Complexes of oxotrichloromolybdenum(
v
) with neutral group 16 donor ligands, MoOCl
3
(L-L) (L-L = RS(CH
2
)
2
SR, R =
i
Pr, Ph; MeS(CH
2
)
3
SMe; MeSe(CH
2
)
2
SeMe; MeSe(CH
2
)
3
SeMe), {MoOCl
2
...(EMe
2
)}
2
(μ-Cl)
2
(E = S, Se, Te), (MoOCl
3
)
2
{
o
-C
6
H
4
(EMe)
2
}
n
(E = Se or Te) and (MoOCl
3
)
2
{MeTe(CH
2
)
3
TeMe}
n
, have been obtained by reaction of the ligands with MoOCl
3
(thf)
2
or MoOCl
3
in either CH
2
Cl
2
or toluene, and characterised by microanalysis, IR and UV-visible spectroscopy and magnetic measurements. The telluroethers are the first examples containing Mo in a positive oxidation state. X-ray crystal structures are reported for the six-coordinate
fac
-MoOCl
3
{MeS(CH
2
)
3
SMe},
mer
-MoOCl
3
{
i
PrS(CH
2
)
2
S
i
Pr} and
mer
-MoOCl
3
{MeSe(CH
2
)
2
SeMe}, as well as the six-coordinate chloride-bridged dimers, {MoOCl
2
(SMe
2
)}
2
(μ-Cl)
2
and {MoOCl
2
(SeMe
2
)}
2
(μ-Cl)
2
. The structure of the mixed-valence decomposition product, Mo
IV
Cl{
o
-C
6
H
4
(TeMe)
2
}
2
(μ-O)Mo
V
OCl
4
, was also determined. In toluene solution MoOCl
4
is reduced by MeS(CH
2
)
3
SMe to produce the Mo(
v
) complex, MoOCl
3
{ MeS(CH
2
)
3
SMe}. Crystal structures of the previously unknown diphosphine analogue, MoOCl
3
{Me
2
P(CH
2
)
2
PMe
2
}, and the mixed-valence derivative Mo
IV
Cl{Me
2
P(CH
2
)
2
PMe
2
}
2
(μ-O)Mo
V
OCl
4
are also reported for comparison and help to clarify earlier contradictory literature reports. In contrast to the dimeric EMe
2
complexes, {MoOCl
2
(EMe
2
)}
2
(μ-Cl)
2
, PMe
3
forms the monomeric complex,
fac
-MoOCl
3
(PMe
3
)
2
.
The synthesis and properties of a systematic series of oxotrichloromolybdenum(
v
) complexes bearing neutral thio-, seleno- and telluroether ligands are described, together with their spectroscopic and structural studies.
Vacuolar pathogens reside in membrane-bound compartments within host cells. Maintaining the integrity of this compartment is paramount to bacterial survival and replication as it protects against ...certain host surveillance mechanisms that function to eradicate invading pathogens. Preserving this compartment during bacterial replication requires expansion of the vacuole membrane to accommodate the increasing number of bacteria, and yet, how this is accomplished remains largely unknown. Here, we show that the vacuolar pathogen Legionella pneumophila exploits multiple sources of host cell fatty acids, including inducing host cell fatty acid scavenging pathways, in order to promote expansion of the replication vacuole and bacteria growth. Conversely, when exogenous lipids are limited, the decrease in host lipid availability restricts expansion of the replication vacuole membrane, resulting in a higher density of bacteria within the vacuole. Modifying the architecture of the vacuole prioritizes bacterial growth by allowing the greatest number of bacteria to remain protected by the vacuole membrane despite limited resources for its expansion. However, this trade-off is not without risk, as it can lead to vacuole destabilization, which is detrimental to the pathogen. However, when host lipid resources become extremely scarce, for example by inhibiting host lipid scavenging, de novo biosynthetic pathways, and/or diverting host fatty acids to storage compartments, bacterial replication becomes severely impaired, indicating that host cell fatty acid availability also directly regulates L. pneumophila growth. Collectively, these data demonstrate dual roles for host cell fatty acids in replication vacuole expansion and bacterial proliferation, revealing the central functions for these molecules and their metabolic pathways in L. pneumophila pathogenesis.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Globally, electronic cigarette (e-cigarette) use among adolescents has increased, along with concerns about potential health implications from exclusive and concurrent tobacco and e-cigarette use ...(i.e., “dual use”). This study used data from a cross-sectional survey administered to 5708 students aged 15–19 in secondary and technical schools throughout two regions of Poland. Data from 2010–2011 (n = 1760); 2013–2014 (n = 1970) and 2015–2016 (n = 1978) were analyzed to assess changes in use of cigarettes and e-cigarettes from 2010–2016, and correlates of exclusive and dual use, daily use, and intensity of product use from 2013–2016. In this sample, e-cigarette trial and past 30-day exclusive e-cigarette use significantly increased over time (2010–2011: 2%; 2013–2014: 8%; 2015–2016: 11% (p < .05)). Dual use increased from 2010–2011 (4%) to 2013–2014 only (23%, p < .05); and remained stable from 2013–2014 to 2015–2016 (24%, p = .60). Most dual users reported using cigarettes before trying e-cigarettes (82% in 2013–2014, 76% in 2015–2016). Analyses comparing dual users to exclusive users showed significant differences in frequency and intensity of product use, similar findings were observed within dual users. Following the introduction of e-cigarettes, both total tobacco use and total cigarette use increased. Among youth in Poland, e-cigarettes do not seem to replace conventional cigarettes, but instead contribute to a more diverse array of available products from which youth can experiment.
•There are concerns about the health effects of concurrent tobacco and electronic cigarette use (i.e., “dual use”).•We assessed changes in cigarette & e-cigarette use, and correlates of exclusive & dual use in Poland from 2010-2016.•Trial and past 30-day exclusive e-cigarette use significantly increased over time.•Dual use increased from 2010-2011 to 2013-2014, and remained stable from 2013-2014 to 2015-2016.•Dual and exclusive users showed differences in frequency of product use; similar findings emerged among dual users.•In Poland, e-cigarettes seem to offer another option for youth experimentation with nicotine.
Background: The aim of this study was to examine palliative care involvement in patients with operative mortality after cardiac surgery, to gain a better understanding of this high-risk population ...and factors influencing referral. Methods: This is a retrospective review using data submitted to the Society of Thoracic Surgeons National Database. Results: The total study population included 93 patients with operative mortality, only 30% of whom had palliative care involvement. The median time from first palliative care involvement to death was 6 days. Nearly 40% of patients had a status labeled as elective at the time of surgery. Conclusion: Our findings suggest that patient mortality risk for elective surgery is being underestimated, or the indications for palliative care consultation in high-risk patients is going unrecognized. Such knowledge may facilitate earlier palliative care involvement, with the goal of improved quality of life for cardiac patients.
Advances in local control techniques, chemotherapy regimens, and imaging modalities have led to improvements in both morbidity and mortality in pediatric sarcoma patients. However, approximately ...one-third of patients develop disease relapse and intracranial metastasis was considered rare. The incidence of sarcoma brain metastasis is thought to have increased and is associated with grim outcomes. This was a retrospective study of 3 deidentified patient charts illustrating the possibility of the central nervous system as a potential site for pediatric sarcoma relapse and investigate the patterns of such relapses. We note this is the first report of infantile fibrosarcoma brain metastasis and a rare report of sarcoma lymph node metastasis. In addition, each patient was treated with targeted therapies, including entrectinib, Ruxolitnib, and pazopanib. Caregivers in cases 2 and 3 reported new-onset neurological manifestations before identification of new brain metastasis, indicating a lag in detection of new intracranial relapse in asymptomatic sarcoma patients. We suggest implementing a brief review of systems screening tool focused on concerning neurological manifestations to screen for new brain metastasis.
Salmonella continues to be a problem associated with low-moisture foods, particularly given enhanced thermal resistance at lower water activity (a
). However, there is a scarcity of thermal ...inactivation models accounting for the effect of a
. The objective of this study was to test multiple secondary models for the effect of product (wheat flour) a
on Salmonella enterica Enteritidis phage type 30 thermal resistance. A full-factorial experimental design included three temperatures (75, 80, and 85°C) and four a
values (~0.30, 0.45, 0.60, and 0.70). Prior to isothermal treatment, sample a
was achieved by equilibrating samples in a humidity-controlled conditioning chamber. Two primary models (log linear and Weibull type) and three secondary models (second-order response surface, modified Bigelow type, and combined effects) were evaluated using the corrected Akaike information criterion and root mean squared errors. Statistical analyses of the primary models favored the log-linear model. Incorporating the three secondary models into the log-linear primary model yielded root mean squared errors of 2.1, 0.78, and 0.96 log CFU/g and corrected Akaike information criterion values of 460, -145, and -19 for the response surface, modified Bigelow, and combined-effects models, respectively. The modified Bigelow-type model, which exponentially scaled both temperature and a
effects on thermal inactivation rates, predicted Salmonella lethality significantly better (P < 0.05) than did the other secondary models examined. Overall, a
is a critical factor affecting thermal inactivation of Salmonella in low-moisture products and should be appropriately included in thermal inactivation models for these types of systems.
ObjectiveTo evaluate heated tobacco product (HTP) awareness, trial and current use among adult cigarette smokers and vaping product users in four countries with varying regulations governing HTP ...sales.DesignData came from Wave 2 of the ITC Four Country Smoking and Vaping Survey, collected from February to July 2018. Respondents were current and former smokers and/or users of vaping products (18 years or older) from Canada (CA; n=3778), England (EN; n=4848), the USA (US; n=2846) and Australia (AU; n=1515). At the time of the survey, only Canada and England permitted the sale of contemporary HTPs (eg, IQOS).ResultsOverall, 30.2% of respondents reported being aware of HTPs (CA=30.4%; EN=31.0%; US=30.2%; AU=27.4%; p=0.346), 2.4% had ever tried HTPs (CA=3.3%; EN=2.4%; US=2.0%; AU=0.9%; p=0.001) and 0.9% currently used HTPs at least monthly (CA=0.8%; EN=1.2%; US=0.7%; AU=0.2%; p<0.001). Trial and current use were higher among those who concurrently smoked and vaped (at least monthly) versus other nicotine use categories (trial: 10.9% v. 1.2%–2.0%, p<0.001; current use: 8.4% v. 0.1%–1.0%, p<0.001). In multivariable analyses, HTP awareness did not differ across countries, whereas odds of trial and current use were lower where HTPs were unavailable. Odds of HTP trial did not differ by regulatory environment when restricting analysis to HTP-aware concurrent smokers–vapers.ConclusionApproximately one third of respondents were aware of HTPs, even in the USA and Australia, where contemporary HTPs were not yet on the market. Trial and use were uncommon, except among concurrent smokers–vapers. Restrictions on availability may have limited HTP use generally, but less so for concurrent smokers–vapers.
The sport sector is advancing its efforts to be environmentally friendly. These efforts now include corporate sponsored environmental initiatives, yet fans’ responsiveness to such efforts remains ...unexamined. Specifically, in this study, the corporate-sponsored environmental initiatives of a college athletic department with an established history of environmental commitments were examined to evaluate the influence of a point of attachment, sport brand-sustainability fit, and receptivity to messaging on the sport organization’s desired outcomes of the campaign (i.e., sustainability behavioral, support for environmental initiative corporate partner). Data were collected from college football fans of an institution in the United States Midwest region using an internet-based survey after the 2019 football season (N = 548). We found that most of our hypotheses were supported. Specifically, attachment to athletics, athletics/sustainability fit, and ascription of responsibility to athletics explained 52.7% of the variance of receptivity to messaging from athletics. In turn, receptivity to sustainable messaging and behaviors explained 45.0% of the support for corporate partners. Our results show that sport practitioners should evaluate the ascription of responsibility their fans place on the sport organization to be environmentally responsible, increasing the receptivity of environmental messages and desired outcomes from such efforts. In addition, this study shows the versatility and applicability of the model to actual sponsored environmental sustainability campaigns of a sport organization.
Heated tobacco products (HTPs), such as IQOS, glo, and Ploom TECH, with a variety of flavored tobacco-containing inserts, have reportedly achieved a significant market share in Japan. We analyzed ...data from Wave 1 of the ITC Japan Survey, a nationally representative web survey conducted in February to March 2018 among 4684 adult participants to estimate the prevalence of HTP use, describe characteristics of HTP users, and explore user preferences for HTP device and flavor. The overall prevalence of monthly HTP use was 2.7% (1.7% daily use). Virtually all HTP users were current cigarette smokers (67.8%) or former smokers (25.0%); only 1.0% of HTP users were never smokers. Among HTP users, IQOS was the most frequently reported brand used (64.5%), and menthol was the most common flavor reported (41.5%). IQOS was used more by younger respondents and those who reported daily use, while Ploom TECH was more popular among older respondents and non-daily HTP users. This is one of the first non-industry funded studies to explore the use of HTPs in Japan.
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