i-Motifs are alternative DNA secondary structures formed in cytosine-rich sequences. Particular examples of these structures, traditionally assumed to be stable only at acidic pH, have been found to ...form under near-physiological conditions. To determine the potential impact of these structures on physiological processes, investigation of sequences with the capacity to fold under physiological conditions is required. Here we describe a systematic study of cytosine-rich DNA sequences, with varying numbers of consecutive cytosines, to gain insights into i-motif DNA sequence and structure stability. i-Motif formation was assessed using ultraviolet spectroscopy, circular dichroism and native gel electrophoresis. We found that increasing cytosine tract lengths resulted in increased thermal stability; sequences with at least five cytosines per tract folded into i-motif at room temperature and neutral pH. Using these results, we postulated a folding rule for i-motif formation, analogous to (but different from) that for G-quadruplexes. This indicated that thousands of cytosine-rich sequences in the human genome may fold into i-motif structures under physiological conditions. Many of these were found in locations where structure formation is likely to influence gene expression. Characterization of a selection of these identified i-motif forming sequences uncovered 17 genomic i-motif forming sequence examples which were stable at neutral pH.
This article reports on the synthesis of a series of poly(alkyl methacrylate) brush-grafted, 23 nm silica nanoparticles (hairy NPs) and the study of the effect of alkyl pendant length on their use ...as oil lubricant additives for friction and wear reduction. The hairy NPs were prepared by surface-initiated reversible addition–fragmentation chain transfer polymerization from trithiocarbonate chain transfer agent (CTA)-functionalized silica NPs in the presence of a free CTA. We found that hairy NPs with sufficiently long alkyl pendant groups (containing >8 carbon atoms, such as 12, 13, 16, and 18 in this study) could be readily dispersed in poly(alphaolefin) (PAO), forming clear, homogeneous dispersions, and exhibited excellent stability at low and high temperatures as revealed by visual inspection and dynamic light scattering studies. Whereas poly(n-hexyl methacrylate) hairy NPs cannot be dispersed in PAO under ambient conditions or at 80 °C, interestingly, poly(2-ethylhexyl methacrylate) hairy NPs can be dispersed in PAO at 80 °C but not at room temperature, with a reversible clear-to-cloudy transition observed upon cooling. High-contact-stress ball-on-flat reciprocating sliding tribological tests at 100 °C showed significant reductions in both the coefficient of friction (up to 38%) and wear volume (up to 90% for iron flat) for transparent, homogeneous dispersions of hairy NPs in PAO at a concentration of 1.0 wt % compared with neat PAO. The formation of a load-bearing tribofilm at the rubbing interface was confirmed using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy.
We demonstrate improved operation of exchange-coupled semiconductor quantum dots by substantially reducing the sensitivity of exchange operations to charge noise. The method involves biasing a double ...dot symmetrically between the charge-state anticrossings, where the derivative of the exchange energy with respect to gate voltages is minimized. Exchange remains highly tunable by adjusting the tunnel coupling. We find that this method reduces the dephasing effect of charge noise by more than a factor of 5 in comparison to operation near a charge-state anticrossing, increasing the number of observable exchange oscillations in our qubit by a similar factor. Performance also improves with exchange rate, favoring fast quantum operations.
The development of high performance lubricants has been driven by increasingly growing industrial demands and environmental concerns. Herein, we demonstrate oil‐soluble polymer brush‐grafted ...inorganic nanoparticles (hairy NPs) as highly effective lubricant additives for friction and wear reduction. A series of oil‐miscible poly(lauryl methacrylate) brush‐grafted silica and titania NPs were synthesized by surface‐initiated atom transfer radical polymerization. These hairy NPs showed exceptional stability in poly(alphaolefin) (PAO) base oil; no change in transparency was observed after being kept at −20, 22, and 100 °C for ≥55 days. High‐contact stress ball‐on‐flat reciprocating sliding tribological tests at 100 °C showed that addition of 1 wt % of hairy NPs into PAO led to significant reductions in coefficient of friction (up to ≈40 %) and wear volume (up to ≈90 %). The excellent lubricating properties of hairy NPs were further elucidated by the characterization of the tribofilm formed on the flat. These hairy NPs represent a new type of lubricating oil additives with high efficiency in friction and wear reduction.
Oil‐soluble polymer brush grafted nanoparticles (hairy NPs) were synthesized and evaluated as lubricant additives. These hairy NPs exhibited exceptional stability in a lubricating base oil at both low and high temperatures. High contact stress tribological tests at 100 °C revealed that the addition of 1 wt % of hairy NPs into the oil led to significant reductions in friction and wear volume.
We present the Lambda Adaptive Multi-Band Deblending Algorithm in R (lambdar), a novel code for calculating matched aperture photometry across images that are neither pixel- nor PSF-matched, using ...prior aperture definitions derived from high-resolution optical imaging. The development of this program is motivated by the desire for consistent photometry and uncertainties across large ranges of photometric imaging, for use in calculating spectral energy distributions. We describe the program, specifically key features required for robust determination of panchromatic photometry: propagation of apertures to images with arbitrary resolution, local background estimation, aperture normalization, uncertainty determination and propagation, and object deblending. Using simulated images, we demonstrate that the program is able to recover accurate photometric measurements in both high-resolution, low-confusion, and low-resolution, high-confusion, regimes. We apply the program to the 21-band photometric data set from the Galaxy And Mass Assembly (GAMA) Panchromatic Data Release (PDR; Driver et al. 2016), which contains imaging spanning the far-UV to the far-IR. We compare photometry derived from lambdar with that presented in Driver et al. (2016), finding broad agreement between the data sets. None the less, we demonstrate that the photometry from lambdar is superior to that from the GAMA PDR, as determined by a reduction in the outlier rate and intrinsic scatter of colours in the lambdar data set. We similarly find a decrease in the outlier rate of stellar masses and star formation rates using lambdar photometry. Finally, we note an exceptional increase in the number of UV and mid-IR sources able to be constrained, which is accompanied by a significant increase in the mid-IR colour–colour parameter-space able to be explored.
The authors prospectively explored the consequences of hip fracture with regard to discharge placement, functional status, and mortality using the Survey on Assets and Health Dynamics Among the ...Oldest Old (AHEAD). Data from baseline (1993) AHEAD interviews and biennial follow-up interviews were linked to Medicare claims data from 1993–2005. There were 495 postbaseline hip fractures among 5,511 respondents aged ≥69 years. Mean age at hip fracture was 85 years; 73% of fracture patients were white women, 45% had pertrochanteric fractures, and 55% underwent surgical pinning. Most patients (58%) were discharged to a nursing facility, with 14% being discharged to their homes. In-hospital, 6-month, and 1-year mortality were 2.7%, 19%, and 26%, respectively. Declines in functional-status-scale scores ranged from 29% on the fine motor skills scale to 56% on the mobility index. Mean scale score declines were 1.9 for activities of daily living, 1.7 for instrumental activities of daily living, and 2.2 for depressive symptoms; scores on mobility, large muscle, gross motor, and cognitive status scales worsened by 2.3, 1.6, 2.2, and 2.5 points, respectively. Hip fracture characteristics, socioeconomic status, and year of fracture were significantly associated with discharge placement. Sex, age, dementia, and frailty were significantly associated with mortality. This is one of the few studies to prospectively capture these declines in functional status after hip fracture.
This article reports on improved lubricating performance by combining oil-soluble poly(lauryl methacrylate) brush-grafted silica nanoparticles (hairy NPs or HNP) and an oil-miscible ...phosphonium-phosphate ionic liquid (IL) as a friction-reducing additive for a polyalphaolefin (PAO) oil. The HNP was synthesized by surface-initiated reversible addition–fragmentation chain transfer polymerization. At a total concentration of 2% and sufficiently high individual concentrations for HNP and IL in PAO, high-contact stress, ball-on-flat reciprocating tribological tests showed that the friction decreased by up to 23% compared with 2% HNP alone in PAO and by up to 35% compared to the PAO mixed with 2% IL. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS) analysis revealed that the tribofilm formed from the PAO containing 1% HNP + 1% IL was enriched with both Si and P, indicating that both hairy NPs and IL were involved in the tribochemical reactions. In addition, the O 1s and Si 2p peaks in the core-level XPS spectra exhibited significant shifts for the mixture of 1% HNP + 1% IL compared to those for 2% HNP, suggesting the possible formation of new covalent bonds. These results indicated that HNP and IL reacted with each other and also with the metal substrate during the rubbing process, which likely strengthened the tribofilm and its bonding with the substrate and thus further improved the lubrication.
Mechanophore Activation at Heterointerfaces Li, Jun; Shiraki, Tomohiro; Hu, Bin ...
Journal of the American Chemical Society,
11/2014, Letnik:
136, Številka:
45
Journal Article
Recenzirano
Silica nanoparticles grafted with poly(methyl acrylate) (PMA) chains anchored by a maleimide–anthracene cycloadduct were synthesized to demonstrate mechanochemically selective activation of ...mechanophores at heterogeneous interfaces. By quantifying the anthracene-containing cleaved PMA polymers, which are generated via retro-4 + 2 cycloaddition reactions, the first-order kinetic coefficient was determined. Activation characteristics of mechanophores anchored to a nanoparticle exhibit behavior similar to mechanophore-linked polymers, e.g., threshold molecular weight and linear increase in rate coefficient with molecular weight above the threshold. This model system is thus valuable as a probe to test stress activation of interfacially bonded mechanophores relevant to the design of fiber-reinforced polymer composites.
Aims
To determine clinical outcomes and explore prognostic factors related to ulcer healing in people with a clinically infected diabetic foot ulcer.
Methods
This multicentre, prospective, ...observational study reviewed participants’ data at 12 months after culture of a diabetic foot ulcer requiring antibiotic therapy. From participants’ notes, we obtained information on the incidence of wound healing, ulcer recurrence, lower extremity amputation, lower extremity revascularization and death. We estimated the cumulative incidence of healing at 6 and 12 months, adjusted for lower extremity amputation and death using a competing risk analysis, and explored the relationship between baseline factors and healing incidence.
Results
In the first year after culture of the index ulcer, 45/299 participants (15.1%) had died. The ulcer had healed in 136 participants (45.5%), but recurred in 13 (9.6%). An ipsilateral lower extremity amputation was recorded in 52 (17.4%) and revascularization surgery in 18 participants (6.0%). Participants with an ulcer present for ~2 months or more had a lower incidence of healing (hazard ratio 0.55, 95% CI 0.39 to 0.77), as did those with a PEDIS (perfusion, extent, depth, infection, sensation) perfusion grade of ≥2 (hazard ratio 0.37, 95% CI 0.25 to 0.55). Participants with a single ulcer on their index foot had a higher incidence of healing than those with multiple ulcers (hazard ratio 1.90, 95% CI 1.18 to 3.06).
Conclusions
Clinical outcomes at 12 months for people with an infected diabetic foot ulcer are generally poor. Our data confirm the adverse prognostic effect of limb ischaemia, longer ulcer duration and the presence of multiple ulcers.
What's new?
This is the first prospective study to estimate the incidence of healing and prognostic factors associated with healing in people with a clinically infected diabetic foot ulcer, and specifically in the presence of competing risks of amputation and death.
Outcomes for people with a clinically infected diabetic foot ulcer are poorer than previously thought; in the first year after presentation with an infected ulcer, 15.1% of our participants had died and 17.4% underwent at least partial lower extremity amputation.
Healing incidence within 1 year was 44.5% (95% CI 38.9 to 50.1). Three key factors served as the best independent predictors of healing: PEDIS (perfusion, extent, depth, infection, sensation) perfusion grade; the absence of multiple foot ulcers; and shorter ulcer duration.
The aim of this study was to validate the Knee Society Clinical Rating System (knee and function scores) and to compare its responsiveness with that of the Western Ontario and McMaster University ...Osteoarthritis Index (WOMAC) and the Medical Outcomes Study Short Form-36 (SF-36).
Patients were recruited as part of a prospective observational study of the outcomes of primary total knee arthroplasty for the treatment of osteoarthritis in four centers in the United States, six centers in the United Kingdom, and two centers in Australia. Independent research assistants at each site collected the Knee Society clinical data. The WOMAC, SF-36, patient satisfaction, and demographic data were obtained with self-administered questionnaires.
A total of 862 eligible patients were recruited, and complete preoperative and twelve-month data were available for 697 (80.9%) of them. The mean age was seventy years (range, thirty-eight to ninety years), and the majority of the patients (58.9%) were women. Low correlations were found among the items of both the knee and the function score at both assessment times. The Knee Society pain and function scores had moderate-to-strong correlations with the corresponding pain and function domains of the WOMAC and SF-36 (r = 0.31 to 0.72). Measurement of the standardized response mean showed the Knee Society knee score to be more responsive (standardized response mean, 2.2) than the WOMAC (standardized response means, 2.0 for pain and 1.4 for function) and the SF-36 (standardized response means, 1.0 for bodily pain and 1.1 for physical functioning). The Knee Society function score was the least responsive measure (standardized response mean, 0.8). Correlation of changes in scores at twelve months with patient reports of satisfaction and improvement in health status showed the WOMAC and SF-36 to be more responsive than the Knee Society scores.
There is a poor correlation among the items of the Knee Society Clinical Rating System, but the rating system has adequate convergent construct validity. The WOMAC and SF-36 are more responsive measures of outcome of total knee arthroplasty. As they are less labor-intensive for researchers to use and as use of these instruments removes observer bias from the study design, they are preferable for knee arthroplasty outcome studies.
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