One-pot asymmetric living copolymerization-induced chiral self-assemblies and circularly polarized luminescence.

Controlled synthesis of conjugated block polymers enables the optimization of their self-assembly and may lead to distinct optical properties and functionalities. Herein, we report a direct chain extension of one-handed helical poly(acyl methane) with 1-ethynyl-4-iodo-2,5-bis(octyloxy)benzene, affording well-defined π-conjugated poly(acyl methane)-b-poly(phenylene ethynylene) copolymers. Although the distinct monomers are polymerized via different mechanisms, the one-pot copolymerization follows a living polymerization manner, giving the desired optically active block copolymers with controllable molar mass and low distribution. The block copolymerization induced chiral self-assembly simultaneously due to the one-handed helicity of the poly(acyl methane) block, giving spherical nanoparticles, one-handed helices, and chiral micelles with controlled dimensions regarding the composition of the generated copolymers. Interestingly, the chiral assemblies exhibit clear circularly polarized luminescence with tunable handedness and a high dissymmetric factor.

First-principles prediction of the thermal conductivity of two configurations of difluorinated graphene monolayer.

Lattice thermal conductivity (κL) plays a crucial role in the thermal management of electronic devices. In this study, we systematically investigate the thermal transport properties of monolayer fluorinated graphene using a combination of machine learning-based interatomic potentials and the phonon Boltzmann transport equation. At a temperature of 300 K, we find that the κL values for chair-configured fluorinated graphene monolayers are 184.24 W m-1 K-1 in the zigzag direction and 205.57 W m-1 K-1 in the armchair direction. For the boat configuration, the κL values are 120.45 W m-1 K-1 and 64.26 W m-1 K-1 in the respective directions. The disparities in κL between these two configurations predominantly stem from differences in phonon relaxation times, which can be elucidated by examining the Grüneisen parameters representing the degree of anharmonicity. A more in-depth analysis of bond strengths, as assessed by the crystal orbital Hamiltonian population, reveals that the stronger in-plane CC bonds in chair-configured fluorinated graphene monolayers are the primary contributors to the observed variations in anharmonicity.

Controlled synthesis of cyclic helical polyisocyanides and bottlebrush polymers using a cyclic alkyne-Pd(II) catalyst.

Cyclic polymers have very unique structure and properties, and thus have drawn intense research attention. However, controlled synthesis of cyclic polymers with predictable molar mass and narrow distribution is still a challenging task. In this study, we developed a novel cyclic catalyst that initiates the ring-expansion polymerisation of isocyanides, producing a series of cyclic helical polymers with predictable molecular weight and low dispersity. Interestingly, the ring-expansion polymerization of the isocyanide macromonomers gives well-defined cyclic bottlebrush polymers. The cyclic topology was demonstrated using transmission electron microscopy.

A study on the influencing factors and related paths of farmer's participation in food safety governance-based on DEMATEL-ISM-MICMAC model.

Farmers' participation in food safety governance is an important part of food safety social co-governance, and the accurate identification of its influencing factors and their related paths is of guiding significance to the scientific decision-making of food safety governance. The system of influencing factors of farmers' participation in food safety governance was constructed from four dimensions, and the influence network of each dimension was revealed by decision laboratory analysis (DEMATEL). The hierarchical structure and correlation path of influencing factors were determined by interpretive structural model (ISM), and the attributes of influencing factors were further classified by cross influence matrix multiplication (MICMAC). The results show that the influencing factors of farmers' participation in food safety governance can be divided into seven levels, among which the level of education and the status of village cadres are the fundamental characteristic factors. The degree of rural informatization, the intensity of government supervision, the promotion of village committees, the response of the government and the degree of disclosure of government information are the deep core factors, and risk cognition, political trust and family eating habits are special factors. Taking the importance and attribute status of farmers' participation in food safety governance into decision-making considerations is of great significance to improve the efficiency of food safety governance.

Self-assembly and interaction mechanisms of edible dock protein and flavonoids regulated by the phenolic hydroxyl position.

In this study, chrysin (Chr), baicalein (Bai), apigenin (Api) and galangin (Gal) were selected as the representative flavonoids with different position of phenolic hydroxyl groups, and edible dock protein (EDP) was used as a material to construct delivery system. Subsequently, the molecular interactions and functional properties of flavonoids-loaded EDP nanomicelles were investigated. Results exhibited that hydrogen bond, hydrophobic interaction and van der Waals force were the main driving forces for self-assembly of flavonoids and EDP molecules. Meanwhile, this self-assembly remarkably enhance the storage and digestion stability of flavonoid compounds. Among four flavonoids, the order of loading ability was: Api > Gal > Bai > Chr. Herein, Api had a largest loading capacity (6.74%) because of its active phenolic hydroxyl group in ring B. These results suggested that the position of phenolic hydroxyl groups in flavonoids is a key factor to regulate its self-assembly with protein molecules.

Cyclic Polymers: Controlled Synthesis, Properties and Perspectives.

Recently, cyclic polymers have attracted increasing interest due to their unique topologies, properties, and functions compared to the linear analogues. This mini-review focuses on the recent advances in the synthesis and applications of cyclic polymers. First, the main synthetic methods for cyclic polymers, namely ring closure and ring expansion methods, are presented and discussed, followed by a review on the exploration of the properties and applications of synthetic cyclic polymers. Finally, a critical assessment of the preliminary studies exploring the efficient synthesis and potential applications of cyclic polymers are presented, and the remaining challenges in the field as well as ideas for solving these challenges will be discussed.

Ketone bodies promote stroke recovery via GAT-1-dependent cortical network remodeling.

Stroke is a leading cause of adult disability worldwide, and better drugs are needed to promote functional recovery after stroke. Growing evidence suggests the critical role of network excitability during the repair phase for stroke recovery. Here, we show that ß-hydroxybutyrate (ß-HB), an essential ketone body (KB) component, is positively correlated with improved outcomes in patients with stroke and promotes functional recovery in rodents with stroke during the repair phase. These beneficial effects of ß-HB depend on HDAC2/HDAC3-GABA transporter 1 (GAT-1) signaling-mediated enhancement of excitability and phasic GABA inhibition in the peri-infarct cortex and structural and functional plasticity in the ipsilateral cortex, the contralateral cortex, and the corticospinal tract. Together with available clinical approaches to elevate KB levels, our results offer a clinically translatable means to promote stroke recovery. Furthermore, GAT-1 can serve as a pharmacological target for developing drugs to promote functional recovery after stroke.

Visible Helicity Induction and Memory in Polyallene toward Circularly Polarized Luminescence, Helicity Discrimination, and Enantiomer Separation.

Inspired by biological helices (e.g., DNA), artificial helical polymers have attracted intense attention. However, precise synthesis of one-handed helices from achiral materials remains a formidable challenge. Herein, a series of achiral poly(biphenyl allene)s with controlled molar mass and low dispersity were prepared and induced into one-handed helices using chiral amines and alcohols. The induced one-handed helix was simultaneously memorized, even after the chiral inducer was removed. The switchable induction processes were visible to naked eye; the achiral polymers exhibited blue emission (irradiated at 365 nm), whereas the induced one-handed helices exhibited cyan emission with clear circularly polarized luminescence. The induced helices formed stable gels in various solvents with helicity discrimination ability: the same-handed helix gels were self-healing, whereas the gels of opposite-handed helicity were self-sorted. Moreover, the induced helices could separate enantiomers via enantioselective crystallization with high efficiency and switchable enantioselectivity.

Tachykinin receptor 3 in the lateral habenula alleviates pain and anxiety comorbidity in mice.

The coexistence of chronic pain and anxiety is a common clinical phenomenon. Here, the role of tachykinin receptor 3 (NK3R) in the lateral habenula (LHb) in trigeminal neuralgia and in pain-associated anxiety was systematically investigated. First, electrophysiological recording showed that bilateral LHb neurons are hyperactive in a mouse model of trigeminal neuralgia made by partial transection of the infraorbital nerve (pT-ION). Chemicogenetic activation of bilateral LHb glutamatergic neurons in naive mice induced orofacial allodynia and anxiety-like behaviors, and pharmacological activation of NK3R in the LHb attenuated allodynia and anxiety-like behaviors induced by pT-ION. Electrophysiological recording showed that pharmacological activation of NK3R suppressed the abnormal excitation of LHb neurons. In parallel, pharmacological inhibition of NK3R induced orofacial allodynia and anxiety-like behavior in naive mice. The electrophysiological recording showed that pharmacological inhibition of NK3R activates LHb neurons. Neurokinin B (NKB) is an endogenous high-affinity ligand of NK3R, which binds NK3R and activates it to perform physiological functions, and further neuron projection tracing showed that the front section of the periaqueductal gray (fPAG) projects NKB-positive nerve fibers to the LHb. Optogenetics combined with electrophysiology recordings characterize the functional connections in this fPAG NKB → LHb pathway. In addition, electrophysiological recording showed that NKB-positive neurons in the fPAG were more active than NKB-negative neurons in pT-ION mice. Finally, inhibition of NKB release from the fPAG reversed the analgesic and anxiolytic effects of LHb Tacr3 overexpression in pT-ION mice, indicating that fPAG NKB → LHb regulates orofacial allodynia and pain-induced anxious behaviors. These findings for NK3R suggest the cellular mechanism behind pT-ION in the LHb and suggest that the fPAG NKB → LHb circuit is involved in pain and anxiety comorbidity. This previously unrecognized pathway might provide a potential approach for relieving the pain and anxiety associated with trigeminal neuralgia by targeting NK3R.

Tuning interfacial thermal conductance of GaN/AlN heterostructure nanowires by constructing core/shell structure.

The ability to tune the interfacial thermal conductance of GaN/AlN heterojunction nanowires (NWs) with a core/shell structure is shown using molecular dynamics and non-equilibrium Green's functions method. In particular, an increase in the shell thickness leads to a significant improvement of interfacial thermal conductance of GaN/AlN core/shell NWs. At room temperature (300 K), the interfacial thermal conductance of NWs with specific core/shell ratio can reach 0.608 nW K-1, which is about twice that of GaN/AlN heterojunction NWs due to the weak phonon scattering and phonon localization. Moreover, changing the core/shell type enables one to vary interfacial thermal conductance relative to that of GaN/AlN heterojunction NWs. The results of the study provide an important guidance for solving the thermal management problems of GaN-based devices.

The role of altered fatty acid in pathological scars and their dermal fibroblasts.

PURPOSE: The proposed pathological mechanism for scar formation is controversial, and increased attention has been paid to the fatty acids (FAs) in the formation of pathological scars. Notably, FAs are known to be important in inflammation and mechanotransduction, which is closely related to scar formation. Therefore, it is necessary to clarify the roles of FA in scar formation. METHODS: Hypertrophic scar and keloid formed for more than a year and without other treatment, as well as normal skin samples were obtained from patients who underwent plastic surgery. Finally, keloids (n = 10), hypertrophic scars (n = 10), and normal skin samples (n = 10) were collected under informed consent. Primary dermal fibroblasts were isolated and cultured. The amount and variety of FAs were detected by lipid chromatography-mass spectrometry. Immunohistochemistry, real-time PCR, and western blotting were used to verify the expression of sterol regulatory element-binding protein-1 (SREBP1) and fatty acid synthase (FASN) in the samples and their fibroblasts. Student's t-test, ANOVA, and orthogonal partial least square discriminant analysis were performed for statistical analysis (∗p < 0.05, ∗∗p < 0.01, ∗∗∗p < 0.001, ∗∗∗∗p < 0.0001). RESULTS: Compared with full-thickness normal skin, there were 27 differential FAs in keloids and 15 differential FAs in hypertrophic scars (∗p < 0.05 and variable influence on projection >1.0). The expression of SREBP1 and FASN was lower in pathological scars both at mRNA and protein levels (all ∗p < 0.05). However, the mRNA levels of SREBP1 (∗∗∗p = 0.0002) and FASN (∗∗∗p = 0.0021) in keloid-derived fibroblasts were higher than that in normal skin fibroblasts (NFBs), while the expression in hypertrophic scar-derived fibroblasts was lower than that in NFBs (both ∗p < 0.05). Whereas there was no significant difference in FASN protein expression between keloid-derived fibroblasts and NFBs (p > 0.05). CONCLUSION: FAs involved in pathological scars are abnormally changed in scar formation. Thus, fatty acid-derived inflammation and de novo synthesis pathway of FA may play a key role in the formation of pathological scars.

Diagnostic cut-off value for Aspergillus fumigatus- and flavus-specific IgG with clinical relevance in chronic pulmonary Aspergillus infection: A pilot study in Taiwan.

BACKGROUND: The diagnostic cut-off value for chronic pulmonary Aspergillosis (CPA) by Aspergillus fumigatus-specific IgG has never been evaluated In Taiwan. The cut-off value for Aspergillus flavus-specific IgG has not been evaluated worldwide. OBJECTIVES: Evaluate diagnostic cut-off value of Aspergillus IgG and its application characteristics. PATIENTS/METHODS: Blood from control groups and treatment-naïve patients with CPA infections was collected for Aspergillus-specific IgG measurements. Controls were patients who had chest radiographic abnormalities and signs of respiratory tract infection, but were negative for Aspergillus and resolved without anti-mould therapy. Confirmation and probability of CPA were defined according to radiological features and positivity for an Aspergillus or galactomannan index. Chest computer tomography patterns were recorded for the presence of aspergilloma or nodules, subacute invasive aspergillosis, chronic cavitary pulmonary aspergillosis and chronic fibrotic pulmonary aspergillosis. RESULTS: A total of 35 cases and 50 disease controls were included. The levels of A. fumigatus- and A. flavus-specific IgG correlated with CPA progression (P < .05) but not with the presence of Aspergillus species from clinical specimens (P > .05). The best cut-off value for A. fumigatus IgG was 21.7 mg/L with area under curve (AUC) for receiver operating characteristic curve (ROC) 0.934 and had 85.7% sensitivity and 92.0% specificity. For A. flavus IgG, the best cut-off value was 22.1 mgA/L and the AUC was 0.928 with 88.2% sensitivity and 94.1% specificity. CONCLUSION: The level of Aspergillus-specific IgG correlated with radiographic characteristics in patients with CPA and the best cut-off values compared to controls were 21.7 mgA/L for A. fumigatus-specific IgG and 22.1 mgA/L for A. flavus-specific IgG.

Direct intramolecular amination of tryptophan esters to prepare pyrrolo[2,3-b]indoles.

A metal-free iodine-catalyzed intramolecular amination has been developed for the practical synthesis of pyrrolo[2,3-b]indoles from readily available tryptophan esters. The transformation has been applied to a wide array of substrates and can be performed on gram scale under very mild conditions.

Biohydrogen production from waste bread in a continuous stirred tank reactor: A techno-economic analysis.

Biohydrogen production from waste bread in a continuous stirred tank reactor (CSTR) was techno-economically assessed. The treating capacity of the H2-producing plant was assumed to be 2 ton waste bread per day with lifetime of 10years. Aspen Plus was used to simulate the mass and energy balance of the plant. The total capital investment (TCI), total annual production cost (TAPC) and annual revenue of the plant were USD931020, USD299746/year and USD639920/year, respectively. The unit hydrogen production cost was USD1.34/m3 H2 (or USD14.89/kg H2). The payback period and net present value (NPV) of the plant were 4.8years and USD1266654, respectively. Hydrogen price and operators cost were the most important variables on the NPV. It was concluded that biohydrogen production from waste bread in the CSTR was feasible for practical application.

Expression of stromal cell-derived factor-1 in diabetic retinopathy.

BACKGROUND: Neovascularization can cause vision loss in proliferative diabetic retinopathy (PDR) and may be affected by many factors. Stromal cell-derived factor-1 (SDF-1) is a potent stimulator of angiogenesis. The study was aimed to investigate the expression of SDF-1 and its correlation with vascular endothelial growth factor (VEGF) in the eyes with diabetic retinopathy. METHODS: The levels of SDF-1 and VEGF were measured by enzyme-linked immunosorbent assay in the vitreous of 41 eyes of 41 patients with PDR and 12 eyes of 12 patients with idiopathic macular hole (IMH). Vitreous fluid samples and fibrovascular preretinal membranes were obtained at vitrectomy. SDF-1 and VEGF were localized using immunohistochemistry. RESULTS: The vitreous concentration of VEGF was significantly higher in eyes with PDR ((2143.7 +/- 1685.21) pg/ml) than in eyes with IMH ((142.42 +/- 72.83) pg/ml, P < 0.001). The vitreous level of SDF-1 was also significantly higher in eyes with PDR ((306.37 +/- 134.25) pg/ml) than in eyes with IMH ((86.91 +/- 55.05) pg/ml, P < 0.001). The concentrations of both VEGF and SDF-1 were higher in eyes with active PDR than in eyes with inactive PDR. Panretinal photocoagulation (PRP) could decrease the SDF-1 levels in the vitreous of PDR patients. The vitreous concentration of SDF-1 correlated with that of VEGF in eyes with PDR (r = 0.61, P < 0.001). The costaining of SDF-1 and VEGF was confined to the vascular components in preretinal membranes. CONCLUSIONS: SDF-1 protein is highly expressed in both the vitreous and preretinal membranes of PDR patients; SDF-1 may be correlated with VEGF in angiogenesis in PDR.

Caspase-dependent retinal ganglion cell apoptosis in the rat model of acute diabetes.

BACKGROUND: Neural apoptosis is generally believed to be mediated by two distinct pathways, caspase-dependant and caspase-independent pathways. This study investigated the apoptotic pathways involved in retinal ganglion cells in acute diabetes in rats. METHODS: Diabetes was induced in male Wistar rats by a peritoneal injection of streptozotocin (STZ). Expression and localization of caspase-3 and apoptosis-inducing factor (AIF) proteins in the retina of diabetic rats was examined by Western blotting and immunohistochemistry analyses. Terminal transferase dUTP nick end labeling (TUNEL) assay and immunofluorescent staining specific for caspase-3 and AIF were applied to analyze for apoptosis of retinal ganglion cells. In addition, a caspase-3 inhibitor DEVD-CHO was injected intravitreally to further determine the apoptotic pathways of retinal ganglion cells triggered in acute diabetes. RESULTS: Two weeks after induction of diabetes, a significant increase in caspase-3 protein expression and localization occurred in the nerve fiber layer, ganglion cell layer, and inner plexiform layer of the retina. Four weeks after the onset of diabetes, the increase in caspase-3 expression was profound eight weeks postinduction of diabetes (P < 0.05). Meanwhile, no AIF protein expression was detected in this study. In addition, intravitreal administration of the caspase-3 inhibitor DEVD-CHO reduced apoptosis of retinal ganglion cells by its direct inhibitory action on caspase-3. CONCLUSION: Caspase-dependent apoptotic pathways may be the main stimulant of STZ-induced retinal ganglion cell apoptosis in acute diabetes.