Robust carboxylic acid-terminated organic thin films and nanoparticle protectants generated from bidentate alkanethiols.

A new carboxylic acid-terminated alkanethiol having bidentate character, 16-(3,5-bis(mercaptomethyl)phenoxy)hexadecanoic acid (BMPHA), was designed as an absorbate and protectant to form thermally stable carboxylic acid-terminated organic thin films on flat gold and nanoparticles, respectively. The structural features of the organic thin films derived from BMPHA were characterized by ellipsometry, X-ray photoelectron spectroscopy (XPS), and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and compared to those derived from mercaptohexadecanoic acid (MHA) and 16-(4-(mercaptomethyl)phenoxy)hexadecanoic acid (MMPHA). This study demonstrates that films derived from BMPHA are less densely packed than films derived from MHA and MMPHA. However, the results of solution-phase thermal desorption tests revealed that the carboxylic acid-terminated films generated from BMPHA exhibit an enhanced thermal stability compared to those generated from MHA and MMPHA. Furthermore, as a nanoparticle protectant, BMPHA can be used to stabilize large gold nanoparticles (~45 nm diameter) in solution, and BMPHA-protected gold nanoparticles exhibited a high thermal stability in solution thermolysis studies.

Diaphragmatic Dysfunction Is Characterized by Increased Duration of Mechanical Ventilation in Subjects With Prolonged Weaning.

BACKGROUND: Diaphragmatic dysfunction is often underdiagnosed and is among the risk factors for failed weaning. The purpose of this study was to determine the prevalence of diaphragmatic dysfunction diagnosed by B-mode ultrasonography and to determine whether prolonged weaning subjects with diaphragmatic dysfunction have increased duration of mechanical ventilation compared with those without diaphragmatic dysfunction. METHODS: This was a prospective observational study in mechanically ventilated subjects who failed ≥3 spontaneous breathing trials or required >7 d of weaning after the first spontaneous breathing trial. Diaphragm thickness was measured in the zone of apposition using a 6-13-MHz ultrasound transducer during a spontaneous breathing trial. The diaphragmatic thickening fraction was calculated as a percentage from the formula: (Thickness at peak inspiration - thickness at end expiration)/thickness at end expiration. Intra-observer and inter-observer reliability were also evaluated. RESULTS: Forty-one subjects (24 males; 62.2 ± 15.9 y old) were included in the study. Of these, the prevalence of ultrasonographic diaphragmatic dysfunction (defined as diaphragmatic thickening fraction of <20% with inspiration) was 34.1% (n = 14). Subjects with diaphragmatic dysfunction had longer ventilation time after inclusion (293.4 ± 194.8 vs 145.1 ± 101.3 h, P = .02) and ICU stay (29.2 ± 11.4 vs 22.4 ± 7.7 d, P = .03) than subjects without diaphragmatic dysfunction. CONCLUSIONS: Diaphragmatic dysfunction as assessed by B-mode ultrasonography is common in subjects with prolonged weaning. Subjects with such diaphragmatic dysfunction show longer mechanical ventilation durations and ICU stays.

High-Level Pressure Support Ventilation Attenuates Ventilator-Induced Diaphragm Dysfunction in Rabbits.

BACKGROUND: The effects of different modes of mechanical ventilation in the same ventilatory support level on ventilator-induced diaphragm dysfunction onset were assessed in healthy rabbits. METHODS: Twenty New Zealand rabbits were randomly assigned to 4 groups (n = 5 in each group). Group 1: no mechanical ventilation; group 2: controlled mechanical ventilation (CMV) for 24 hours; group 3: assist/control ventilation (A/C) mode for 24 hours; group 4: high-level pressure support ventilation (PSV) mode for 24 hours. Heart rate, mean arterial blood pressure, PH, partial pressure of arterial oxygen/fraction of inspired oxygen and partial pressure of arterial carbon dioxide were monitored and diaphragm electrical activity was analyzed in the 4 groups. Caspase-3 was evaluated by protein analysis and diaphragm ultra structure was assessed by electron microscopy. RESULTS: The centroid frequency and the ratio of high frequency to low frequency were significantly reduced in the CMV, A/C and PSV groups (P < 0.001). The percent change in centroid frequency was significantly lower in the PSV group than in the CMV and A/C groups (P = 0.001 and P = 0.028, respectively). Electromyography of diaphragm integral amplitude decreased by 90% ± 1.48%, 67.8% ± 3.13% and 70.2% ± 4.72% in the CMV, A/C and PSV groups, respectively (P < 0.001). Caspase-3 protein activation was attenuated in the PSV group compared with the CMV and A/C groups (P = 0.035 and P = 0.033, respectively). Irregular swelling of mitochondria along with fractured and fuzzy cristae was observed in the CMV group, whereas mitochondrial cristae were dense and rich in the PSV group. The mitochondrial injury scores (Flameng scores) in the PSV group were the lowest among the 3 ventilatory groups (0.93 ± 0.09 in PSV versus 2.69 ± 0.05 in the CMV [P < 0.01] and PSV versus A/C groups [2.02 ± 0.08, P < 0.01]). CONCLUSIONS: The diaphragm myoelectric activity was reduced in the PSV group, although excessive oxidative stress and ultra-structural changes of diaphragm were found. However, partial diaphragm electrical activity was retained and diaphragm injury was minimized using the PSV mode.