials can maintain gender inequality in traditionally male-dominated occupations. Studies 1 and 2 demonstrated the existence of subtle but systematic wording differences within a randomly sampled set of job advertisements. Results indicated that job advertisements for male-dominated areas employed greater masculine wording (i.e., words associated with male stereotypes, such as leader, competitive, dominant) than advertisements within female-dominated areas. No difference in the presence of feminine wording (i.e., words associated with female stereotypes, such as support, understand, interpersonal) emerged across male- and female-dominated areas. Next, the consequences of highly masculine wording were tested across 3 experimental studies. When job advertisements were constructed to include more masculine than feminine wording, participants perceived more men within these occupations (Study 3), and importantly, women found these jobs less appealing (Studies 4 and 5). Results confirmed that perceptions of belongingness (but not perceived skills) mediated the effect of gendered wording on job appeal (Study 5). The function of gendered wording in maintaining traditional gender divisions, implications for gender parity, and theoretical models of inequality are discussed. (PsycINFO Database Record (c) 2011 APA, all rights reserved)