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•Polymer brush surface modification of filler particles reduces shrinkage stress compared to conventional silane treatment.•Level of shrinkage stress reduction is proportional to ...oligomer length and inversely proportional to reactive groups number.•Reduced shrinkage stress is due to delayed development of stress with respect to double bond conversion development.
This research explores the use of polymer brushes for surface treatment of fillers used in polymer-based dental restoratives with focus on shrinkage stress reduction. The influence of interfacial reactive groups on shrinkage stress is explored.
Oligomers of varying lengths and with varying number of reactive groups along the length were synthesized by modifying commercial oligomers. Surface of silica fillers (OX50) was treated with methylaminopropyltrimethoxysilane and this was further reacted with the synthesized oligomers to obtain a series of polymer brushes on the surface. Fillers modified with γ-methacryloxypropyltrimethoxysilane were used as a control. Filler surface treatment was confirmed using diffuse reflectance spectroscopy and thermogravimetric analysis. Fillers were added at 30 wt % to a resin made of BisGMA/TEGDMA and polymerization kinetics, shrinkage stress, volumetric shrinkage, flexural strength and modulus, viscosity were measured.
Composites with polymer brush functionalized fillers showed up to a 30 % reduction in shrinkage stress as compared to the control, with no reduction in flexural strength and modulus. Shrinkage stress reduced with increasing length of the polymer brush and increased with increase in number of reactive groups along the length of the polymer brush.
The interface between inorganic fillers and an organic polymer matrix has been utilized to reduce shrinkage stress in a composite with no compromise in mechanical properties. This study gives insights into the stress development mechanism at the interface.
A scalable synthesis of high refractive index, optically transparent photopolymers from a family of low-viscosity multifunctional thiol and alkyne monomers via thiol–yne “click” is described herein. ...The monomers designed to incorporate high refractive index cores consisting of aryl and sulfide groups with high intrinsic molar refraction were synthesized starting from commercially available low-cost raw materials. The low-viscosity (<500 cP) thiol–yne resins formulated with these new multifunctional monomers and a phosphine oxide photoinitiator underwent efficient thiol–yne polymerizations upon exposure to 405 nm light at 30 mW/cm2. In contrast to the previously reported thiol–ene systems, the kinetic profile of these photopolymerizations showed significant dependence on the nature of the thiol and alkyne monomers. However, the ability of the thiol–yne reaction to introduce a large number of sulfide linkages compared to that of thiol–ene systems yielded cross-linked high optical quality photopolymers with a polymer refractive index that exceeds 1.68 (n D/20 °C). Interestingly, the photopolymer formed from the least sterically hindered alkynyl thioether monomer 2b with flexible thioether core and the dithiol 1a exhibited unprecedented difference in the polymer refractive index as compared to that of the resin with polymerization-induced changes reaching up to 0.08. Furthermore, the implementation of these low-viscosity thiol–yne resins was demonstrated by preparing two-stage photopolymeric holographic materials with a dynamic range of ∼0.02 and haze < 1.5% in two-dimensional high refractive index structures.
Childhood blindness from retinopathy of prematurity (ROP) is increasing as a result of improvements in neonatal care worldwide. We evaluate the effectiveness of artificial intelligence (AI)-based ...screening in an Indian ROP telemedicine program and whether differences in ROP severity between neonatal care units (NCUs) identified by using AI are related to differences in oxygen-titrating capability.
External validation study of an existing AI-based quantitative severity scale for ROP on a data set of images from the Retinopathy of Prematurity Eradication Save Our Sight ROP telemedicine program in India. All images were assigned an ROP severity score (1-9) by using the Imaging and Informatics in Retinopathy of Prematurity Deep Learning system. We calculated the area under the receiver operating characteristic curve and sensitivity and specificity for treatment-requiring retinopathy of prematurity. Using multivariable linear regression, we evaluated the mean and median ROP severity in each NCU as a function of mean birth weight, gestational age, and the presence of oxygen blenders and pulse oxygenation monitors.
The area under the receiver operating characteristic curve for detection of treatment-requiring retinopathy of prematurity was 0.98, with 100% sensitivity and 78% specificity. We found higher median (interquartile range) ROP severity in NCUs without oxygen blenders and pulse oxygenation monitors, most apparent in bigger infants (>1500 g and 31 weeks' gestation: 2.7 2.5-3.0 vs 3.1 2.4-3.8;
= .007, with adjustment for birth weight and gestational age).
Integration of AI into ROP screening programs may lead to improved access to care for secondary prevention of ROP and may facilitate assessment of disease epidemiology and NCU resources.
A new addition-fragmentation chain transfer (AFT) capable moiety was incorporated into a dimethacrylate monomer that participated readily in network formation by copolymerizing with multifunctional ...methacrylates or acrylates. The process of AFT occurred simultaneously with photopolymerization of the AFT monomer (AFM) and other (meth)acrylate monomers leading to polymer stress relaxation via network reconfiguration. At low loading levels of the AFM, a significant reduction in shrinkage stress, especially for acrylate monomers, was observed with nominal effects on conversion. At higher loading levels of the AFM, the photopolymerization reaction kinetics and final double bond conversion were significantly lowered along with a delay in the gel-point conversion. Electron paramagnetic resonance studies during polymerization revealed the presence of a distinct radical species that was present in proportional quantities to the AFM content in the system. The lifetime and the character of the persistent radicals were altered due to the presence of the distinctive radical, in turn affecting the polymerization kinetics. With polymerization conducted at higher irradiance, the differential conversion between the control resin and samples with moderate AFM content was minimal, especially for the methacrylate-based formulations.
The ubiquilin family (UBQLN) of proteins consists of five closely related members (UBQLN1, UBQLN2, UBQLN3, UBQLN4, and UBQLNL) that have a high degree of similarity at the level of both amino acid ...and domain structure. The role of UBQLN1 and UBQLN2 in regulating processes involved in cancer progression and tumorigenesis is still not completely understood. MYC is an oncogene and is well known to play important roles in cancer progression and metastasis. Herein, we show that the loss of UBQLN1 and UBQLN2 causes increased cell viability, cell proliferation, cell migration, clonogenic potential, and cell cycle progression, which is associated with increased MYC expression. UBQLN1 and UBQLN2 interact with phosphorylated MYC and facilitate its degradation. The overexpression of UBQLN1 reverses the increased expression of MYC following the loss of UBQLN2. Further, we present evidence that decreasing MYC levels back to baseline can reverse phenotypes driven by the loss of UBQLN1 or UBQLN2. Finally, we show that loss of UBQLN1 drives tumorigenesis and lung metastasis in mice which are associated with an increase in the expression of MYC, proteins involved in cell cycle progression, and EMT. Taken together, our results suggest for the first time a novel role of UBQLN1 and UBQLN2 in regulating MYC in lung adenocarcinoma cells.
To describe aggressive posterior retinopathy of prematurity (APROP) in a subset of premature babies, having gestational age (GA) of ≥28 weeks and birth weight (BW) of ≥1000 g.
Retrospective ...observational case series.
Case records of 99 babies, who were diagnosed to have APROP between July 2002 and October 2010 were reviewed. Fundus fluorescein angiography (FFA) was carried out in 19 babies.
The mean GA was 31.7 weeks (range 28-35 weeks) and mean BW was 1572 g (range 1000-2310 g). All these babies received supplemental unblended oxygen 3 days or longer after birth. Of the 52 babies who had an eye exam in the neonatal intensive care unit prior to discharge, 35 babies had loss of vascularised retina from zone II to zone I and four babies from zone III to zone I, when examined as an outpatient. FFA revealed large geographic areas of vaso-obliteration (more than 30 disc areas) posterior to the shunt vessels within vascularised retina.
Features of severe capillary bed loss in the vascularised retina were seen in our cases. Oxygen could be a precipitating factor in causing this retinopathy of prematurity in large babies.
To analyse the profile and implication of genetic testing in a cohort of retinoblastoma (RB) patients and their families conducted on a single day during World Retinoblastoma Awareness Week 2017.
...Retrospective analysis of blood samples were collected from 411 subjects, including 113 probands at a camp organised for RB awareness and were analysed for RB1 mutations by Sanger sequencing and Multiplex Ligation-dependent Probe Amplification (MLPA). If germline mutations were detected, the parents and siblings of the proband were tested for the same mutation.
Germline RB1 mutations were identified in 61/113(54%) probands with a mutation detection rate of 96% (47/49) and 22% (14/64) for bilateral and unilateral RB, respectively. Ten novel pathogenic mutations were identified. Splice mutation was most common (31%) followed by nonsense mutation (26%). The mean age at RB diagnosis was significantly lower in patients having germline RB1 mutation (mean 10.7 months ±2.5) compared to those without (mean 27.2 months ±6.5) (p = <0.0001). Parental transmission of the mutant allele was detected in 15/61(25%) cases of which 11(18%) parents were unaffected indicating incomplete penetrance. The origin of the variant allele was both paternal (n = 7) and maternal (n = 4) wherein 5 were bilateral and 6 unilateral.
The detection of a germline mutation impacts the proband and family members due to its implications on change in prognosis, frequency of subsequent evaluations, screening for ocular and non-ocular cancers, and surveillance of family and future progeny.
Abstract Objectives To examine effects of shrinkage and modulus on the dynamic development of shrinkage stress as a function of methacrylate conversion and filler loading in a model photocurable ...dimethacrylate-based resin with a silanized barium glass filler. Methods BisGMA/TEGDMA samples with filler loading levels of 0–70 wt% were evaluated. Irradiation times and intensities were varied to achieve a wide range of conversion. Shrinkage stress measurements were accompanied with real-time conversion monitoring, while shrinkage and modulus measurements were made at different static conversion points. Results Shrinkage increased nearly linearly with respect to conversion, while for a given value of conversion, it decreased proportionally with increasing filler content. Modulus advanced in an exponential fashion with conversion and also increased incrementally with filler content; however, modulus values rose disproportionately rapidly for the highest filler loading. At either high or low filler loading levels, stress at limiting conversion, which was inversely proportional to the filler load, was high while at an intermediate filler content, a minimum in stress was observed due to the combined effects of filler based shrinkage reduction, restricted limiting conversion and only moderately enhanced modulus. The level of polymerization stress predicted from the conversion-indexed shrinkage and modulus measurements over-estimated the experimental stress states as modulus evolved due to system compliance that to some degree mimics the clinical situation presented by photocuring bonded composite restorations. Significance Measurement of monomer conversion provides a common basis by which different material properties can be rationally compared.
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