Particle-Polymer Union with Changeable Wettability for Constructing Bijels Using a Simple Mixing Method.

Bicontinuous emulsion gels (bijels) are nonequilibrium dispersed systems with particle-stabilized continuous fluid domains, and the internal connectivity of channels brings the possibility of efficient mass transport, endowing bijels great potential in diverse applications. Different from the common method to produce bijels, the spinodal decomposition, which needs precise temperature control and is restricted by the selection of liquid pairs, in this work, a direct mixing method was performed to construct bijels, simplifying the fabrication process. The hydrophilic rod-shaped cellulose nanocrystalline (CNC) particles were in situ combined with the hydrophobic polymer, aminopropyl-terminated polydimethylsiloxane (PDMS-NH2), to acquire a controllable interfacial wettability of CNC. The CNC@mPDMS-NH2 complexes were adsorbed at the water-toluene interface and achieved a change of Pickering emulsion types, oil-in-water, bijel, and water-in-oil, through tuning the interfacial performance of CNC@mPDMS-NH2 complexes. A three-dimensional scanning image and curvature calculation were applied to verify the obtained bijel, further demonstrating the successful preparation of the bicontinuous structure. This work enriched the members of particles for stabilizing bijels and was considered to be scalable in manufacturing for applications on a large scale.

Developing Safe Organohydrogel Sunscreens Using Polyelectrolyte-Betaine Surfactant Complexes.

Oil-in-water emulsions are extensively used in skincare products due to their improved texture, stability, and effectiveness. There is limited success in developing effective delivery systems that can selectively target the active sunscreen ingredients onto the skin surface. Herein, an organohydrogel was prepared by physical cross-linking of an oil-in-water nanoemulsion with chitosan under neutral pH conditions. In the presence of a small quantity of coconut oil, lauramidopropyl betaine and glycerol were able to emulsify the active sunscreen ingredients into nanoscale droplets with enhanced ultraviolet light absorption. A facile pH-triggered interfacial cross-linking approach was applied to transform the nanoemulsion into an organohydrogel sunscreen. Furthermore, the organohydrogel sunscreen displayed encouraging characteristics including efficient UV-blocking capacity, resistance to water, simple removal, and minimal skin penetration. This facile approach provides an effective pathway for scaling up the organohydrogels, which are highly suitable for the safe application of sunscreen.

Biologically Derived Nanoarchitectonic Coatings for the Engineering of Hemostatic Needles.

Bleeding after venipuncture could cause blood loss, hematoma, bruising, hemorrhagic shock, and even death. Herein, a hemostatic needle with antibacterial property is developed via coating of biologically derived carboxymethyl chitosan (CMCS) and Cirsium setosum extract (CsE). The rapid transition from films of the coatings to hydrogels under a wet environment provides an opportunity to detach the coatings from needles and subsequently seal the punctured site. The hydrogels do not significantly influence the healing process of the puncture site. After hemostasis, the coatings on hemostatic needles degrade in 72 h without inducing a systemic immune response. The composition of CMCS can inhibit bacteria of Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus by destroying the membrane of bacteria. The hemostatic needle with good hemostasis efficacy, antibacterial property, and safety is promising for the prevention of bleeding-associated complications in practical applications.

Metal ions confinement defines the architecture of G-quartet, G-quadruplex fibrils and their assembly into nematic tactoids.

G-quadruplex, assembled from a square array of guanine (G) molecules, is an important structure with crucial biological roles in vivo but also a versatile template for ordered functional materials. Although the understanding of G-quadruplex structures is the focus of numerous studies, little is known regarding the control of G-quartet stacking modes and the spontaneous orientation of G-quadruplex fibrils. Here, the effects of different metal ions and their concentrations on stacking modes of G-quartets are elucidated. Monovalent cations (typically K+) facilitate the formation of G-quadruplex hydrogels with both heteropolar and homopolar stacking modes, showing weak mechanical strength. In contrast, divalent metal ions (Ca2+, Sr2+, and Ba2+) at given concentrations can control G-quartet stacking modes and increase the mechanical rigidity of the resulting hydrogels through ionic bridge effects between divalent ions and borate. We show that for Ca2+ and Ba2+ at suitable concentrations, the assembly of G-quadruplexes results in the establishment of a mesoscopic chirality of the fibrils with a regular left-handed twist. Finally, we report the discovery of nematic tactoids self-assembled from G-quadruplex fibrils characterized by homeotropic fibril alignment with respect to the interface. We use the Frank-Oseen elastic energy and the Rapini-Papoular anisotropic surface energy to rationalize two different configurations of the tactoids. These results deepen our understanding of G-quadruplex structures and G-quadruplex fibrils, paving the way for their use in self-assembly and biomaterials.

Guanine Analogue-Based Assemblies: Construction and Luminescence Functions.

As one of the natural nucleobases, guanine has attracted increasing interest in molecular self-assembly science because of its abundant interaction sites and high electron cloud density. Guanines, guanine derivatives, and guanine-rich DNA sequence are able to self-assemble into versatile aggregate structures by the means of hydrogen bonds and π-π, ion-dipole, solvophobic, and electrostatic interactions. Recent advances have shown that many guanine analogue-based (G-based) luminescent aggregates exhibit promising applications for fluorescent and chemiluminescent sensing and circularly polarized luminescence (CPL). This perspective summarizes the state-of-art strategies for constructing G-based assemblies and presents representative examples for luminescence functions. Finally, the inspirations are provided for exploiting unique G-based systems and luminescent G-based assemblies.

Feedback-controlled topological reconfiguration of molecular assemblies for programming supramolecular structures.

In biology, nonequilibrium assembly is characterized by fuel-driven switching between associating and nonassociating states of biomolecules. This dynamic assembly model has been used routinely to describe the nonequilibrium processes in synthetic systems. Here, we present a G-quartet-based nonequilibrium system based on fuel-driven co-assembly of guanosine 5'-monophosphate disodium salt hydrate and urease. Addition of lanthanum(III) ions to the system caused macroscopic dynamic switching between precipitates and hydrogels. Interestingly, combined analyses of the nonequilibrium systems demonstrated that molecules could switch between two distinct associating states without undergoing a nonassociating state. This finding suggested a nonequilibrium assembly mechanism of topological reconfiguration of molecular assemblies. We detailed quantitatively the nonequilibrium assembly mechanism to precisely control the phase behaviors of the active materials; thus, we were able to use the materials for transient-gel-templated polymerization and transient circuit connection. This work presents a new nonequilibrium system with unusual phase behaviors, and the resultant active hydrogels hold promise in applications such as fluid confinements and transient electronics.

Respiratory failure as the prominent manifestation of entecavir-associated mitochondrial myopathy: a case report.

BACKGROUND: Mitochondrial myopathy caused by the long-term use of nucleos(t)ide analogue in patients with chronic hepatitis B (CHB) is mostly characterized by myasthenia and myalgia. Cases with respiratory failure as the prominent manifestation and multisystem symptoms have not been reported. CASE REPORT: We report a case of mitochondrial myopathy associated with the long-term use of entecavir for CHB. The patient was a 54-year-old male who was treated with entecavir for 9 years. During the treatment, hepatitis B virus (HBV) DNA was negative and liver function was normal. However, generalized fatigue, poor appetite, dysosmia and other discomforts gradually presented starting at the 5th year of treatment, and respiratory failure was the prominent manifestation in the later stage of disease progression. The diagnosis was based on histopathology examination. The dysosmia, hypoxemia and digestive tract symptoms were gradually improved after withdrawal of entecavir. DISCUSSION: Mitochondrial myopathy is a rare side effect of entecavir and can be diagnosed by muscle biopsy. Although the incidence is extremely low, but the severe cases can lead to respiratory failure. We should receive adequate attention in clinical practice.

Durability of hepatitis B surface antigen seroclearance and subsequent risk for hepatocellular carcinoma: A meta-analysis.

Hepatitis B surface antigen (HBsAg) seroclearance is regarded as the ideal endpoint for antiviral treatment. However, reports on the durability of and outcomes after HBsAg seroclearance are few, which has become a focus in clinical practice. This meta-analysis was performed to evaluate the durability and hepatocellular carcinoma (HCC) incidence after HBsAg seroclearance after treatment cessation. We searched PubMed, Embase, Medline and Web of Science for studies that reported the durability and HCC incidence after HBsAg seroclearance published between 1 January 2000 and 31 January 2020. Data were analysed by a random-effects model. Thirty-eight studies and 43,924 patients were finally included. The results showed that HBsAg seroclearance was durable, with a pooled recurrence rate of 6.19% (95% CI: 4.10%-8.68%). There was no significant difference in recurrence rates after different seroclearance methods or among recurrence types and different regions. Anti-HBs seroconversion resulted in a significantly reduced recurrence rate (RR = 0.25, p < .001). Patients who experienced HBsAg seroclearance had significantly lower HCC incidence than HBsAg-positive (RR = 0.41, p < .001). The pooled HCC incidence after HBsAg seroclearance was 1.88%; this rate was reduced to 0.76% among patients without baseline cirrhosis. In conclusion, the analysis during an average follow-up of 4.74 years suggested that in patients who experienced sustained HBsAg seroclearance and anti-HBs seroconversion, this was associated with low HCC incidence. Patients without baseline cirrhosis benefited even more. We emphasize the importance of gaining HBsAg seroclearance while highlighting the benefits of achieving this as early as possible.

Functional cure for chronic hepatitis B: accessibility, durability, and prognosis.

Hepatitis B surface antigen (HBsAg) clearance is regarded as the ideal endpoint for antiviral treatment in terms of drug withdrawal safety and improvements in prognosis. However, the overall rate of HBsAg clearance is low and differs based on treatment method and course. The recent application of combined and extended treatment strategies have improved the HBsAg clearance rate, and several patients achieved HBsAg clearance in clinical treatment. In addition, the durability of and clinical outcomes after HBsAg clearance have become the focus of both researchers and clinicians. This article reviews HBsAg clearance in terms of accessibility, durability, improvements in prognosis and relevant advances.

Sono-Fenton Chemistry Converts Phenol and Phenyl Derivatives into Polyphenols for Engineering Surface Coatings.

We report a sono-Fenton strategy to mediate the supramolecular assembly of metal-phenolic networks (MPNs) as substrate-independent coatings using phenol and phenyl derivatives as building blocks. The assembly process is initiated from the generation of hydroxyl radicals (. OH) using high-frequency ultrasound (412 kHz), while the metal ions synergistically participate in the production of additional . OH for hydroxylation/phenolation of phenol and phenyl derivatives via the Fenton reaction and also coordinate with the phenolic compounds for film formation. The coating strategy is applicable to various phenol and phenyl derivatives and different metal ions including FeII , FeIII , CuII , and CoII . In addition, the sono-Fenton strategy allows real-time control over the assembly process by turning the high-frequency ultrasound on or off. The properties of the building blocks are maintained in the formed films. This work provides an environmentally friendly and controllable method to expand the application of phenolic coatings for surface engineering.

Cubic Liquid Crystals of Polyoxometalate-Based Ionic Liquids.

Thermotropic ionic liquid crystals of polyoxometalate (POM)-based ionic liquids (POM-based ILs), which are formed by a POM, K7PW11O39, and cationic surfactants, tetra-n-alkylammonium bromide ((CnH2n+1)4N+Br-, n = 6 and 7), are first proposed. As a model system, the cubic phase structure of a POM-based IL, {(C7H15)4N+}7PW11O39, was determined to form in a wide range of temperatures, exhibiting good thermostability, excellent mechanical strength, and high viscosity. Furthermore, the lyotropic ionic liquid crystals formed by {(C7H15)4N+}7PW11O39 in solvents such as chloroform or toluene still maintained a cubic structure. These cubic ionic liquid crystals (CILCs) were used as anticorrosion coatings both in acidic and neutral environments. The electrochemical measurements of Cu and Fe surfaces coated by CILCs showed an excellent ability of anticorrosion, indicating that the metals can be perfectly protected by the CILC coatings with high resistance and low capacitance. We assume that the CILCs may serve as barriers to stop oxygen diffusing to metals and interrupt the electron tunnels between the metal surfaces and the electrolyte solutions. Such environmentally friendly CILCs of POMs-based ILs are convenient for coating and removal, being vital to versatile industrial and academic applications.

Single network double cross-linker (SNDCL) hydrogels with excellent stretchability, self-recovery, adhesion strength, and conductivity for human motion monitoring.

Hydrogels, as a kind of soft materials, are good candidates for smart skin-like materials. A double network is usually fabricated to improve the mechanical properties of hydrogels, and involves two different kinds of networks. In this work, a novel strategy for preparing single network double cross-linker (SNDCL) hydrogels was proposed and the prepared hydrogels exhibited excellent mechanical properties, including stretchability, compressibility, self-recovery, adhesion, shape memory and mechanical strength. N,N'-Methylenebisacrylamide forms covalent bonds with the network, while citric acid can form multiple weak interactions due to the polycarboxylic structure. This improves the tensile properties (6564%) and compressive properties of the hydrogel, and the hydrogels also exhibit long-lasting self-adhesion ability on various substrates. In addition, the hydrogels with multiple properties can be used as flexible strain sensors, allowing the monitoring of body movements. The hydrogels can hopefully be used in wearable electronic sensor devices and for healthcare monitoring.

A Three-in-One Immunotherapy Nanoweapon via Cascade-Amplifying Cancer-Immunity Cycle against Tumor Metastasis, Relapse, and Postsurgical Regrowth.

The antitumor immune response involves a cascade of three phases, namely, antigen presentation (Phase I), lymphocyte activation and proliferation/differentiation (Phase II), and tumor elimination (Phase III). Therefore, an ideal immunotherapy nanoplatform is one that can simultaneously execute these three phases. However, it is of great challenge to develop a single immunotherapy nanoplatform which can deliver individual immunoagent to their on-demand target sites for simultaneously tailoring three phases because of the different target sites restricted by three phases. Herein, for the first time we reported a three-in-one immunotherapy nanoplatform that can simultaneously execute these three phases. Chlorin e6 (Ce6)-conjugated hyaluronic acid (HC), dextro-1-methyl tryptophan (1-mt)-conjugated polylysine (PM) and anti-PD-L1 monoclonal antibodies (aPD-L1) were rationally designed as aPD-L1@HC/PM NPs via an assembling strategy. The step-by-step detachment of the antigen from near-infrared light irradiated HC component, the indoleamine-pyrrole 2,3-dioxygenase (IDO) pathway inhibitor 1-mt, and the anti-PD-L1 toward their on-demand target sites demonstrated the simultaneous tailoring of Phase I, Phase II, and Phase III, respectively, of the immunotherapy. The aPD-L1@HC/PM NPs were verified to be an excellent immunotherapy nanoplatform against tumor metastasis, relapse, and postsurgical regrowth because of the cascade-amplifying cancer-immunity cycle. The present all-immunity-phase-boosted immunotherapy strategy is of great interest for designing excellent immunotherapy treatments.

Foxp3+Helios+ regulatory T cells are associated with monocyte subsets and their PD-1 expression during acute HIV-1 infection.

BACKGROUND: Helios has been reported to stabilize regulatory T (Treg) suppressive function. Programmed cell death protein 1 (PD-1) expression in three human monocyte subsets modulates immune responses. Recently, our team reported that three monocyte subsets are associated with T helper cell differentiation in HIV-1-infected patients. Until now, the effects of monocyte subsets and their PD-1 expression on Foxp3+Helios+ Treg cells have not been fully characterized, especially during acute HIV-1 infection. RESULTS: The frequency of Foxp3+Helios+CD45RA+ Treg cells is significantly higher in patients with acute HIV-1 infection than those of healthy controls and chronic HIV-1-infected patients undergoing combined antiretroviral therapy. The frequency of Foxp3+Helios+CD45RA+ Treg cells is inversely correlated with CD4 T-cell counts and the CD4/CD8 ratio in chronic HIV-1-infected patients. During acute HIV-1 infection, the frequency of Foxp3+Helios+CD45RA+ Treg cells is inversely correlated with the frequency of the intermediate CD14++CD16+ monocyte subset, but positively correlated with PD-1 expression in both intermediate CD14++CD16+ and non-classical CD14+CD16++ monocyte subsets. CONCLUSIONS: In this study, the perturbations of Foxp3+Helios+ Treg cells were characterized, and the association between monocyte subsets and their PD-1 expression and Foxp3+Helios+ Treg cells was evaluated during HIV-1 infection. Our observations provide new evidence of the roles for Foxp3+Helios+ Treg cells and PD-1 expression on monocyte subsets in HIV pathogenesis.

Diagnostic effect of shear wave elastography imaging for differentiation of malignant liver lesions: a meta-analysis.

BACKGROUND: Shear wave elastography (SWE) imaging have been proposed for characterization of focal liver lesions. We conducted a meta-analysis to evaluate the accuracy and clinical utility of SWE imaging for differentiation of malignant and benign hepatic lesions. METHODS: PubMed, Embase, Web of Science, and the Cochrane Library were systematically reviewed to search for studies published between January 1, 1990, and November 30, 2018. The studies published in English relating to the evaluation the diagnostic accuracy of SWE imaging for distinguishing malignant and benign liver lesions were retrieved and examined for pooled sensitivity, specificity, likelihood ratios, and diagnostic odds ratios, using bivariate random-effects models. The hierarchical summary receiver operating characteristic (HSROC) curve was estimated to assess the SWE imaging accuracy. The clinical utility of SWE imaging for differentiation of malignant liver lesions was evaluated by Fagan plot. RESULTS: A total of 15 studies, involving 1894 liver lesions in 1728 patients, were eligible for the meta-analysis. The pooled sensitivity and specificity for identification of malignant liver lesions were 0.82 (95% CI: 0.77-0.86) and 0.82 (95% CI: 0.76-0.87), respectively. The AUC was 0.89 (95% CI: 0.86-0.91). When the pre-test probability was 50%, after SWE imaging measurement over the cut-off value (positive result), the corresponding post-test probability for the presence of malignant liver lesions was 82%; the post-test probability was 18% after negative measurement. CONCLUSIONS: SWE imaging showed high sensitivity and specificity in differentiating malignant and benign liver lesions and may be promising for noninvasive evaluation of liver lesions. TRIAL REGISTRATION: The review was registered in the International Prospective Register of Systematic Reviews (PROSPERO): CRD42018104510 .

Ionic-surfactants-based thermotropic liquid crystals.

Thermotropic liquid crystals (TLCs) are a series of soft materials with ordered arrangements of repeating structural units in a certain range of temperature. Specifically, the TLCs constructed by the electrostatic combination between ionic surfactants and other oppositely charged groups have received great attention in the field of optoelectronic devices, material transportation and separation, smart materials as well as biosensing. As typical amphiphilic molecules, ionic surfactants with charged head-groups and long alkyl tails exhibit unique self-assembly behaviors, being preferable as flexible building blocks of TLCs. In this review, we have discussed the TLCs formed by salt-free catanionic surfactants and ionic surfactants with other functional groups, including metal ions, nanoclusters, biomolecules, and polyelectrolytes. The design of such TLC molecules, the influencing factors of the mesophases, and the related applications of the TLCs are discussed in detail. Because of their easy preparation and variable structure, these TLCs are expected to greatly widen the application scope of the relevant functional molecules. At the end of this review, we put forward some ideas with regard to the aspects that are required to be improved and propose the possible development trend in this direction. It is expected that through this review, the important roles of ionic surfactants in building TLCs will be highlighted and thus, more studies will be inspired to exploit more TLCs based on ionic surfactants with excellent properties.

Rational Design of IR820- and Ce6-Based Versatile Micelle for Single NIR Laser-Induced Imaging and Dual-Modal Phototherapy.

Phototherapy as a promising cancer diagnostic and therapeutic strategy has aroused extensive attention. However, single-wavelength near-infrared (NIR) light-triggered combinational treatment of photothermal therapy (PTT) and photodynamic therapy (PDT) is still a great challenge. Herein, a multifunctional micelle activated by a single-wavelength laser for simultaneous PTT and PDT as well as fluorescence imaging is developed. Briefly, new indocyanine green (IR820) is conjugated to d-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) via the linker 6-aminocaproic acid, and then, chlorin e6 (Ce6) is encapsulated into the micelles formed by TPGS-IR820 conjugates to fabricate TPGS-IR820/Ce6 micelles. As the well-designed TPGS-IR820 conjugate shares a similar peak absorption wavelength with Ce6, this micelle can be applied with a single NIR laser (660 nm). The stable micelles exhibit excellent photothermal conversion efficiency in vitro and in vivo as well as high singlet oxygen generation capacity in tumor cells. After efficient cellular internalization, the as-prepared micelles display outstanding anticancer activity upon single NIR laser irradiation in vitro and in vivo. Furthermore, TPGS-IR820/Ce6 micelles show negligible systemic toxicity. The highly safe and effective TPGS-IR820/Ce6 micelles can offer an innovative strategy to construct single NIR light-induced PTT and PDT combined phototherapy nanoplatforms via suitable modification of organic phototherapeutic agents.

Effect of Cationic Surfactants with Different Counterions on the Growth of Au Nanoclusters.

The influence of a series of cationic surfactants composed of cetyltrimethylammonium cations with different counterions (Br-, Cl-, OH-, C7H8O3S-, [CeCl3Br]-, and NO3-) on the aging process of gold nanoclusters (Au NCs) was studied. The finely different points of Au NCs treated by different surfactants were demonstrated by UV-vis and fluorescence spectra, transmission electron microscopy images, etc. Because of the difference of counterions, these surfactants have diverse physicochemical properties in surface activity, specific conductivity, pH, and viscosity, which may account for the difference of Au NCs in the aging process. In addition, the affinity of the counterions in surfactants to the surface of Au has also been demonstrated completely. This affinity may further guide the difference of the synthesized Au nanomaterials.

Hydrogels Based on Ag+ -Modulated Assembly of 5'-Adenosine Monophosphate for Enriching Biomolecules.

Supramolecular hydrogels obtained by combining 5'-adenosine monophosphate (AMP) with Ag+ were fabricated in this work. Their gelation capability was enhanced by increasing the concentration of Ag+ or decreasing the pH. The gels are very sensitive to light, which endows them with potential applications as visible-light photosensitive materials. Coordination between the nucleobase of AMP and Ag+ , as well as π-π stacking of nucleobases, are considered to be the main driving forces for self-assembly. The hydrogels successfully achieved the encapsulation and enrichment of biomolecules. Hydrogen bonding between the amino group of guest molecules and silver nanoparticles along the nanofibers drives the enrichment and is considered to be a crucial interaction.

Ultrafine Au and Ag Nanoparticles Synthesized from Self-Assembled Peptide Fibers and Their Excellent Catalytic Activity.

The self-assembly of an amphiphilic peptide molecule to form nanofibers facilitated by Ag(+) ions was investigated. Ultrafine AgNPs (NPs=nanoparticles) with an average size of 1.67 nm were synthesized in situ along the fibers due to the weak reducibility of the -SH group on the peptide molecule. By adding NaBH4 to the peptide solution, ultrafine AgNPs and AuNPs were synthesized with an average size of 1.35 and 1.18 nm, respectively. The AuNPs, AgNPs, and AgNPs/nanofibers all exhibited excellent catalytic activity toward the reduction of 4-nitrophenol, with turnover frequency (TOF) values of 720, 188, and 96 h(-1) , respectively. Three dyes were selected for catalytic degradation by the prepared nanoparticles and the nanoparticles showed selective catalysis activity toward the different dyes. It was a surprising discovery that the ultrafine AuNPs in this work had an extremely high catalytic activity toward methylene blue, with a reaction rate constant of 0.21 s(-1) and a TOF value of 1899 h(-1) .