Ionic Materials for Applications in Sensing and Optoelectronics

Organic salts consist of bulky anions and/or cations whose properties can be tailored for specific purposes. Ionic liquids (ILs) are (semi)organic salts with melting points below 100 ºC. They typically exhibit neglible vapor pressures, high thermal stability, wide liquidus range, and tunable solubility. Moreover specific functions can be built into their respective ions. The first part of the dissertation involves discussions of chiral ionic liquids with additional protic, magnetic, and magneto-luminescent properties, respectively. In addition to their enantioselective sensing capabilities, the ILs may find use in chiral separations and catalysis. The second part of the dissertation involves discussions of fluorescent one-dimensional (1D) nano and microstructures from a group of uniform materials based on organic salts (GUMBOS). These GUMBOS are essentially ‘frozen’ ILs with melting points that range from 25 ºC to 250 ºC. Similar to their liquid ‘cousins’, GUMBOS can be tailored for a variety of applications. Further tunability is obtained through size-confinement effects as a result of the nano (and micro) scale of these materials. The 1D nanomaterials were prepared according to templated and self-assembly methods. In one study a porous alumina membrane was used as a sacrificial template for growing nanotubes, nanowires and nanoarrays from rhodamine 6G tetraphenylborate GUMBOS, [R6G][TPB]. These materials may find possible use in sensing, lasing and waveguiding applications. In another study a series of 1D thiacarbocyanine (TC) GUMBOS nano and microsized structures were obtained by ionic self-assembly through a modified reprecipitation approach. Blended nanomaterials consisting of multiple fluorophores were also prepared, exhibiting Förster Resonance Energy Transfer (FRET). The TC nano and microscale structures offer promise as multicolor-imaging and bioimaging agents, and in (bio)sensing applications

Improved nutritional outcomes with neurally adjusted ventilatory assist (NAVA) in premature infants: a single tertiary neonatal unit's experience.

During neurally adjusted ventilatory assist (NAVA)/non-invasive (NIV) NAVA, a modified nasogastric feeding tube with electrodes, monitors the electrical activity of the diaphragm (Edi). The Edi waveform determines the delivered pressure from the ventilator. Infant breathing is in synchrony with the ventilator and therefore is more comfortable with less work of breathing. Our aim was to determine if infants on NAVA had improved nutritional outcomes compared to infants managed on conventional respiratory support. A retrospective study was undertaken. Infants on NAVA were matched with two conventionally ventilated controls by gestational age, birth weight, sex, antenatal steroid exposure, and whether inborn or transferred ex utero. NAVA/NIV-NAVA was delivered by the SERVO-n® Maquet Getinge group ventilator. Conventional ventilation included pressure and volume control ventilation, and non-invasive ventilation included nasal intermittent positive pressure ventilation, triggered biphasic positive airway pressure, continuous positive airway pressure and heated humidified high flow oxygen. The measured outcome was discharge weight z scores. Eighteen "NAVA" infants with median gestational age (GA) of 25.3 (23.6-27.1) weeks and birth weight (BW) of 765 (580-1060) grams were compared with 36 controls with GA 25.2 (23.4-28) weeks (p = 0.727) and BW 743 (560-1050) grams (p = 0.727). There was no significant difference in the rates of postnatal steroids (61% versus 36% p = 0.093), necrotising enterocolitis (22% versus 11% p = 0.279) in the NAVA/NIV NAVA compared to the control group. There were slightly more infants who were breastfed at discharge in the NAVA/NIV NAVA group compared to controls: breast feeds (77.8% versus 58.3%), formula feeds (11.1% versus 30.6%), and mixed feeds (11.1% versus 11.1%), but this difference was not significant (p = 0.275). There was no significant difference in the birth z scores 0.235 (-1.56 to 1.71) versus -0.05 (-1.51 to -1.02) (p = 0.248) between the groups. However, the discharge z score was significantly in favour of the NAVA/NIV-NAVA group: -1.22 (-2.66 to -0.12) versus -2.17 (-3.79 to -0.24) in the control group (p = 0.033).Conclusion: The combination of NAVA/NIV-NAVA compared to conventional invasive and non-invasive modes may contribute to improved nutritional outcomes in premature infants

Long‐Chain Polyunsaturated Fatty Acids and Lipid Peroxidation Products in Donor Human Milk in the United Kingdom: Results From the LIMIT 2‐Centre Cross‐Sectional Study

Background: Donor human milk is increasingly used as alternative to mother’s own milk to feed preterm infants, however, it may provide less long-chain polyunsaturated fatty acid (LCPUFA), and more oxidised lipids, which may be detrimental for preterm infant health and development. Levels have not been reported for donor human milk in the U.K. Methods: Donor human milk (n=19) from two neonatal units, milk from preterm mothers from a neonatal unit (n=10), and term mothers from the community (n=11) were analysed for fatty acid, malondialdehyde, 4-hydroxy-2-nonenal, and hexanal content. Study registration: NCT03573531 Results: Donor human milk had significantly lower absolute LCPUFA content compared to term milk (P<0.001) and significantly lower omega-3 PUFAs than preterm milk (P<0.05), although relative LCPUFA composition did not differ. Exclusive donor human milk feeding leads to significantly lower fat (3.7 vs. 6.7 g/d) and LCPUFA (DHA: 10.6 vs. 16.8 mg/d; ARA: 17.4 vs. 25.2 mg/d) intake than recommended by ESPGHAN, and provides only 17.3% and 43.1% of the in utero accreted ARA and DHA. Donor human milk also had the highest proportion of lipid peroxidation. Conclusions: This study confirms that donor human milk in the U.K. has insufficient levels of LCPUFAs for preterm infants. It demonstrates for the first time that donor human milk has the highest level of lipid peroxidation, compared to preterm or term milk. This has important implications for preterm infant nutrition, as exclusive donor human milk feeding might not be suitable long-term, and may contribute to the development of major preterm neonatal morbidities

Improved respiratory parameters with skin-to-skin contact in premature infants with bronchopulmonary dysplasia on NIV-NAVA.

AIM: To determine if skin-to-skin contact (SSC) improved respiratory parameters in premature infants with evolving or established bronchopulmonary dysplasia (BPD) on non-invasive neutrally adjusted ventilator assist (NIV-NAVA). METHODS: Premature infants (<32 weeks gestational age) with BPD on NIV-NAVA were studied. Continuous readings from the Edi catheter (modified nasogastric feeding tube inserted for NAVA ventilation) were compared: pre-SSC (baby in incubator) and end-SSC (just before end of SSC). RESULTS: Sixty-five episodes of SSC were recorded in 12 premature infants with median gestational age at birth of 24.4 (23.1-27.0) weeks and birth weight of 642 (530-960) grams. Peak Edi (uV) in end-SSC 11.5 (2.7-38.7) was significantly lower compared to pre-SSC 15.8 (4.0-36.6), p < 0.001. P mean (cmH2 O) was significantly lower in end-SSC 9.7 (7.3-15.4) compared to pre-SSC 10.3 (7.5-15.5), p = 0.008. Respiratory rate (breaths/min) was significantly lower in end-SSC 52.9 (31.1-78.1) compared to pre-SSC 53.4 (35.1-74.1), p = 0.031. There was no significant difference in inspired oxygen requirement or time on back-up mode in end-SSC 40.0 (22.1-56.1) and 5.9 (0.0-56.0) compared to pre-SSC 39.0 (26.0-56.1) and 5.1 (0.0-29.3), p = 0.556 and p = 0.853 respectively. CONCLUSION: SSC improved respiratory parameters in premature infants with evolving or established BPD on NIV-NAVA

Nontemplated approach to tuning the spectral properties of cyanine-based fluorescent NanoGUMBOS

Template-free controlled aggregation and spectral properties in fluorescent organic nanoparticles (FONs) is highly desirable for various applications. Herein, we report a nontemplated method for controlling the aggregation in near-infrared (NIR) cyanine-based nanoparticles derived from a group of uniform materials based on organic salts (GUMBOS). Cationic heptamethine cyanine dye 1,1′,3,3,3′,3′-hexamethylindotricarbocyanine (HMT) was coupled with five different anions, viz., [NTf2-], [BETI -], [TFPB-], [AOT-], and [TFP4B-], by an ion-exchange method to obtain the respective GUMBOS. The nanoGUMBOS obtained via a reprecipitation method were primarily amorphous and spherical (30-100 nm) as suggested by selected area electron diffraction (SAED) and transmission electron microscopy (TEM). The formation of tunable self-assemblies within the nanoGUMBOS was characterized using absorption and fluorescence spectroscopy in conjunction with molecular dynamics simulations. Counterion-controlled spectral properties observed in the nanoGUMBOS were attributed to variations in J/H ratios with different anions. Association with the [AOT-] anion afforded predominant J aggregation enabling the highest fluorescence intensity, whereas [TFP4B-] disabled the fluorescence due to predominant H aggregation in the nanoparticles. Analyses of the stacking angle of the cations based on molecular dynamic simulation results in [HMT][NTf2], [HMT][BETI], and [HMT][AOT] dispersed in water and a visual analysis of the representative simulation snapshots also imply that the type of aggregation was controlled through the counterion associated with the dye cation. © 2010 American Chemical Society

Extremely preterm infants receiving standard care receive very low levels of arachidonic and docosahexaenoic acids

Background & aims Adequate supply of arachidonic (ARA) and docosahexaenoic (DHA) acids is essential for brain development, and extremely preterm infants may be at risk of deficiency. Current levels of ARA and DHA given to extremely preterm infants and the amounts available for accretion have not been established, although recent evidence suggests DHA intake is at a level likely to lead to severe deficits. This study quantified the omega-6 and omega-3 polyunsaturated fatty acid (PUFA) intakes from all sources in the first six weeks of life of preterm infants in standard care. In addition, the relationship between blood levels of circulating cytokines and PUFAs was explored. Methods Single centre longitudinal study with omega-6 and omega-3 PUFA intake data analysed from all sources for 17 infants born <28 weeks gestation. At six weeks of age the infants' whole-blood fatty acid levels were measured along with a range of cytokines and chemokines analysed by Luminex® multiplex array. Results ARA intake was significantly below international recommendations in weeks 1–5 (all p < 0.05), and DHA intake was significantly below recommendations in week 1 (p < 0.0001). The amounts of ARA and DHA available for accretion were significantly below estimated accretion rates in all weeks (all p < 0.001). Mean ARA and DHA intakes were correlated with their respective blood levels (r = 0.568, p = 0.017 and r = 0.704, p = 0.002). There were significant relationships between MIP-1β and blood DHA levels (rs = 0.559, p = 0.02) and between RANTES and omega-6:omega-3 PUFA ratio (rs = −0.498, p = 0.042). Conclusions This study establishes that extremely preterm infants receive insufficient intakes of ARA and DHA. Moreover, blood fatty acid levels may provide a useful measure of intake, where establishing sufficient consumption could have clinical importance. There may also be important interactions between long-chain PUFA status and markers of inflammation, which requires further study

Рідке мило на основі соапстоків після нейтралізації олій та жирів в нейтралізуючому розчині, що містить етанол

Development and application of statistical models for medical scientific researc

A comparison of the diagnostic value of MRI and ¹⁸F-FDG-PET/CT in suspected spondylodiscitis.

Purpose The purpose of this study was to evaluate the diagnostic value of 18F-fluorodeoxyglucose (FDG) positron emission tomography and computed tomography (PET/CT scan) and magnetic resonance imaging (MRI) in diagnosing spondylodiscitis and its complications, such as epidural and paraspinal abscesses.Methods From January 2006 to August 2013 patients with a clinical suspicion of spondylodiscitis, with an infection, or with fever of unknown origin were retrospectively included if 18F-FDG-PET/CT and MRI of the spine were performed within a 2-week time span. Imaging results were compared to the final clinical diagnosis and follow-up data were collected.Results Sixty-eight patients were included of whom 49 patients were diagnosed with spondylodiscitis. MRI showed an overall sensitivity of 67 % and specificity of 84 %. Diagnostic accuracy was 58 %, when MRI was performed within 2 weeks after the start of symptoms and improved to 82 %, when performed more than 2 weeks after onset of symptoms. 18F-FDG-PET/CT showed a sensitivity of 96 % and a specificity of 95 %, with no relation to the interval between the scan and the start of symptoms.Conclusions As compared to MRI, 18F-FDG-PET/CT has superior diagnostic value for detecting early spondylodiscitis. After 2 weeks both techniques perform similarly

Clientelism as civil society? Unpacking the relationship between clientelism and democracy at the local level in South Africa

This article, building on analyses from the global south, attempts to reframe democratic expectations by considering where previously maligned practices such as clientelism may hold moments of democracy. It does so by comparing the theory of civil society with that of clientelism, and its African counterpart neo-patrimonialism. It argues that clientelism as civil society may fulfil democratic tasks such as holding the (local) state accountable, strengthening civil and political liberties and providing channels of access for previously marginalised groups. Clientelism is not necessarily a reflection of imposed power relations but, at times, can demonstrate a conscious political strategy, to generate development, on the part of its protagonists.IS