Selective and Efficient Removal of Volatile Organic Compounds by Channel-type Gamma-Cyclodextrin Assembly through Inclusion Complexation

Cyclodextrins (CD), produced from enzymatic degradation of starch, are a form of biorenewable cyclic oligosaccharide which has an outstanding capability to form inclusion complexes with a variety of molecules including pollutants due to their toroid-shaped molecular structure. In this study, by a simple reprecipitation method, we obtained "channel-type" packing from γ-CD where CD molecules are stacked on top of each other to form long cylindrical channels. The γ-CD "channel-type" crystals have shown very effective removal of organic volatile compounds (VOCs; aniline and toluene) from the surroundings, whereas cage-type γ-CD could not entrap VOCs from the same environment. Encapsulation capability of channel-type γ-CD is at a ∼2:1 and ∼1:1 molar ratio for aniline/CD and toluene/CD, respectively. Thus, channel-type γ-CD crystals have shown higher removal efficiency for aniline compared to toluene. Channel-type γ-CD is also able to remove aniline selectively from surroundings. Additionally, computational modeling studies suggested that single γ-CD cavity can host two molecules of aniline or toluene for the complexation, yet, aniline is more insistent to make a complex with the γ-CD cavity when compared to toluene. We show that channel-type γ-CD can remove VOCs molecules (aniline and toluene) as efficiently as activated carbon. Hence, being a starch-based biorenewable cyclic oligosaccharide in the form of white powder, the use of "channel-type" γ-CD crystals could be a competitive alternative to activated carbon as an adsorbent for the VOC removal/filtering. © 2017 American Chemical Society

Fabrication of flexible polymer-GaN core-shell nanofibers by the combination of electrospinning and hollow cathode plasma-assisted atomic layer deposition

Here we demonstrate the combination of electrospinning and hollow cathode plasma-assisted atomic layer deposition (HCPA-ALD) processes by fabricating flexible polymer-GaN organic-inorganic core-shell nanofibers at a processing temperature much lower than that needed for the preparation of conventional GaN ceramic nanofibers. Polymer-GaN organic-inorganic core-shell nanofibers fabricated by the HCPA-ALD of GaN on electrospun polymeric (nylon 6,6) nanofibers at 200 °C were characterized in detail using electron microscopy, energy dispersive X-ray analysis, selected area electron diffraction, X-ray diffraction, X-ray photoelectron spectroscopy, photoluminescence measurements, and dynamic mechanical analysis. Although transmission electron microscopy studies indicated that the process parameters should be further optimized for obtaining ultimate uniformity and conformality on these high surface area 3D substrates, the HCPA-ALD process resulted in a ∼28 nm thick polycrystalline wurtzite GaN layer on polymeric nanofibers of an average fiber diameter of ∼70 nm. Having a flexible polymeric core and low processing temperature, these core-shell semiconducting nanofibers might have the potential to substitute brittle ceramic GaN nanofibers, which have already been shown to be high performance materials for various electronic and optoelectronic applications. This journal is © The Royal Society of Chemistry

Polymer-free nanofibers from vanillin/cyclodextrin inclusion complexes: High thermal stability, enhanced solubility and antioxidant property

Vanillin/cyclodextrin inclusion complex nanofibers (vanillin/CD-IC NFs) were successfully obtained from three modified CD types (HPβCD, HPγCD and MβCD) in three different solvent systems (water, DMF and DMAc) via an electrospinning technique without using a carrier polymeric matrix. Vanillin/CD-IC NFs with uniform and bead-free fiber morphology were successfully produced and their free-standing nanofibrous webs were obtained. The polymer-free CD/vanillin-IC-NFs allow us to accomplish a much higher vanillin loading (∼12%, w/w) when compared to electrospun polymeric nanofibers containing CD/vanillin-IC (∼5%, w/w). Vanillin has a volatile nature yet, after electrospinning, a significant amount of vanillin was preserved due to complex formation depending on the CD types. Maximum preservation of vanillin was observed for vanillin/MβCD-IC NFs which is up to ∼85% w/w, besides, a considerable amount of vanillin (∼75% w/w) was also preserved for vanillin/HPβCD-IC NFs and vanillin/HPγCD-IC NFs. Phase solubility studies suggested a 1:1 molar complexation tendency between guest vanillin and host CD molecules. Molecular modelling studies and experimental findings revealed that vanillin:CD complexation was strongest for MβCD when compared to HPβCD and HPγCD in vanillin/CD-IC NFs. For vanillin/CD-IC NFs, water solubility and the antioxidant property of vanillin was improved significantly owing to inclusion complexation. In brief, polymer-free vanillin/CD-IC NFs are capable of incorporating a much higher loading of vanillin and effectively preserve volatile vanillin. Hence, encapsulation of volatile active agents such as flavor, fragrance and essential oils in electrospun polymer-free CD-IC NFs may have potential for food related applications by integrating the particularly large surface area of NFs with the non-toxic nature of CD and inclusion complexation benefits, such as high temperature stability, improved water solubility and an enhanced antioxidant property, etc. © 2016 The Royal Society of Chemistry

Highly Fluorescent Pyrene-Functional Polystyrene Copolymer Nanofibers for Enhanced Sensing Performance of TNT

A pyrene-functional polystyrene copolymer was prepared via 1,3-dipolar cycloaddition reaction (Sharpless-type click recation) between azide-functional styrene copolymer and 1-ethynylpyrene. Subsequently, nanofibers of pyrene-functional polystyrene copolymer were obtained by using electrospinning technique. The nanofibers thus obtained, found to preserve their parent fluorescence nature, confirmed the avoidance of aggregation during fiber formation. The trace detection of trinitrotoluene (TNT) in water with a detection limit of 5 nM was demonstrated, which is much lower than the maximum allowable limit set by the U.S. Environmental Protection Agency. Interestingly, the sensing performance was found to be selective toward TNT in water, even in the presence of higher concentrations of toxic metal pollutants such as Cd2+, Co2+, Cu2+, and Hg2+. The enhanced sensing performance was found to be due to the enlarged contact area and intrinsic nanoporous fiber morphology. Effortlessly, the visual colorimetric sensing performance can be seen by naked eye with a color change in a response time of few seconds. Furthermore, vapor-phase detection of TNT was studied, and the results are discussed herein. In terms of practical application, electrospun nanofibrous web of pyrene-functional polystyrene copolymer has various salient features including flexibility, reproducibility, and ease of use, and visual outputs increase their value and add to their advantage. © 2015 American Chemical Society

Effects of hospital facilities on patient outcomes after cancer surgery: an international, prospective, observational study

Background Early death after cancer surgery is higher in low-income and middle-income countries (LMICs) compared with in high-income countries, yet the impact of facility characteristics on early postoperative outcomes is unknown. The aim of this study was to examine the association between hospital infrastructure, resource availability, and processes on early outcomes after cancer surgery worldwide.Methods A multimethods analysis was performed as part of the GlobalSurg 3 study-a multicentre, international, prospective cohort study of patients who had surgery for breast, colorectal, or gastric cancer. The primary outcomes were 30-day mortality and 30-day major complication rates. Potentially beneficial hospital facilities were identified by variable selection to select those associated with 30-day mortality. Adjusted outcomes were determined using generalised estimating equations to account for patient characteristics and country-income group, with population stratification by hospital.Findings Between April 1, 2018, and April 23, 2019, facility-level data were collected for 9685 patients across 238 hospitals in 66 countries (91 hospitals in 20 high-income countries; 57 hospitals in 19 upper-middle-income countries; and 90 hospitals in 27 low-income to lower-middle-income countries). The availability of five hospital facilities was inversely associated with mortality: ultrasound, CT scanner, critical care unit, opioid analgesia, and oncologist. After adjustment for case-mix and country income group, hospitals with three or fewer of these facilities (62 hospitals, 1294 patients) had higher mortality compared with those with four or five (adjusted odds ratio [OR] 3.85 [95% CI 2.58-5.75]; p<0.0001), with excess mortality predominantly explained by a limited capacity to rescue following the development of major complications (63.0% vs 82.7%; OR 0.35 [0.23-0.53]; p<0.0001). Across LMICs, improvements in hospital facilities would prevent one to three deaths for every 100 patients undergoing surgery for cancer.Interpretation Hospitals with higher levels of infrastructure and resources have better outcomes after cancer surgery, independent of country income. Without urgent strengthening of hospital infrastructure and resources, the reductions in cancer-associated mortality associated with improved access will not be realised

20-Year Risks of Breast-Cancer Recurrence after Stopping Endocrine Therapy at 5 Years

The administration of endocrine therapy for 5 years substantially reduces recurrence rates during and after treatment in women with early-stage, estrogen-receptor (ER)-positive breast cancer. Extending such therapy beyond 5 years offers further protection but has additional side effects. Obtaining data on the absolute risk of subsequent distant recurrence if therapy stops at 5 years could help determine whether to extend treatment