Crystallization-induced phase separation and segmental relaxations in poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blends was systematically investigated by melt-rheology and broadband dielectric spectroscopy in the presence of multiwall carbon nanotubes (MWNTs). Different functionalized MWNTs (amine, -NH2; acid, -COOH) were incorporated in the blends by melt-mixing above the melting temperature of PVDF, where the blends are miscible, and the crystallization induced phase separation was probed in situ by shear rheology. Interestingly, only -NH2 functionalized MWNTs (a-MWNTs) aided in the formation of β-phase (trans-trans) crystals in PVDF, whereas both the neat blends and the blends with -COOH functionalized MWNTs (c-MWNTs) showed only α-phase (trans-gauche-trans-gauche') crystals as inferred from wide-angle X-ray diffraction (WXRD) and Fourier transform infrared (FTIR). Furthermore, blends with only a-MWNTs facilitated in heterogeneous nucleation in the blends manifesting in an increase in the calorimetric crystallization temperature and hence, augmented the rheologically determined crystallization induced phase separation temperature. The dielectric relaxations associated with the crystalline phase of PVDF (αc) was completely absent in the blends with a-MWNTs in contrast to neat blends and the blends with c-MWNTs in the dielectric loss spectra. The relaxations in the blends investigated here appeared to follow Havriliak-Negami (HN) empirical equations, and, more interestingly, the dynamic heterogeneity in the system could be mapped by an extra relaxation at higher frequency at the crystallization-induced phase separation temperature. The mean relaxation time (τHN) was evaluated and observed to be delayed in the presence of MWNTs in the blends, more prominently in the case of blends with a-MWNTs. The latter also showed a significant increase in the dielectric relaxation strength (Δε). Electron microscopy and selective etching was used to confirm the localization of MWNTs in the amorphous phases of the interspherulitic regions as observed from scanning electron microscopy (SEM). The evolved crystalline morphology, during crystallization-induced phase separation, was observed to have a strong influence on the charge transport processes in the blends. These observations were further supported by the specific interactions (like dipole induced dipole interaction) between a-MWNTs and PVDF, as inferred from FTIR, and the differences in the crystalline morphology as observed from WXRD and polarized optical microscopy (POM).
the upsurge of multidrug resistant bacterial infections with declining pipeline of newer antibiotics has made it imperative to develop newer molecules or tailor the existing molecules for more effective antimicrobial therapies. Since antiquity, the use of curcumin, in the form of Curcuma longa paste, to treat infectious lesions is unperturbed despite its grave limitations like instability and aqueous insolubility. Here, we utilized "click" chemistry to address both the issues along with improvisation of its antibacterial and antibiofilm profile. We show that soluble curcumin disrupts several bacterial cellular processes leading to the fenton's chemistry mediated increased production of reactive oxygen species and increased membrane permeability of both Gram-positive and Gram-negative bacteria. We here report that its ability to induce oxidative stress can be harnessed to potentiate activities of ciprofloxacin, meropenem, and vancomycin. In addition, we demonstrated that the soluble curcumin reported herein even sensitizes resistant Gram-negative clinical isolates to the Gram-positive specific antibiotic vancomycin, thereby expanding the antibacterial spectrum of this drug. This work shows that the soluble curcumin can be used to enhance the action of existing antimicrobials against both Gram-positive and Gram-negative bacteria thus strengthening the antibiotic arsenal for fighting resistant bacterial infections for many years to come. There is a coercing need to find new drug alternatives for the treatment of multidrug resistant (MDR) bacterial infections, which presently affects almost 180 million people across the globe and is anticipated to increase up to 225 million by 2030 1,2. A number of drugs, which has been introduced in last 2 decades for the treatment of MDR infections helped only for short term in managing infections due to acquisition and dissemination of the newer resistance 3. As per the recent data mining, the current assessment of the pipeline shows about 42 new antibiotics in development among which 11 are in Phase I clinical trials, 13 in Phase II, 13 in Phase III, four have submitted marketing authorization applications, and only one drug has received a complete response letter. However, given the irrevocability that some of these "in development" antibiotics will be declined for approval, and that resistance will eventually develop with time to those that will be consented for use, it is unblemished that we will have too few drugs to meet current and anticipated patient needs 4. The global menace of resistance can be understood with the fact that we are helpless against carbapenem-resistant/extended spectrum β-lactamase (ESBL)-producing Enterobacteriaceae, Acinetobacter baumannii, Pseudomonas aeruginosa, and Methicillin resistant Staphylococcus aureus as they are resistant to all or nearly all of the antibiotics available today whom the World Health Organization considers critical threats 5. The studies indicate that the upsurge of resistant strains can only
Periodontitis is a biofilm-associated irreversible inflammation of the periodontal tissues.
Surface-functionalized multiwall carbon nanotubes (MWCNTs) are incorporated in poly(methyl methacrylate)/styrene acrylonitrile (PMMA/SAN) blends and the pretransitional regime is monitored in situ by melt rheology and dielectric spectroscopy. As the blends exhibit weak dynamic asymmetry, the obvious transitions in the melt rheology due to thermal concentration fl uctuations are weak. This is further supported by the weak temperature dependence of the correlation length ( ξ ≈ 10-12 Å) in the vicinity of demixing. Hence, various rheological techniques in both the temperature and frequency domains are adopted to evaluate the demixing temperature. The spinodal decomposition temperature is manifested in an increase in the miscibility gap in the presence of MWCNTs. Furthermore, MWCNTs lead to a signifi cant slowdown of the segmental dynamics in the blends. Thermally induced phase separation in the PMMA/SAN blends lead to selective localization of MWCNTs in the PMMA phase. This further manifests itself in a signifi cant increase in the melt conductivity. on the length scale and is too small to infl uence the rheological fi ngerprints. At this length scale, concentration fl uctuation is very weak due to overlapping segmental dynamics and cooperative volume compositions. [ 4 ] In the recent past, dynamic shear rheological studies has gained interest to investigate the phase separation in partially miscible polymer blends. Rheological measurements provide key fi ngerprints that can be used to deduce the critical point of demixing in the blends. Most of the rheological material functions are directly or indirectly related to the concentration fl uctuation and results in various rheological fi ngerprints in the vicinity of phase separation. [5][6][7] The demixing in blends has been studied extensively using scattering and turbidity measurements. These techniques work well when the size of heterogeneity is as large as 100 nm and the difference in refractive index is < 0.01. [ 8 ] However, probing the demixing in polymer
The recent emergence of hypervirulent clinical variants of Klebsiella pneumoniae (hvKP) causing community-acquired, invasive, metastatic, life-threatening infections of lungs, pleura, prostate, bones, joints, kidneys, spleen, muscles, soft-tissues, skin, eyes, central nervous system (CNS) including extrahepatic abscesses, and primary bacteremia even in healthy individuals has posed stern challenges before the existing treatment modalities. There is therefore an urgent need to look for specific and effective therapeutic alternatives against the said bacterial infection or recurrence. A new type of MoS 2 -modified curcumin nanostructure has been developed and evaluated as a potential alternative for the treatment of multidrug-resistant isolates. The curcumin quantum particles have been fabricated with MoS 2 via a seed-mediated hydrothermal method, and the resulting MoS 2 -modified curcumin nanostructures (MQCs) have been subsequently tested for their antibacterial and antibiofilm properties against hypervirulent multidrug-resistant Klebsiella pneumoniae isolates. In the present study, we found MQCs inhibiting the bacterial growth at a minimal concentration of 0.0156 μg/mL, while complete inhibition of bacterial growth was evinced at concentration 0.125 μg/mL. Besides, we also investigated their biocompatibility both in vitro and in vivo. MQCs were found to be nontoxic to the SiHa cells at a dose as high as 1024 μg/ mL on the basis of the tested adhesion, spreading of the cells, and also on the various serological, biochemical, and histological investigations of the vital organs and blood of the Charles Foster Rat. These results suggest that MQCs have potent antimicrobial activities against hvKP and other drug resistant isolates and therefore may be used as broad spectrum antibacterial and antibiofilm agents.
Correction for 'Quantum curcumin mediated inhibition of gingipains and mixed-biofilm of Porphyromonas gingivalis causing chronic periodontitis' by Ashish Kumar Singh et al., RSC Adv., 2018, 8, 40426-40445.
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