40 research outputs found
A review of the use of information and communication technologies for dietary assessment
Presently used dietary-assessment methods often present difficulties for researchers and respondents, and misreporting errors are common. Methods using information and communication technologies (ICT) may improve quality and accuracy. The present paper presents a systematic literature review describing studies applying ICT to dietary assessment. Eligible papers published between January 1995 and February 2008 were classified into four assessment categories: computerised assessment; personal digital assistants (PDA); digital photography; smart cards. Computerised assessments comprise frequency questionnaires, 24 h recalls (24HR) and diet history assessments. Self-administered computerised assessments, which can include audio support, may reduce literacy problems, be translated and are useful for younger age groups, but less so for those unfamiliar with computers. Self-administered 24HR utilising computers yielded comparable results as standard methods, but needed supervision if used in children. Computer-assisted interviewer-administered recall results were similar to conventional recalls, and reduced inter-interviewer variability. PDA showed some advantages but did not reduce underreporting. Mobile phone meal photos did not improve PDA accuracy. Digital photography for assessing individual food intake in dining facilities was accurate for adults and children, although validity was slightly higher with direct visual observation. Smart cards in dining facilities were useful for measuring food choice but not total dietary intake. In conclusion, computerised assessments and PDA are promising, and could improve dietary assessment quality in some vulnerable groups and decrease researcher workload. Both still need comprehensive evaluation for micronutrient intake assessment. Further work is necessary for improving ICT tools in established and new methods and for their rigorous evaluatio
Mechanistic features of isomerizing alkoxycarbonylation of methyl oleate.
The weakly coordinated triflate complex
[(P∧P)Pd(OTf)]+(OTf)− (1) (P∧
P = 1,3-bis(di-tert-butylphosphino)
propane) is a suitable reactive precursor for
mechanistic studies of the isomerizing alkoxcarbonylation of
methyl oleate. Addition of CH3OH or CD3OD to 1 forms the
hydride species [(P∧P)PdH(CH3OH)]+(OTf)− (2-CH3OH)
or the deuteride [(P∧P)PdD(CD3OD)]+(OTf)− (2DCD3OD),
respectively. Further reaction with pyridine cleanly
affords the stable and isolable hydride [(P∧P)PdH-
(pyridine)]+(OTf)− (2-pyr). This complex yields the hydride
fragment free of methanol by abstraction of pyridine with BF3·OEt2, and thus provides an entry to mechanistic observations
including intermediates reactive toward methanol. Exposure of methyl oleate (100 equiv) to 2D-CD3OD resulted in rapid
isomerization to the thermodynamic isomer distribution, 94.3% of internal olefins, 5.5% of α,β-unsaturated ester and <0.2% of
terminal olefin. Reaction of 2-pyr/BF3·OEt2 with a stoichiometric amount of 1-13C-labeled 1-octene at −80 °C yields a 50:50
mixture of the linear alkyls [(P∧P)Pd13CH2(CH2)6CH3]+ and [(P∧P)PdCH2(CH2)6
13CH3]+ (4a and 4b). Further reaction with
13CO yields the linear acyls [(P∧P)Pd13C(=O)12/13CH2(CH2)6
12/13CH3(L)]+ (5-L; L = solvent or 13CO). Reaction of 2-pyr/
BF3·OEt2 with a stoichiometric amount of methyl oleate at −80 °C also resulted in fast isomerization to form a linear alkyl
species [(P∧P)PdCH2(CH2)16C(=O)OCH3]+ (6) and a branched alkyl stabilized by coordination of the ester carbonyl group as
a four membered chelate [(P∧P)PdCH{(CH2)15CH3}C(=O)OCH3]+ (7). Addition of carbon monoxide (2.5 equiv) at −80 °C
resulted in insertion to form the linear acyl carbonyl [(P∧P)PdC(=O)(CH2)17C(=O)OCH3(CO)]+ (8-CO) and the fivemembered
chelate [(P∧P)PdC(=O)CH{(CH2)15CH3}C(=O)OCH3]+ (9). Exposure of 8-CO and 9 to 13CO at −50 °C
results in gradual incorporation of the 13C label. Reversibility of 7 + CO ⇄ 9 is also evidenced by ΔG = −2.9 kcal mol−1 and
ΔG‡ = 12.5 kcal mol−1 from DFT studies. Addition of methanol at −80 °C results in methanolysis of 8-L (L = solvent) to form
the linear diester, 1,19-dimethylnonadecandioate, whereas 9 does not react and no branched diester is observed. DFT yields a
barrier for methanolysis of ΔG‡ = 29.7 kcal mol−1 for the linear (8) vs ΔG‡ = 37.7 kcal mol−1 for the branched species (9)
Contemporary Use of Laser During Percutaneous Coronary Interventions: Insights from the Laser Veterans Affairs (LAVA) Multicenter Registry
Background. The contemporary use and outcomes of excimer laser coronary atherectomy (ELCA) in percutaneous coronary intervention (PCI) are not well described. Methods. We examined the baseline clinical and angiographic characteristics and procedural outcomes of 130 target lesions in 121 consecutive PCIs (n = 116 patients) in which ELCA was performed at three United States Department of Veterans Affairs (VA) medical centers between 2008 and 2016. Results. Mean age was 68.5 +/- 9 years and 97% of the patients were men. Patients had high prevalence of diabetes mellitus (63%), prior coronary artery bypass graft surgery (41%), and prior myocardial infarction (60%). The most common target vessel was the left anterior descending (32%), followed by the right coronary artery (30%), circumflex artery (20%), and saphenous vein graft (12%). The target lesions were highly complex, with moderate/severe calcification in 62% and in-stent restenosis in 37%. The most common indication for ELCA was balloon-uncrossable lesions (43.8%), followed by balloon-undilatable lesions (40.8%) and thrombotic lesions (12.3%). Use of ELCA was associated with high technical success rate (90.0%) and procedural success rate (88.8%), and low major adverse cardiac event (MACE) rate (3.45%). Mean procedure time was 120 min (interquartile range [IQR], 81-191 min), air kerma radiation dose was 2.76 Gy (IQR, 1.32-5.01 Gy), and contrast volume was 273 mL (IQR, 201-362 mL). Conclusion. In a contemporary multicenter United States registry, ELCA was commonly used in highly complex lesions and was associated with high technical and procedural success rates and low incidence of MACE
Mechanistic Features of Isomerizing Alkoxycarbonylation of Methyl Oleate
The weakly coordinated triflate complex [(P<sup>∧</sup>P)ÂPdÂ(OTf)]<sup>+</sup>(OTf)<sup>−</sup> (<b>1</b>) (P<sup>∧</sup>P = 1,3-bisÂ(di-<i>tert</i>-butylÂphosphino)Âpropane)
is a suitable reactive precursor for mechanistic studies of the isomerizing
alkoxcarbonylation of methyl oleate. Addition of CH<sub>3</sub>OH
or CD<sub>3</sub>OD to <b>1</b> forms the hydride species [(P<sup>∧</sup>P)ÂPdHÂ(CH<sub>3</sub>OH)]<sup>+</sup>(OTf)<sup>−</sup> (<b>2-CH</b><sub><b>3</b></sub><b>OH</b>) or the
deuteride [(P<sup>∧</sup>P)ÂPdDÂ(CD<sub>3</sub>OD)]<sup>+</sup>(OTf)<sup>−</sup> (<b>2</b><sup><b>D</b></sup><b>-CD</b><sub><b>3</b></sub><b>OD</b>), respectively.
Further reaction with pyridine cleanly affords the stable and isolable
hydride [(P<sup>∧</sup>P)ÂPdHÂ(pyridine)]<sup>+</sup>(OTf)<sup>−</sup> (<b>2-pyr</b>). This complex yields the hydride
fragment free of methanol by abstraction of pyridine with BF<sub>3</sub>·OEt<sub>2</sub>, and thus provides an entry to mechanistic
observations including intermediates reactive toward methanol. Exposure
of methyl oleate (100 equiv) to <b>2</b><sup><b>D</b></sup><b>-CD</b><sub><b>3</b></sub><b>OD</b> resulted
in rapid isomerization to the thermodynamic isomer distribution, 94.3%
of internal olefins, 5.5% of α,β-unsaturated ester and
<0.2% of terminal olefin. Reaction of <b>2</b>-<b>pyr</b>/BF<sub>3</sub>·OEt<sub>2</sub> with a stoichiometric amount
of 1-<sup>13</sup>C-labeled 1-octene at −80 °C yields
a 50:50 mixture of the linear alkyls [(P<sup>∧</sup>P)ÂPd<sup>13</sup><i>C</i>H<sub>2</sub>(CH<sub>2</sub>)<sub>6</sub>CH<sub>3</sub>]<sup>+</sup> and [(P<sup>∧</sup>P)ÂPdCH<sub>2</sub>(CH<sub>2</sub>)<sub>6</sub><sup>13</sup><i>C</i>H<sub>3</sub>]<sup>+</sup> (<b>4a</b> and <b>4b</b>).
Further reaction with <sup>13</sup>CO yields the linear acyls [(P<sup>∧</sup>P)ÂPd<sup>13</sup>CÂ(î—»O)<sup>12/13</sup>CH<sub>2</sub>(CH<sub>2</sub>)<sub>6</sub><sup>12/13</sup>CH<sub>3</sub>(L)]<sup>+</sup> (<b>5-L</b>; L = solvent or <sup>13</sup>CO).
Reaction of <b>2-pyr</b>/BF<sub>3</sub>·OEt<sub>2</sub> with a stoichiometric amount of methyl oleate at −80 °C
also resulted in fast isomerization to form a linear alkyl species
[(P<sup>∧</sup>P)ÂPdCH<sub>2</sub>(CH<sub>2</sub>)<sub>16</sub>CÂ(î—»O)ÂOCH<sub>3</sub>]<sup>+</sup> (<b>6</b>) and a branched
alkyl stabilized by coordination of the ester carbonyl group as a
four membered chelate [(P<sup>∧</sup>P)ÂPdCHÂ{(CH<sub>2</sub>)<sub>15</sub>CH<sub>3</sub>}ÂCÂ(î—»O)ÂOCH<sub>3</sub>]<sup>+</sup> (<b>7</b>). Addition of carbon monoxide (2.5 equiv) at −80
°C resulted in insertion to form the linear acyl carbonyl [(P<sup>∧</sup>P)ÂPdCÂ(î—»O)Â(CH<sub>2</sub>)<sub>17</sub>CÂ(î—»O)ÂOCH<sub>3</sub>(CO)]<sup>+</sup> (<b>8-CO</b>) and the five-membered
chelate [(P<sup>∧</sup>P)ÂPdCÂ(î—»O)ÂCHÂ{(CH<sub>2</sub>)<sub>15</sub>CH<sub>3</sub>}ÂCÂ(î—»O)ÂOCH<sub>3</sub>]<sup>+</sup> (<b>9</b>). Exposure of <b>8-CO</b> and <b>9</b> to <sup>13</sup>CO at −50 °C results in gradual incorporation
of the <sup>13</sup>C label. Reversibility of <b>7</b> + CO
⇄ <b>9</b> is also evidenced by Δ<i>G</i> = −2.9 kcal mol<sup>–1</sup> and Δ<i>G</i><sup>⧧</sup> = 12.5 kcal mol<sup>–1</sup> from DFT
studies. Addition of methanol at −80 °C results in methanolysis
of <b>8-L</b> (L = solvent) to form the linear diester, 1,19-dimethylnonadecandioate,
whereas <b>9</b> does not react and no branched diester is observed.
DFT yields a barrier for methanolysis of Δ<i>G</i><sup>⧧</sup> = 29.7 kcal mol<sup>–1</sup> for the linear
(<b>8</b>) vs Δ<i>G</i><sup>⧧</sup> =
37.7 kcal mol<sup>–1</sup> for the branched species (<b>9</b>)
Mechanistic Features of Isomerizing Alkoxycarbonylation of Methyl Oleate
The weakly coordinated triflate complex [(P<sup>∧</sup>P)ÂPdÂ(OTf)]<sup>+</sup>(OTf)<sup>−</sup> (<b>1</b>) (P<sup>∧</sup>P = 1,3-bisÂ(di-<i>tert</i>-butylÂphosphino)Âpropane)
is a suitable reactive precursor for mechanistic studies of the isomerizing
alkoxcarbonylation of methyl oleate. Addition of CH<sub>3</sub>OH
or CD<sub>3</sub>OD to <b>1</b> forms the hydride species [(P<sup>∧</sup>P)ÂPdHÂ(CH<sub>3</sub>OH)]<sup>+</sup>(OTf)<sup>−</sup> (<b>2-CH</b><sub><b>3</b></sub><b>OH</b>) or the
deuteride [(P<sup>∧</sup>P)ÂPdDÂ(CD<sub>3</sub>OD)]<sup>+</sup>(OTf)<sup>−</sup> (<b>2</b><sup><b>D</b></sup><b>-CD</b><sub><b>3</b></sub><b>OD</b>), respectively.
Further reaction with pyridine cleanly affords the stable and isolable
hydride [(P<sup>∧</sup>P)ÂPdHÂ(pyridine)]<sup>+</sup>(OTf)<sup>−</sup> (<b>2-pyr</b>). This complex yields the hydride
fragment free of methanol by abstraction of pyridine with BF<sub>3</sub>·OEt<sub>2</sub>, and thus provides an entry to mechanistic
observations including intermediates reactive toward methanol. Exposure
of methyl oleate (100 equiv) to <b>2</b><sup><b>D</b></sup><b>-CD</b><sub><b>3</b></sub><b>OD</b> resulted
in rapid isomerization to the thermodynamic isomer distribution, 94.3%
of internal olefins, 5.5% of α,β-unsaturated ester and
<0.2% of terminal olefin. Reaction of <b>2</b>-<b>pyr</b>/BF<sub>3</sub>·OEt<sub>2</sub> with a stoichiometric amount
of 1-<sup>13</sup>C-labeled 1-octene at −80 °C yields
a 50:50 mixture of the linear alkyls [(P<sup>∧</sup>P)ÂPd<sup>13</sup><i>C</i>H<sub>2</sub>(CH<sub>2</sub>)<sub>6</sub>CH<sub>3</sub>]<sup>+</sup> and [(P<sup>∧</sup>P)ÂPdCH<sub>2</sub>(CH<sub>2</sub>)<sub>6</sub><sup>13</sup><i>C</i>H<sub>3</sub>]<sup>+</sup> (<b>4a</b> and <b>4b</b>).
Further reaction with <sup>13</sup>CO yields the linear acyls [(P<sup>∧</sup>P)ÂPd<sup>13</sup>CÂ(î—»O)<sup>12/13</sup>CH<sub>2</sub>(CH<sub>2</sub>)<sub>6</sub><sup>12/13</sup>CH<sub>3</sub>(L)]<sup>+</sup> (<b>5-L</b>; L = solvent or <sup>13</sup>CO).
Reaction of <b>2-pyr</b>/BF<sub>3</sub>·OEt<sub>2</sub> with a stoichiometric amount of methyl oleate at −80 °C
also resulted in fast isomerization to form a linear alkyl species
[(P<sup>∧</sup>P)ÂPdCH<sub>2</sub>(CH<sub>2</sub>)<sub>16</sub>CÂ(î—»O)ÂOCH<sub>3</sub>]<sup>+</sup> (<b>6</b>) and a branched
alkyl stabilized by coordination of the ester carbonyl group as a
four membered chelate [(P<sup>∧</sup>P)ÂPdCHÂ{(CH<sub>2</sub>)<sub>15</sub>CH<sub>3</sub>}ÂCÂ(î—»O)ÂOCH<sub>3</sub>]<sup>+</sup> (<b>7</b>). Addition of carbon monoxide (2.5 equiv) at −80
°C resulted in insertion to form the linear acyl carbonyl [(P<sup>∧</sup>P)ÂPdCÂ(î—»O)Â(CH<sub>2</sub>)<sub>17</sub>CÂ(î—»O)ÂOCH<sub>3</sub>(CO)]<sup>+</sup> (<b>8-CO</b>) and the five-membered
chelate [(P<sup>∧</sup>P)ÂPdCÂ(î—»O)ÂCHÂ{(CH<sub>2</sub>)<sub>15</sub>CH<sub>3</sub>}ÂCÂ(î—»O)ÂOCH<sub>3</sub>]<sup>+</sup> (<b>9</b>). Exposure of <b>8-CO</b> and <b>9</b> to <sup>13</sup>CO at −50 °C results in gradual incorporation
of the <sup>13</sup>C label. Reversibility of <b>7</b> + CO
⇄ <b>9</b> is also evidenced by Δ<i>G</i> = −2.9 kcal mol<sup>–1</sup> and Δ<i>G</i><sup>⧧</sup> = 12.5 kcal mol<sup>–1</sup> from DFT
studies. Addition of methanol at −80 °C results in methanolysis
of <b>8-L</b> (L = solvent) to form the linear diester, 1,19-dimethylnonadecandioate,
whereas <b>9</b> does not react and no branched diester is observed.
DFT yields a barrier for methanolysis of Δ<i>G</i><sup>⧧</sup> = 29.7 kcal mol<sup>–1</sup> for the linear
(<b>8</b>) vs Δ<i>G</i><sup>⧧</sup> =
37.7 kcal mol<sup>–1</sup> for the branched species (<b>9</b>)
Recurrent cardiovascular events with paclitaxel-eluting versus bare-metal stents in saphenous vein graft lesions: Insights from the sos (stenting of saphenous vein grafts) trial
The Stenting of Saphenous Vein Grafts (SOS) trial demonstrated a reduction in clinical and angiographic adverse events with paclitaxel-eluting stents (PES) compared to bare-metal stents (BMS) in saphenous vein graft (SVG) lesions, but the rate of recurrent adverse events has not been described. METHODS: We performed a post hoc, landmark analysis to evaluate the risk of event recurrence following a non-fatal initial event among the SOS trial patients (pts). RESULTS: During a median follow-up of 35 months, the 80 pts enrolled in SOS experienced a total of 78 major cardiovascular events (MACE): 51 in the BMS group and 27 in PES group. No MACE were found in 28 pts (35) while 52 pts (65) had at least one event. The initial event was death in 13 pts (16). Among the 39 pts whose initial event was not fatal, 12 (31) had one or more subsequent MACE (50 of which were definitely related to the study SVG). The mean and median number of MACE per patient was significantly higher in patients receiving BMS versus PES (1.3 ± 1.2 and 1 ± 1.26 versus 0.6 ± 0.7 and 1 ± 0.825, p ≤ 0.005 and p ≤ 0.008, respectively). The rate of a second MACE following an initial event was 17 in the PES group and 37 in the BMS group (p ≤ 0.24). Ten of 12 pts with recurrent events had received a BMS (83). Conclusion: Pts undergoing SVG stenting had a high rate of recurrent events after an initial non-fatal event. These events were often related to the target vessel and most occurred in pts who had received a BMS, further supporting the benefit of PES over BMS in SVG lesions