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1.
Macromol Rapid Commun ; 45(12): e2300665, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38444218

ABSTRACT

Glycidyl ethers are prepared from a series of furan-based diols and cured with a diamine to form thermosets. The furan diols demonstrate lower toxicity than bisphenol-A in a prior study. The diglycidyl ethers show improved thermal stability compared to the parent diols. Cured thermosets are prepared at elevated temperature using isophorone diamine (IPDA). Glass transition temperatures are in the range of 30-54 °C and depend on the structure of the furan diol. Coatings are prepared on steel substrates and show very high hardness, good adhesion, and a range of flexibility. Properties compare favorably with a control based on a bisphenol-A epoxy resin. The study demonstrates that epoxy resins based on furan diols, which have been shown to have lower toxicity than bisphenol-A, can form thermosets having properties comparable to a standard epoxy resin system; and thus, are viable as replacements for bisphenol-A epoxy resins.


Subject(s)
Epoxy Resins , Furans , Epoxy Resins/chemistry , Furans/chemistry , Benzhydryl Compounds/chemistry , Temperature , Molecular Structure , Epoxy Compounds/chemistry , Phenols/chemistry
2.
Stem Cells ; 35(11): 2280-2291, 2017 11.
Article in English | MEDLINE | ID: mdl-28833807

ABSTRACT

Multipotent mesenchymal stem cells (MSCs) have enormous potential in tissue engineering and regenerative medicine. However, until now, their development for clinical use has been severely limited as they are a mixed population of cells with varying capacities for lineage differentiation and tissue formation. Here, we identify receptor tyrosine kinase-like orphan receptor 2 (ROR2) as a cell surface marker expressed by those MSCs with an enhanced capacity for cartilage formation. We generated clonal human MSC populations with varying capacities for chondrogenesis. ROR2 was identified through screening for upregulated genes in the most chondrogenic clones. When isolated from uncloned populations, ROR2+ve MSCs were significantly more chondrogenic than either ROR2-ve or unfractionated MSCs. In a sheep cartilage-repair model, they produced significantly more defect filling with no loss of cartilage quality compared with controls. ROR2+ve MSCs/perivascular cells were present in developing human cartilage, adult bone marrow, and adipose tissue. Their frequency in bone marrow was significantly lower in patients with osteoarthritis (OA) than in controls. However, after isolation of these cells and their initial expansion in vitro, there was greater ROR2 expression in the population derived from OA patients compared with controls. Furthermore, osteoarthritis-derived MSCs were better able to form cartilage than MSCs from control patients in a tissue engineering assay. We conclude that MSCs expressing high levels of ROR2 provide a defined population capable of predictably enhanced cartilage production. Stem Cells 2017;35:2280-2291.


Subject(s)
Chondrogenesis/genetics , Mesenchymal Stem Cells/metabolism , Receptor Tyrosine Kinase-like Orphan Receptors/genetics , Wnt-5a Protein/genetics , Animals , Cell Differentiation , Cell Proliferation , Cells, Cultured , Humans , Receptor Tyrosine Kinase-like Orphan Receptors/metabolism , Sheep , Tissue Engineering , Wnt-5a Protein/metabolism
3.
Chemistry ; 21(18): 6801-5, 2015 Apr 27.
Article in English | MEDLINE | ID: mdl-25753376

ABSTRACT

A widely used principle is that shifts in the wavenumber of carboxylate stretching modes upon bonding with a metal center can be used to infer if the geometry of the bonding is monodentate or bidentate. We have tested this principle with ab initio modeling for aqueous metal carboxylate complexes and have shown that it does indeed hold. Modeling of the bonding of acetate and formate in aqueous solution to a range of cations was used to predict the infrared spectra of the metal-carboxylate complexes, and the wavenumbers of the symmetric and antisymmetric vibrational modes are reported. Furthermore, we have shown that these shifts in wavenumber occur primarily due to how bonding with the metal changes the carboxylate C-O bond lengths and O-C-O angle.

4.
Spectrochim Acta A Mol Biomol Spectrosc ; 134: 535-42, 2015 Jan 05.
Article in English | MEDLINE | ID: mdl-25048288

ABSTRACT

The infrared spectra of six aqueous carboxylate anions have been calculated at the M05-2X/cc-pVTZ level of theory with the SMD solvent model, and validated against experimental data from the literature over the region of 1700 cm(-1) to 1250 cm(-1); this region corresponds to the stretching modes of the carboxylate group, and is often interrogated when probing bonding of carboxylates to other species and surfaces. The anions studied here were formate, acetate, oxalate, succinate, glutarate and citrate. For the lowest energy conformer of each anion, the carboxylate moiety antisymmetric stretching peak was predicted with a mean signed error of only 4 cm(-1) using the SMD solvent model, while the symmetric peak was slightly overestimated. Performing calculations in vacuum and scaling was found to generally over-predict the antisymmetric vibrational frequencies and under predict the symmetric peak. Different conformers of the same anion were found to have only slightly different spectra in the studied region and the inclusion of explicit water molecules was not found to significantly change the calculated spectra when the implicit solvent model is used. Overall, the use of density functional theory in conjunction with an implicit solvent model was found to result in infra-red spectra that are the best reproduction of the features found experimentally for the aqueous carboxylate ions in the important 1700 cm(-1) to 1250 cm(-1) region. The development of validated model chemistries for simulating the stretching modes of aqueous carboxylate ions will be valuable for future studies that investigate how carboxylate anions complex with multivalent metal cations and related species in solution.


Subject(s)
Anions/chemistry , Carboxylic Acids/chemistry , Models, Molecular , Quantum Theory , Spectrophotometry, Infrared , Water/chemistry
5.
Phys Ther ; 95(3): 350-9, 2015 Mar.
Article in English | MEDLINE | ID: mdl-25212521

ABSTRACT

BACKGROUND: A low-cost virtual reality system that translates movements of the hand, fingers, and thumb into game play was designed to provide a flexible and motivating approach to increasing adherence to home-based rehabilitation. OBJECTIVE: Effectiveness depends on adherence, so did patients use the intervention to the recommended level? If not, what reasons did they give? The purpose of this study was to investigate these and related questions. DESIGN: A prospective cohort study, plus qualitative analysis of interviews, was conducted. METHODS: Seventeen patients recovering from stroke recruited to the intervention arm of a feasibility trial had the equipment left in their homes for 8 weeks and were advised to use it 3 times a day for periods of no more than 20 minutes. Frequency and duration of use were automatically recorded. At the end of the intervention, participants were interviewed to determine barriers to using it in the recommended way. RESULTS: Duration of use and how many days they used the equipment are presented for the 13 participants who successfully started the intervention. These figures were highly variable and could fall far short of our recommendations. There was a weak positive correlation between duration and baseline reported activities of daily living. Participants reported lack of familiarity with technology and competing commitments as barriers to use, although they appreciated the flexibility of the intervention and found it motivating. LIMITATIONS: The small sample size limits the conclusions that can be drawn. CONCLUSIONS: Level of use is variable and can fall far short of recommendations. Competing commitments were a barrier to use of the equipment, but participants reported that the intervention was flexible and motivating. It will not suit everyone, but some participants recorded high levels of use. Implications for practice are discussed.


Subject(s)
Home Care Services , Patient Compliance , Stroke Rehabilitation , Upper Extremity , User-Computer Interface , Video Games , Activities of Daily Living , Adult , Aged , Aged, 80 and over , Feasibility Studies , Female , Humans , Male , Middle Aged , Outcome Assessment, Health Care , Prospective Studies
6.
J Phys Chem B ; 116(39): 11999-2006, 2012 Oct 04.
Article in English | MEDLINE | ID: mdl-22920269

ABSTRACT

Aqueous pK(a) values are calculated from first principles for a set of carboxylic acids using the SMD solvation model with various model chemistries, thermodynamic cycles, and treatments of explicit solvation. In all, 108 unique theoretical protocols are examined. The direct (D) and water proton exchange (PX) cycles are trialled along with a new approach, termed the semidirect (SD) cycle. The SD thermodynamic cycle offers some improvements over the D and PX schemes, as it bypasses the gas-phase heterolytic bond dissociation calculation required in the conventional D approach while also avoiding an aqueous OH(-) calculation required by the PX method when using water as the reference acid. With all three cycles, the recommended model chemistry employs M05-2X/cc-pVTZ Gibbs energies of solvation with a single discrete water molecule and a high-level composite method for the gas-phase reaction energies. With the SD cycle, these calculations result in a mean unsigned error of less than 1 pK(a) units, with respective mean signed error and maximum unsigned error of less than 0.5 and 2 pK(a) units. Similar results are obtained with the D and PX cycles, and further improvement is required in both the gas and aqueous phase ab initio energy calculations before we can truly discriminate between the thermodynamic cycles investigated here.

7.
Aphasiology ; 24(2): 188-209, 2010 Feb.
Article in English | MEDLINE | ID: mdl-20186261

ABSTRACT

Background: The causal basis of the different patterns of language recovery following stroke in bilingual speakers is not well understood. Our approach distinguishes the representation of language from the mechanisms involved in its control. Previous studies have suggested that difficulties in language control can explain selective aphasia in one language as well as pathological switching between languages. Here we test the hypothesis that difficulties in managing and resolving competition will also be observed in those who are equally impaired in both their languages even in the absence of pathological switching.Aims: To examine difficulties in language control in bilingual individuals with parallel recovery in aphasia and to compare their performance on different types of conflict task.Methods & Procedures: Two right-handed, non-native English-speaking participants who showed parallel recovery of two languages after stroke and a group of non-native English-speaking, bilingual controls described a scene in English and in their first language and completed three explicit conflict tasks. Two of these were verbal conflict tasks: a lexical decision task in English, in which individuals distinguished English words from non-words, and a Stroop task, in English and in their first language. The third conflict task was a non-verbal flanker task.Outcomes & Results: Both participants with aphasia were impaired in the picture description task in English and in their first language but showed different patterns of impairment on the conflict tasks. For the participant with left subcortical damage, conflict was abnormally high during the verbal tasks (lexical decision and Stroop) but not during the non-verbal flanker task. In contrast, for the participant with extensive left parietal damage, conflict was less abnormal during the Stroop task than the flanker or lexical decision task.Conclusions: Our data reveal two distinct control impairments associated with parallel recovery. We stress the need to explore the precise nature of control problems and how control is implemented in order to develop fuller causal accounts of language recovery patterns in bilingual aphasia.

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