Smectic C Self-Assembly in Mesogen-Free Liquid Crystalline Chiral Polyethers with Sulfonylated Methyl-Branched Side Chains.

To realize advanced electrical applications for ferroelectric liquid crystalline polymers, high spontaneous polarization (Ps ) is highly desired. However, current ferroelectric liquid crystalline polymers usually exhibit a low Ps . In this work, mesogen-free, chiral polyethers containing sulfonylated methyl-branched alkyl side chains with a (CH2 )3 O spacer between the sulfonyl and the branched alkyl groups are designed and synthesized. In contrast to the linear n-alkyl side chains, the methyl-branched alkyl side chains induce chain tilting in the smectic layers. When double chirality exists in both the main chain and the side chains, a crystalline structure is observed after mechanical stretching. Intriguingly, when single chirality exists in either the backbone or the side chains, a liquid crystalline smectic C phase is obtained. The electric displacement-electric field study, however, does not show typical ferroelectric switching, although the dielectric constants are relatively high for these liquid crystalline polymers. This is likely because the dipole-dipole interactions among neighboring sulfonyl groups along the main chain are so strong that the ferroelectric switching is hindered in the samples. For the future work, it is desired to weaken the dipole-dipole interaction to achieve ferroelectricity in these mesogen-free liquid crystalline polymers.

Biological interactions of polystyrene nanoplastics: Their cytotoxic and immunotoxic effects on the hepatic and enteric systems.

As emerging pollutants in the environment, nanoplastics (NPs) can cross biological barriers and be enriched in organisms, posing a greatest threat to the health of livestock and humans. However, the size-dependent toxic effects of NPs in higher mammals remain largely unknown. To determine the size-dependent potential toxicities of NPs, we exposed mouse (AML-12) and human (L02) liver cell lines in vitro, and 6-week-old C57BL/6 mice (well-known preclinical model) in vivo to five different sizes of polystyrene NPs (PS-NPs) (20, 50, 100, 200 and 500 nm). We found that ultra-small NPs (20 nm) induced the highest cytotoxicity in mouse and human liver cell lines, causing oxidative stress and mitochondrial membrane potential loss on AML-12 cells. Unexpectedly in vivo, after long-term oral exposure to PS-NPs (75 mg/kg), medium NPs (200 nm) and large NPs (500 nm) induced significant hepatotoxicity, evidenced by increased oxidative stress, liver dysfunction, and lipid metabolism disorders. Most importantly, medium or large NPs generated local immunotoxic effects via recruiting and activating more numbers of neutrophils and monocytes in the liver or intestine, which potentially resulted in increased proinflammatory cytokine secretion and the tissue damage. The discrepancy in in vitro-in vivo toxic results might be attributed to the different properties of biodistribution and tissue accumulation of different sized NPs in vivo. Our study provides new insights regarding the hepatotoxicity and immunotoxicity of NPs on human and livestock health, warranting us to take immense measures to prevent these NPs-associated health damage.

Engineering self-assembly of giant molecules in the condensed state based on molecular nanoparticles.

In biological systems, it is well-known that the activities and functions of biomacromolecules are dictated not only by their primary chemistries, but also by their secondary, tertiary, and quaternary hierarchical structures. Achieving control of similar levels in synthetic macromolecules is yet to be demonstrated. Most of the critical molecular parameters associated with molecular and hierarchical structures, such as size, composition, topology, sequence, and stereochemistry, are heterogenous, which impedes the exploration and understanding of structure formation and manipulation. Alternatively, in the past few years we have developed a unique giant molecule system based on molecular nanoparticles, in which the above-mentioned molecular parameters, as well as interactions, are precisely defined and controlled. These molecules could self-assemble into a myriad of unconventional and unique structures in the bulk, thin films, and solution. Giant molecules thus offer a robust platform to manipulate the hierarchical structures via precise and modular assemblies of building blocks in an amplified size level compared with small molecules. It has been found that they are not only scientifically intriguing, but also technologically relevant.

[Characteristics, Sources, and Risk Assessment of Perlyfluoroalkyl Substances in Surface Water and Sediment of Luoma Lake].

Through the investigation and detection of the surface water and sediments of Luoma Lake, the structure and occurrence characteristics of PFASs (perlyfluoroalkyl substances) in the two types of media were analyzed, and the principal component analysis method was used to analyze the characteristics of such substances in the surface water. The source was analyzed, and the potential health risks of such substances were evaluated using the risk quotient method. The results showed that a total of 13 PFASs were detected in the surface sediments of Luoma Lake, and one more species was detected in the surface water (PFTeA); ρ(ΣPFASs) in the surface water ranged from 46.09 to 120.34 ng·L-1, and ω(ΣPFASs) in sediments ranged from 2.22 to 9.55 ng·g-1. PFPeA was the major component in surface water, and the mass fraction of PFPeA was 38%. PFBA was the major component in sediment, and the mass fraction of PFPeA was 61%. The multi-media PFASs in Luoma Lake were mainly short-chain substances; the high concentration area of PFASs in the surface water of Luoma Lake was concentrated and distributed at the mouth of the northern rivers. Its concentration showed a decreasing trend from north to south, and the content of PFASs in the sediments showed a decreasing trend from southwest to northeast. The distribution of ΣPFASs, PFBA, and PFOS in the sediments of Luoma Lake and the TOC content in the sediment were related; the principal component analysis showed that the PFASs in the surface water of Luoma Lake were mainly from textile flame retardant, rubber product emulsification, food packaging processes and paper surface treatment industries, the metal electroplating industry, and leather and textile manufacturing industries. PFASs in the surface water of Luoma Lake were at a relatively low health risk level.

Systematic review and meta-analysis of randomized controlled trials of Simethicone for gastrointestinal endoscopic visibility.

BACKGROUND: The value of supplemental use of Simethicone in endoscopy including capsule endoscopy (CE), colonoscopy and esophagogastroduodenoscopy is not addressed and is controversial. METHODS: A systematic review and meta-analysis of randomized controlled studies on the use of Simethicone for endoscopy were carried out. The effects of this preparation on the following endpoints were examined: small bowel visualization quality (SBVQ), completion rate, gastric transit time, small bowel transit time, diagnostic yield, efficacy of bowel preparation, degree of air bubbles and duration time. RESULTS: A total of 13 studies were eligible in this meta-analysis; 4 studies comparing purgative or fasting plus Simethicone with purgative or fasting alone for capsule endoscopy were identified. For patients who had supplemental Simethicone before CE, the SBVQ was significantly better ([odds ratio] OR = 2.84, 95% CI: 1.74-4.65, p = 0.00), and the completion rate was comparable (OR = 0.80, 95% CI: 0.44-1.44, p = 0.454). Also, 7 studies comparing purgative plus Simethicone with purgative alone for colonoscopy were identified. For patients who had supplemental Simethicone before colonoscopy, the efficacy of colon preparation was comparable (OR = 2.06, 95% CI: 0.56-7.53, p = 0.27), but the air bubbles were significantly decreased (OR = 39.32, 95% CI: 11.38-135.86, p = 0.00). CONCLUSION: Supplemental use of Simethicone before endoscopy improves the SBVQ, especially for patients who received no purgative, but does not affect the CE completion rate. It decreases air bubbles in the colonic lumen, but does not improve bowel preparation. And its effect on diagnostic yield remains controversial.

Polymer/lipid interplay in altering in vitro supersaturation and plasma concentration of a model poorly soluble drug.

Supersaturation drug delivery system (SDDS) based on amorphous solid dispersion (ASD) is a widely used strategy to improve oral absorption of poorly water-soluble drugs by achieving a supersaturated state where drug concentration is significantly higher than drug solubility. However, dissolved drugs tend to recrystallize in gastrointestinal (GI) tract if without effective stabilizing excipients. In this paper, well-recognized polymer (polyvinylpyrrolidone, PVP) and lipid (phosphatidylcholine, PC) excipients are combined as ASD carrier, aiming at investigating the effects on evolution of in vitro supersaturation and in vivo plasma concentration of a model poorly soluble drug indomethacin (IND). Fundamental aspects including polymer/lipid composition ratio, drug loading (DL) degree and administration dose were investigated. The in vitro dissolution profiles of ASDs were assessed by supersaturation degree, duration, maximum achievable drug concentration and dose-normalized efficiency, and correlated with in vivo pharmacokinetic data. Results showed that both in vitro and in vivo concentration-time profiles of IND were significantly varying with abovementioned factors. Solution viscosity, solid-state properties and morphology of ASDs were related to the results. This study revealed fundamental mechanisms of PVP/PC mixture effect on IND supersaturation and oral bioavailability, demonstrating that polymer/lipid mixture could be used as a promising carrier to alter supersaturation profile and oral bioavailability of SDDS products.

Investigation of 3D ordered macroporous carbon with different polymer coatings and their application as an oral vaccine carrier.

3-D ordered macroporous carbon with different polymer coatings were developed as new oral vaccine immunological systems. Poly dimethyl diallyl ammonium (PDDA), polyethyleneimine (PEI) and chitosan (CTS), three different polymers with electropositive or adsorption-promoting properties, were chosen as the coating materials to endow the vaccine delivery systems with different surface properties. The bovine serum albumin (BSA) was used as a model vaccine. The three different polymer coated systems exhibited similar release rate which minimized the influence of release rate. The measured value of immunoglobulin G (IgG) titers suggested that the sustained release rate of BSA from polymer coated systems exhibited no strengthened effect on the immune response but could delay the appearance of the peak of the IgG titers compared with uncoated system. The electrostatic attraction between the mucosal and positively charged carrier would be useful during the whole immune experiment. In addition, using the coating material with the ability of enhancing mucosal adsorption was important in the mid-late period of immune. The immunoglobulin A (IgA) titers induced by the polymer coated systems were significantly higher than that induced by the oral BSA solution or i.m. BSA with Freund's complete adjuvant (FCA) which suggested the successful mucosal immune response of the three different coated systems. Overall, this work provides valuable information for the development of oral vaccine delivery system.

Hyaluronic acid oligosaccharide modified redox-responsive mesoporous silica nanoparticles for targeted drug delivery.

A redox-responsive delivery system based on colloidal mesoporous silica (CMS) has been developed, in which 6-mercaptopurine (6-MP) was conjugated to vehicles by cleavable disulfide bonds. The oligosaccharide of hyaluronic acid (oHA) was modified on the surface of CMS by disulfide bonds as a targeting ligand and was able to increase the stability and biocompatibility of CMS under physiological conditions. In vitro release studies indicated that the cumulative release of 6-MP was less than 3% in the absence of glutathione (GSH), and reached nearly 80% within 2 h in the presence of 3 mM GSH. Confocal microscopy and fluorescence-activated cell sorter (FACS) methods were used to evaluate the cellular uptake performance of fluorescein isothiocyanate (FITC) labeled CMS, with and without oHA modification. The CMS-SS-oHA exhibited a higher cellular uptake performance via CD44 receptor-mediated endocytosis in HCT-116 (CD44 receptor-positive) cells than in NIH-3T3 (CD44 receptor-negative) cells. 6-MP loaded CMS-SS-oHA exhibited greater cytotoxicity against HCT-116 cells than NIH-3T3 cells due to the enhanced cell uptake behavior of CMS-SS-oHA. This study provides a novel strategy to covalently link bioactive drug and targeting ligand to the interiors and exteriors of mesoporous silica to construct a stimulus-responsive targeted drug delivery system.