Aqueous phase behavior of a 1-O-phytanyl-beta-D-xyloside/water system. Glycolipid-based bicontinuous cubic phases of crystallographic space groups Pn3m and Ia3d

Temperature- and concentration-dependent aqueous phase diagram of a novel alkylglycoside, 1-O-phytanyl-beta-D-xyloside (beta-Xyl(Phyt)), was studied using small-angle X-ray scattering, polarizing optical microscopy, and differential scanning calorimetry. The phases found in this system include an Lc phase, an Lalpha phase, an HII phase, two inverted cubic phases of crystallographic space groups Pn3m and Ia3d, and a fluid isotropic phase, FI. The phase diagram of the beta-Xyl(Phyt)/water system is similar to that for the 1-monooleylglycerol (MO)/water system, suggesting that the phase behavior is largely determined by the overall molecular shape rather than the details of surfactant molecular structure. Moreover, the structural parameters of the beta-Xyl(Phyt) liquid crystals are also similar to those of the MO/water, due primarily to the similar molecular dimensions of two molecules. As compared to the MO/water system, however, the beta-Xyl(Phyt)/water system displays a lower value of TK ( approximately 8.(5) degrees C) and a wider temperature window for the mesophases (8.(5)-120 degrees C). Moreover, beta-Xyl(Phyt) is chemically more robust than MO, as the ether linkage is more stable against hydrolysis than the ester linkage and the phytanyl chain is fully saturated.     

Horse heart cytochrome c entrapped into the hydrated liquid-crystalline phases of phytantriol: X-ray diffraction and Raman spectroscopic characterization

Small angle X-ray diffraction (SAXD), resonance Raman (RR) spectroscopy with 413 nm excitation, and non-resonance Raman technique with 785 nm excitation were used to probe the influence of entrapped cytochrome c (Cyt c) on the structure of hydrated phytantriol (Phyt) liquid-crystalline phases as well as conformational changes of heme group and secondary structure of the protein. SAXD measurements indicated that incorporation of Cyt c affects both nanostructure dimensions and type of liquid-crystalline phases of hydrated Phyt. The unit cell dimensions decrease with increasing Cyt c concentration for all phases. In addition, protein perturbs the nanostructure of Q(230) and Q(224) liquid-crystalline phases of hydrated Phyt to such an extent that they transform into the Q(229) phase with the Im3m space group. RR data revealed that entrapment of oxidized Cyt c into the Q(230) phase at 1 wt.% content results in near complete reduction of central iron ion of the heme group, while its low-spin state and six-ligand coordination configuration are preserved. Based on the analysis of heme out-of-plane folding vibration near 568 cm(-1) (γ(21)) and ν(48) mode at 633 cm(-1), it was demonstrated that the protein matrix tension on the heme group is relaxed upon incorporation of protein into Q(230) phase. Non-resonant Raman bands of difference spectra showed the preservation of α-helix secondary structure of Cyt c in the liquid-crystalline phase at relatively high (5 wt.%) content. The Cyt c induced spectroscopic changes of Phyt bands were found to be similar as decrease in temperature.     

Diversifying the solid state and lyotropic phase behavior of nonionic urea-based surfactants

The solid state and lyotropic phase behavior of 10 new nonionic urea-based surfactants has been characterized. The strong homo-urea interaction, which can prevent urea surfactants from forming lyotropic liquid crystalline phases, has been ameliorated through the use of isoprenoid hydrocarbon tails such as phytanyl (3,7,11,15-tetramethyl-hexadecyl) and hexahydrofarnesyl (3,7,11-trimethyl-dodecyl) or the oleyl chain (cis-octadec-9-enyl). Additionally, the urea head group was modified by attaching either a hydroxy alkyl (short chain alcohol) moiety to one of the nitrogens of the urea or by effectively "doubling" the urea head group by replacing it with a biuret head group. The solid state phase behavior, including the liquid crystal-isotropic liquid, polymorphic, and glass transitions, is interpreted in terms of molecular geometries and probable hydrogen-bonding interactions. Four of the modified urea surfactants displayed ordered lyotropic liquid crystalline phases that were stable in excess water at both room and physiological temperatures, namely, 1-(2-hydroxyethyl)-1-oleyl urea (oleyl 1,1-HEU) with a 1D lamellar phase (Lalpha), 1-(2-hydroxyethyl)-3-phytanyl urea (Phyt 1,3-HEU) with a 2D inverse hexagonal phase (HII), and 1-(2-hydroxyethyl)-1-phytanyl urea (Phyt 1,1-HEU) and 1-(2-hydroxyethyl)-3-hexahydrofarnesyl urea (Hfarn 1,3-HEU) with a 3D bicontinuous cubic phase (QII). Phyt 1,1-HEU exhibited rich mesomorphism (QII1, QII2, Lalpha, LU, and HII), as did one other surfactant, oleyl 1,3-HEU (QII1, QII2, Lalpha, LU, and HII), in the study group. LU is an unusual phase which is mobile and isotropic but possesses shear birefringence, and has been very tentatively assigned as an inverse sponge phase. Three other surfactants exhibited a single lyotropic liquid crystalline phase, either Lalpha or HII, at temperatures >50 degrees C. The 10 new surfactants are compared with other recently reported nonionic urea surfactants. Structure-property correlations are examined for this novel group of self-assembling amphiphiles.     

Aqueous chlorination of sulfamethazine and sulfamethoxypyridazine: Kinetics and transformation products identification

Sulfonamides (SNs) are synthetic antimicrobial agents. These substances are continually introduced into the environment, and they may spread and maintain bacterial resistance in the different compartments. The chlorination of 2 SNs, namely, sulfamethazine (SMT) and sulfamethoxypyridazine (SMP), was investigated to study their reactivity with chlorine at typical concentrations for water treatment conditions. Experiments conducted in purified water show an acceleration of SMT and SMP degradation of a factor 1.5 by comparison to drinking water matrix. This difference is due to pH variation and competitive reactions between SNs and mineral and organic compounds, with chlorine in drinking water. In the presence of an excess of chlorine (6.7 μmol·L⁻¹) in ultrapure water at pH 7.2, second‐order degradation rate constants were equal to 4.5 × 10²M⁻¹·s⁻¹ and 5.2 × 10²M⁻¹·s⁻¹ for SMT and SMP, respectively. The structures of transformation products were investigated by liquid chromatography tandem mass spectrometry analyses with equimolar concentrations between chlorine and SNs. SO₂ elimination, cyclization, and electrophilic substitutions were the main pathways of by‐products formation. Moreover, the toxicity of the proposed structures was predicted by using toxicity estimation software tool program. The results indicated that most by‐products may present developmental toxicity.     

Dual cross-linked networks hydrogels with unique swelling behavior and high mechanical strength: based on silica nanoparticle and hydrophobic association

A series of physically cross-linked hydrogels composed poly(acrylic acid) and octylphenol polyoxyethylene acrylate with high mechanical strength are reported here with dual cross-linked networks that formed by silica nanoparticles (SNs) and hydrophobic association micro-domains (HAMDs). Acrylic acid (AA) and octylphenol polyoxyethylene acrylate with 10 ethoxyl units (OP-10-AC) as basic monomers in situ graft from the SNs surface to build poly(acrylic acid) hydrophilic backbone chains with randomly distributed OP-10-AC hydrophobic side chains. The entanglements among grafted backbone polymer chains and hydrophobic branch architecture lead to the SNs and HAMDs play the role of physical cross-links for the hydrogels network structure. The rheological behavior and polymer concentration for gelation process are measured to examine the critical gelation conditions. The correlation of the polymer dual cross-linked networks with hydrogels swelling behavior, gel-to-sol phase transition, and mechanical strength are addressed, and the results imply that the unique dual cross-linking networks contribute the hydrogels distinctive swelling behavior and excellent tensile strength. The effects of SNs content, molecular weight of polymer backbone, and temperature on hydrogels properties are studied, and the results indicate that the physical hydrogel network integrity is depended on the SNs and HAMDs concentration.     

Dissolvable Carboxymethylcellulose Microneedles for Noninvasive and Rapid Administration of Diclofenac Sodium

The aim of this study is to prepare dissolvable biopolymeric microneedle (MN) patches composed solely of sodium carboxymethylcellulose (CMC), a water-soluble cellulose derivative with good film-forming ability, by micromolding technology for the transdermal delivery of diclofenac sodium salt (DCF). The MNs with ≈456 µm in height displayed adequate morphology, thermal stability up to 200 °C, and the required mechanical strength for skin insertion (>0.15 N needle⁻¹). Experiments in ex vivo abdominal human skin demonstrate the insertion capability of the CMC_DCF MNs up to 401 µm in depth. The dissolution of the patches in saline buffer results in a maximum cumulative release of 98% of diclofenac after 40 min, and insertion in a skin simulant reveals that all MNs completely dissolve within 10 min. Moreover, the MN patches are noncytotoxic toward human keratinocytes. These results suggest that the MN patches produced with CMC are promising biopolymeric systems for the rapid administration of DCF in a minimally invasive manner.     

Oil‐Soluble Polymer Brush Grafted Nanoparticles as Effective Lubricant Additives for Friction and Wear Reduction

The development of high performance lubricants has been driven by increasingly growing industrial demands and environmental concerns. Herein, we demonstrate oil‐soluble polymer brush‐grafted inorganic nanoparticles (hairy NPs) as highly effective lubricant additives for friction and wear reduction. A series of oil‐miscible poly(lauryl methacrylate) brush‐grafted silica and titania NPs were synthesized by surface‐initiated atom transfer radical polymerization. These hairy NPs showed exceptional stability in poly(alphaolefin) (PAO) base oil; no change in transparency was observed after being kept at ?20, 22, and 100 °C for ≥55 days. High‐contact stress ball‐on‐flat reciprocating sliding tribological tests at 100 °C showed that addition of 1 wt % of hairy NPs into PAO led to significant reductions in coefficient of friction (up to ≈40 %) and wear volume (up to ≈90 %). The excellent lubricating properties of hairy NPs were further elucidated by the characterization of the tribofilm formed on the flat. These hairy NPs represent a new type of lubricating oil additives with high efficiency in friction and wear reduction.     

Solvation Modulation Enhances Anion-Derived Solid Electrolyte Interphase for Deep Cycling of Aqueous Zinc Metal Batteries

Stable Zn anodes with a high utilization efficiency pose a challenge due to notorious dendrite growth and severe side reactions. Therefore, electrolyte additives are developed to address these issues. However, the additives are always consumed by the electrochemical reactions over cycling, affecting the cycling stability. Here, hexamethylphosphoric triamide (HMPA) is reported as an electrolyte additive for achieving stable cycling of Zn anodes. HMPA reshapes the solvation structures and promotes anion decomposition, leading to the in situ formation of inorganic-rich solid-electrolyte-interphase. More interestingly, this anion decomposition does not involve HMPA, preserving its long-term impact on the electrolyte. Thus, the symmetric cells with HMPA in the electrolyte survive ≈500 h at 10 mA cm⁻² for 10 mAh cm⁻² or ≈200 h at 40 mA cm⁻² for 10 mAh cm⁻² with a Zn utilization rate of 85.6 %. The full cells of Zn||V₂O₅ exhibit a record-high cumulative capacity even under a lean electrolyte condition (E/C ratio=12 μL mAh⁻¹), a limited Zn supply (N/P ratio=1.8) and a high areal capacity (6.6 mAh cm⁻²).     

Probing the interaction between peptides and metal oxides using point mutants of a TiO2-binding peptide

An increasing number of peptides with specific binding affinity to inorganic materials are being isolated using combinatorial peptide libraries without prior knowledge about the interaction between peptides and target materials. The lack of understanding of the mechanism and the contribution of constituent amino acids to the peptides' inorganic-binding ability poses an obstacle to optimizing and tuning of the binding affinity of peptides to inorganic materials and thus hinders the practical application of these peptides. Using the phage surface display technique, we previously identified a disulfide-bond-constrained peptide (-CHKKPSKSC-, STB1) cognitive of TiO2. In the present study, the interaction of STB1 with TiO2 was probed using a series of point mutants of STB1 displayed on phage surfaces. Their binding affinity was measured using a quartz crystal microbalance with energy dissipation measurement and compared on the basis of the delta f or delta D values. The three K residues of STB1 were found to be essential and sufficient for phage particle binding to TiO2. One mutant with five K residues showed not stronger but weaker binding affinity than STB1 due to its conformational restriction, as illustrated by molecular dynamics simulation, to align five K residues in a way conducive to their simultaneous interaction with the TiO2 surface. The contextual influence of noncharged residues on STB1's binding affinity was also investigated. Our results may provide insight into the electrostatic interaction between peptides and inorganic surfaces.     

The charge‐transfer complex trans‐STB–TCNQF4

In the crystal structure of the title charge‐transfer complex, namely trans‐stilbene–2,2′‐(2,3,5,6‐tetra­fluoro­benzene‐1,4‐diyl­idene)­propane­di­nitrile (1/1) (trans‐STB–TCNQF₄), C₁₄H₁₂·C₁₂F₄N₄, the planar STB and TCNQF₄ mol­ecules are stacked alternately. The structure is not isostructural with that of STB–TCNQ. No anomaly was found in the displacement parameters of any atoms, while the bond length of the central C=C moiety was shorter than the corresponding bond in ethyl­ene. This suggests that the central C=C moiety of the STB mol­ecule vibrates with a large amplitude, similar to the case in free STB and STB–TCNQ.     

Effect of fluorosurfactant on capillary instabilities in nanoimprinted polymer patterns

Surface forces play a paramount role in most aspects of Nanoimprint Lithography. In particular, subjecting nanoimprinted patterns to moderate heating allows surface tension to smooth out undesirable roughness and defects in the patterns, but this “thermal reflow” treatment can induce structural decay or even collapse of the patterns by capillary instability if this process is not carefully controlled. Adhesion between the mold and polymer film can also cause the imprinted structure to tear or fracture. Fluorinated surfactants (FS) are attractive for reducing mold adhesion, yet the effects of these additives on nanostructure stability during thermal reflow are not well understood. Here we present thermal stability studies of line-space grating patterns created by Thermal Embossing Nanoimprint Lithography (TENIL) on model polystyrene (PS) films with FS additives. As expected by energy considerations, FS segregates to the air interface, where it seems to facilitate mold release. This also reduces the surface energy and thus reduces the driving force for pattern “slumping” (height decay). However, the beneficial effects of the surfactant are counterbalanced by the fact that the FS decreases the effective film viscosity, which accelerates nanopattern leveling. The net effect is that the pattern height decay is strongly a function of FS concentration. This enhanced film fluidity in the presence of FS also makes the pattern more susceptible to an undulatory capillary instability under thermal reflow conditions. Surface phase segregation of FS and PS is also observed in conjunction with both slumping and lateral capillary instabilities, which may be useful for producing chemically patterned surfaces. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2591–2600, 2009     

Influences of Electrolytes, Polymers and a Surfactant on Rheological Properties of Bentonite–Water Systems

Characteristic rheological properties, such as viscosity, shear stress, yield point, gel strength and thixotropy, of natural Ca- bentonite and Na-peptized bentonite were studied after adding LiCl, KCl, CaCl2, MgCl2·6H2O electrolytes; (NaPO3)n, polyvinyl pyrolidone (PVP) polymers and an anionic surfactant (linear alkyl benzene sulphonate, LABS). Changes in flow properties under the influence of various additives at different quantities were investigated in these slurries. The experimental results are discussed in terms of bentonite forms, types and concentrations of additives and influence of exchangeable cations. Bivalent and monovalent cations display entirely different rheological properties in two groups of muds. Furthermore, the difference in the degree of activity of PVP polymer on the viscosity of two mud systems depend on the clay mineral structure. The slurry prepared with Na-bentonite contains a minimum number of tactoids and a maximum number of sheet-bearing clay particles, which reduces the surface area of the clay minerals and increases viscosity by adding PVP polymer.     

The effects of silica nanoparticles on blue-phase liquid crystals

We investigate the effects of hydrophobic silica nanoparticles (SNs) on blue-phase liquid crystals (BPLCs). The optical microscope and reflection spectra observation reveal that a tiny hydrophobic SN dopant stabilises the BPLC phase, and widens the temperature range of the BP I phase. Furthermore, the doped dilute SNs can fine-tune their positions to relax the formation stress of the BPLC lattices, and slightly increase the platelet sizes of the BPLCs. The doped SNs also decrease the driving voltage and response time of the BPLC cell, because the added SNs decrease the elastic constant of the LC host and the relaxation time constant of the BPLC mixture.     

Hydrogel‐coated polyurethane/urea shape memory polymer foams

Shape memory polymers (SMPs) are a class of responsive polymers that have attracted attention in designing biomedical devices because of their potential to improve minimally invasive surgeries. Use of porous SMPs in vascular grafts has been proposed because porosity aids in transfer of fluids through the graft and growth of vascular tissue. However, porosity also allows blood to leak through grafts so preclotting the materials is necessary. Here hydrogels have been synthesized from acrylic acid and N‐hydroxyethyl acrylamide and coated around a porous SMP produced from lactose functionalized polyurea‐urethanes. The biocompatibility of the polymers used to prepare the cross‐linked shape memory material is demonstrated using an in vitro cell assay. As expected, the hydrogel coating enhanced fluid uptake abilities without hindering the shape memory properties. These results indicate that hydrogels can be used in porous SMP materials without inhibiting the shape recovery of the material. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1389–1395     

H2S‐Activable MOF Nanoparticle Photosensitizer for Effective Photodynamic Therapy against Cancer with Controllable Singlet‐Oxygen Release

Photodynamic therapy (PDT) has emerged as an important minimally invasive tumor treatment technology. The search for an effective photosensitizer to realize selective cancer treatment has become one of the major foci in recent developments of PDT technology. Controllable singlet‐oxygen release based on specific cancer‐associated events, as another major layer of selectivity mode, has attracted great attention in recent years. Here, for the first time, we demonstrated that a novel mixed‐metal metal–organic framework nanoparticle (MOF NP) photosensitizer can be activated by a hydrogen sulfide (H₂S) signaling molecule in a specific tumor microenvironment for PDT against cancer with controllable singlet‐oxygen release in living cells. The effective removal of tumors in vivo further confirmed the satisfactory treatment effect of the MOF NP photosensitizer.     

A Hydrogel Microneedle Assay Combined with Nucleic Acid Probes for On-Site Detection of Small Molecules and Proteins

Point-of-care testing (POCT) of clinical biomarkers is critical to health monitoring and timely treatment, yet biosensing assays capable of detecting biomarkers without the need for costly external equipment and reagents are limited. Blood-based assays are, specifically, challenging as blood collection is invasive and follow-upprocessing is required. Here, we report a versatile assay that employs hydrogel microneedles (HMNs) to extract interstitial fluid (ISF), in a minimally invasive manner integrated with graphene oxide-nucleic acid (GO.NA)-based fluorescence biosensor to sense the biomarkers of interest in situ. The HMN-GO.NA assay is supplemented with a portable detector, enabling a complete POCT procedure. Our system could successfully measure four clinically important biomarkers (glucose, uric acid (UA), insulin, and serotonin) ex vivo, in addition, to accurately detecting glucose and UA in vivo.     

Novel epoxy nanocomposite of low Dk introduced fluorine‐containing POSS structure

A nanoporous additives, polyhedral oilgomeric silisesquioxane containing eight functional hexafluorine groups, octakis(dimethylsiloxyhexafluoropropyl ether)silsesquioxane (OF) has been synthesized and blended with the UV‐cured epoxy resin. The OF containing (10%) epoxy has significantly lower dielectric constant (2.65) than the plain epoxy (3.71). The incorporation of fluorine containing additives is well‐known to reduce dielectric constant due to lower its polarizability. In addition, the presence of the bulky POSS structure is able to create additional free space or pores and further reduces the dielectric constant of the epoxy matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 502–510, 2007     

Photodynamic therapy treatment of early oral and laryngeal cancers

Photodynamic therapy (PDT) is a nonsurgical, minimally invasive treatment that uses a light source to activate light-sensitive drugs or photosensitizers in the treatment of cancer and other diseases. PDT has been successfully employed to treat early carcinomas of the oral cavity and larynx preserving normal tissue and vital functions of speech and swallowing. Two hundred seventy-six patients with early carcinomas of the oral cavity and larynx were treated from 1990 to 2006. Cure rates with a single treatment for early laryngeal and oral cancers were 91% and 94%, respectively. PDT is an effective primary and alternative treatment modality for early oral cavity and laryngeal cancers.     

Heating/Solvent Responsive Shape‐Memory Polymers for Implant Biomedical Devices in Minimally Invasive Surgery: Current Status and Challenge

This review is about the fundamentals and practical issues in applying both heating and solvent responsive shape memory polymers (SMPs) for implant biomedical devices via minimally invasive surgery. After revealing the general requirements in the design of biomedical devices based on SMPs and the fundamentals for the shape‐memory effect in SMPs, the underlying mechanisms, characterization methods, and several representative biomedical applications, including vascular stents, tissue scaffolds, occlusion devices, drug delivery systems, and the current R&D status of them, are discussed. The new opportunities arising from emerging technologies, such as 3D printing, and new materials, such as vitrimer, are also highlighted. Finally, the major challenge that limits the practical clinical applications of SMPs at present is addressed.     

Electrochemical Oxidation of Sulfonamides with Boron-Doped Diamond and Pt Anodes

Electrochemical oxidation processes usually favored specific degradation pathways depending on anode materials. In this work, a series of sulfonamides (SNs) were degraded by electrochemical oxidation. Compared to Pt anodes (0.1567–0.1795 h⁻¹), degradation rates of SNs were much higher at boron-doped diamond (BDD) anodes (2.4290–13.1950 h⁻¹). However, the same intermediates were detected in the two anode systems. Due to the strong oxidizing ability of BDD anodes, a large amount of intermediates with high toxicities were initially generated and then finally reduced in the BDD anode systems, while the amount of intermediates continuously increased in the Pt anode systems. Additionally, SNs were degraded faster in Na₂SO₄ than NaH₂PO₄ electrolytes at BDD anodes, while they were similar at Pt anodes. This study demonstrated that the degradation pathways of SNs at BDD and Pt anodes were similar, but the evolutions of intermediate amounts and toxicities were different due to their varied oxidizing abilities.