Alterations in oxidative stress biomarkers and helper T-cell subgroups in patients with periodontitis and IgA nephropathy.

OBJECTIVE: Investigating the changes in the oxidative stress levels and helper T lymphocyte (Th) subsets in patients with periodontitis and IgA nephropathy (IgAN) to determine their relationship. BACKGROUND: IgAN has a high prevalence, poor prognosis, and no effective cure. Accumulating evidence has implicated a close relationship between periodontitis and chronic kidney diseases, in which both IgAN and chronic periodontitis show chronic inflammation and abnormal metabolism. However, few studies have been conducted on the relationship between the two diseases from this perspective. METHODS: We divided 86 IgAN patients into patients with healthy periodontium (IgAN-H, n = 34) and patients with periodontitis IgAN (IgAN-P, n = 52); moreover, we divided 72 systemically healthy participants into patients with periodontitis (H-P, n = 35) and participants with healthy periodontium (H-H, n = 37). The proportions of Th subsets in peripheral blood were estimated using flow cytometry. Cytokine levels in plasma were assessed using cytokine assay kits. Enzyme-linked immunosorbent assay was used to evaluate the plasma levels of oxidative stress. RESULTS: Our results from analyzing the Th cell subsets indicated that Th2 cell counts in the IgAN-P group were significantly lower than those in the IgAN-H group, while Th17 cell counts were increased (p < 0.05). Moreover, the Th1/Th2 ratio and interleukin-6 levels in the IgAN-P group were significantly higher than those in the H-H group (p < 0.01). Compared with that in the H-H group, in the remaining three groups, plasma total oxidation state (TOS) levels were increased (p < 0.01), while plasma total antioxidant state (TAS) levels were decreased (p < 0.05). Furthermore, estimated glomerular filtration rate was negatively correlated with the probing depth and gingival bleeding index. IgAN was a risk factor for periodontitis, while TAS was a protective factor for periodontitis. The oxidative stress index (OSI) might be valuable for distinguishing periodontitis patients from healthy controls (area under the receiver operator characteristic curve = 0.951). CONCLUSION: IgAN is an independent risk factor of periodontitis, and the Th17 cell-mediated inflammatory response might be associated with the occurrence of periodontitis in patients with IgAN. Patients with coexisting IgAN and periodontitis exhibit increased oxidative stress, in which TOS and OSI are potential biomarkers for diagnosing periodontitis.

Effect of type 2 diabetes mellitus and periodontitis on the Th1/Th2 and Th17/Treg paradigm.

PURPOSE: To investigate the effect of type 2 diabetes mellitus (T2DM) and periodontitis on the Th1/Th2/Th17/Treg paradigm. METHODS: A total of 107 volunteers (aged 18-78 years) were recruited. Peripheral blood samples from patients with periodontitis and T2DM (n= 43), patients with periodontitis only (n= 20), patients with T2DM only (n= 23), and healthy controls (n= 21) were collected. Blood pressure, glycated hemoglobin, fasting plasma glucose, probing depth, gingival index, and clinical attachment loss were measured. The circulating proportions of Th1, Th2, Th17, and Treg cells were estimated by flow cytometry. The data were analyzed by a 2x2 factorial ANOVA. RESULTS: We observed higher ratios of Th1/Th2 and Th17/Treg cells among patients with T2DM (P< 0.05) than among healthy controls. The proportion of Th17 cells in patients with periodontitis and T2DM was higher than that in other groups (P< 0.05). T2DM exhibited a predominant effect on the proportion of Th1 cells (F= 18.127, P= 0.000) and the Th17/Treg ratio (F= 45.384, P= 0.000). A significant "T2DM x periodontitis" interaction effect on the proportion of Th2, Th17, Treg cells, and the Th1/Th2 ratio (P< 0.05) was also noticed. The area under curve of Th17 was 0.711 (95% CI= 0.584 to 0.803, P< 0.01) in the receiver operating characteristic curve analysis. CLINICAL SIGNIFICANCE: The results suggest that the proportion of Th2, Th17, Treg cells and the Th1/Th2 ratio is indicative of immune activation and inflammation, which are evident in patients with type 2 diabetes mellitus (T2DM) and periodontitis. The data indicate that the high expression of Th17 cells may be a relevant biological factor that can be associated with an increased risk of developing chronic periodontitis in patients with T2DM.

Sequential posterior interosseous artery perforator flap for reconstruction of dorsal hand defects.

Dorsal hand defects accompanied by exposure of bones and tendons remain a huge challenge for plastic surgeons. The pedicled perforator flaps have unique advantages in resurfacing the defects. This study aimed to investigate the clinical efficacy of the sequential posterior interosseous artery perforator flap for repairing dorsal hand defects. This study was composed of an anatomical study and clinical application. Anatomically, 30 adult upper limb specimens injected with red latex were dissected, the perforators from the branches of the posterior interosseous artery were observed in the dorsal forearm, and the sequential flap based on them was designed based on the anatomical characteristics. Clinically, nine cases of soft tissue defects on the dorsum of the hand were treated by this flap. Anatomically, the posterior interosseous artery divided into an ascending branch and a descending branch, and the descending branch traveled 1.0 ± 0.3 cm down to divide into the ulnar and radial terminal branches. The ulnar terminal branch presented constantly, and the radial terminal branch had an occurrence rate of 93.33%. Clinically, all flaps survived completely and possessed a soft texture and satisfactory appearance, as well as a nonbloated pedicle, and the donor region had a natural color and appearance with only a linear scar left behind. The sequential posterior interosseous artery perforator flap could become a useful option for repairing dorsal hand defects, as it has the advantages of being easy to perform without sacrificing the main vessels and avoiding donor area skin grafting.

Clinical Outcomes of Self-Made Polyurethane-Covered Stent Implantation for the Treatment of Coronary Artery Perforations.

OBJECTIVES: The present study aimed to investigate the short- and long-term clinical outcomes of self-made polyurethane-covered stents (PU-CS) in patients for the management of coronary artery perforation (CAP) during percutaneous coronary intervention (PCI). BACKGROUND: Coronary artery perforation is reckoned as a serious complication in PCI and associated with considerable morbidity and mortality. Covered stents have been used for treating the life-threatening CAP during PCI. But in some catheterization laboratories, no commercial CS is immediately available when there is an urgent need for CS to rescue the coronary rupture site. METHODS: We retrospectively identified 24 patients who underwent 31 self-made PU-CS implantations due to CAP in Zhongshan Hospital, Fudan University, from June 2015 to January 2020. RESULTS: The total procedural success rate of CS to seal the perforation was 79.2%. Nine patients (37.5%) developed cardiac tamponade, of which 8 patients (33.3%) underwent pericardiocentesis and 4 patients (16.7%) underwent cardiac surgeries. Except for 4 cardiac death cases (16.7%), none of myocardial infarction (MI), target lesion revascularization (TLR), and stent thrombosis (ST) was reported during hospital stay. Data from 22 patients (91.7%) were available at 610.4 ± 420.9 days of follow-up. Major adverse cardiac events (MACE) occurred in 6 patients (27.3%), including 5 cases of cardiac death and one TLR case. CONCLUSIONS: Self-made PU-CS demonstrates high rates of successful delivery and sealing of severe CAP during PCI. Although the in-hospital mortality remains high after PU-CS implantation, the long-term follow-up shows favorable clinical outcomes, indicating the feasibility of PU-CS in treating CAP.

Improving the Enzymatic Stability and the Pharmacokinetics of Oligonucleotides via DNA-Backboned Bottlebrush Polymers.

Herein, we design and synthesize site-specifically PEGylated oligonucleotide hairpins and demonstrate that their ability to undergo hybridization chain reaction is nearly unaffected by the PEGylation. The resulting DNA-backboned bottlebrush polymers with PEG side chains exhibit increased resistance against nucleolytic degradation, enhanced thermal stabilities, and elevated blood retention times in vivo, which collectively pave the way for more therapeutically focused DNA nanostructure designs.

Calcium-Induced Molecular Rearrangement of Peptide Folds Enables Biomineralization of Vaterite Calcium Carbonate.

Proteins can control mineralization of CaCO3 by selectively triggering the growth of calcite, aragonite or vaterite phases. The templating of CaCO3 by proteins must occur predominantly at the protein/CaCO3 interface, yet molecular-level insights into the interface during active mineralization have been lacking. Here, we investigate the role of peptide folding and structural flexibility on the mineralization of CaCO3. We study two amphiphilic peptides based on glutamic acid and leucine with ß-sheet and α-helical structures. Though both sequences lead to vaterite structures, the ß-sheets yield free-standing vaterite nanosheet with superior stability and purity. Surface-spectroscopy and molecular dynamics simulations reveal that reciprocal structuring of calcium ions and peptides lead to the effective synthesis of vaterite by mimicry of the (001) crystal plane.

Facile Synthesis of Optically Active and Magnetic Nanoparticles Carrying Helical Poly(phenyl isocyanide) Arms and Their Application in Enantioselective Crystallization.

In this paper, the facile synthesis of hybrid Fe3 O4 magnetic nanoparticles carrying helical poly(phenyl isocyanide) (PPI) arms via both "grafting from" and "grafting onto" strategies is reported. First, alkyne-Pd(II) catalysts are anchored onto the surface of the Fe3 O4 magnetic nanoparticle, which promote the polymerization of enantiopure phenyl isocyanide, affording the expected hybrid magnetic nanoparticle with Fe3 O4 in core and helical PPI as arms. The nanoparticle also exhibits highly optical activity due to the excess of one-handed helicity of the PPI arms. Moreover, the hybrid magnetic nanoparticle can be alternatively synthesized via "grafting onto" strategy. A triethoxysilanyl-terminated single handed helical PPI bearing l-alanine ester pendants is prepared and grafted onto the surface of Fe3 O4 nanoparticle. The generated hybrid magnetic nanoparticles show both magnetic character and optical activity. Taking advantage of these properties, they can be used in enantioselective crystallization of racemic threonine. The enantiomeric excess (ee) of the induced crystals is up to 93%. Moreover, the nanoparticles can be facilely recovered and recycle used for at least four times in enantioselective crystallization without significantly loss of its enantioselectivity.

Depth-Profiling the Nuclease Stability and the Gene Silencing Efficacy of Brush-Architectured Poly(ethylene glycol)-DNA Conjugates.

PEGylation of an oligonucleotide using a brush polymer can improve its biopharmaceutical characteristics, including enzymatic stability and biodistribution. Herein, we quantitatively explore the nuclease accessibility of the nucleic acid as a function of "depth" toward the backbone of the brush polymer. It is found that protein accessibility decreases as the nucleotide is located closer to the backbone. Thus, by moving the conjugation point from the terminus of the nucleic acid strand to an internal position, much smaller brushes can be used to achieve the same level of steric shielding. This finding also makes it possible to assess antisense gene regulation efficiency of these brush-DNA conjugates as a function of their nuclease stability.

The relationship between periodontal disease and gastric cancer: A bidirectional Mendelian randomization study.

BACKGROUND: Previous observational studies have suggested a possible association between periodontal disease and gastric cancer (GC); however, a causal relationship has not yet been established. This study aimed to explore the causal relationship between the 2 through a 2-sample bidirectional Mendelian randomization (MR) study. METHODS: Genome-wide association studies (GWAS) summary statistics were obtained from publicly available GWAS and relevant databases. Two-sample bidirectional MR analysis was conducted to investigate the causal relationship between periodontal disease and GC using the inverse-variance weighted (IVW) method selected as the primary analytical approach. Cochran Q test, MR-PRESSO, MR-pleiotropy, and leave-one-out analyses were performed to assess heterogeneity, pleiotropy, and sensitivity. RESULTS: In European ancestry, IVW analysis revealed no causal relationship between periodontal disease and GC (OR = 1.873; 95% CI [4.788e-10, 7.323e + 09]; P = .956), or between loose teeth and GC (OR = 1.064; 95% CI [0.708, 1.598]; P = .765). In East Asian ancestry, there was no causal relationship between periodontitis and GC according to IVW (OR = 0.948; 95% CI [0.886, 1.015]; P = .126). Conversely, according to the results of the IVW analysis, there was no causal relationship between GC and periodontal disease, regardless of European or East Asian ancestry. Furthermore, there was no heterogeneity or pleiotropy in the causal relationships between these variables (all P > .05), suggesting a certain level of reliability in our results. CONCLUSION: Within the limitations of this MR study, we found no mutual causal relationship between periodontal disease and GC. This finding can prevent overtreatment by clinical physicians and alleviate the psychological burden on patients.

Effect of poly(L-lactic acid)/poly(ethylene glycol)-poly(L-lactic acid) block copolymer blend film on preservation of Chinese winter jujube (Ziziphus Jujuba Mill. cv. Dongzao).

The effect of poly(L-lactic acid)/poly(ethylene glycol)-poly(L-lactic acid) block film on preservation of Chinese winter jujube (Ziziphus Jujuba Mill.cv.Dongzao) was investigated. Eight arm poly(ethylene glycol)-poly(L-lactic acid) block copolymer (8-PEG/PLLA) and net structure 8-PEG/PLLA (NET-PEL) were successfully synthetized by ring-opening polymerization, and different percentages (5, 10, and 20 %) of them were blended with PLLA to prepared blends films. Mechanical properties, modulated different scanning calorimetry (MDSC), gas and water vapor permeability results showed that 8-PEG/PLLA and NET-PEL block copolymer greatly increased the toughness of blend films, could be decrease PLLA segment glass transition temperature (Tg)from 59.5 °C to 41.6-46.7 °C and cold crystallization temperature(Tcc)from 89.4 °C to 73.5-77.7 °C, and increased the oxygen (O2), carbon dioxide (CO2), and water vapor transmission rate. The an appropriate gas concentration [O2 (2.56-3.51 %), CO2 (5.05-5.56 %)] was created inside the PLLA/NET-PEL20% (NEPEL20)group, which could restrain increase of total soluble solids (TSS), malonaldehyde content. The firmness, color luminosity (L*), total phenols, and ascorbic acid were maintained at higher level，and kept its commercial value after 40 days of storage. The present data indicated that treating post-harvest winter jujubes with NEPEL20 MAP packaging was an effective method for preservation of postharvest winter jujube.

Fabrication and design of poly(l-lactic acid) membrane for passive MAP packaging of Brassica chinensis L.

PLDx L copolymers were synthesized from physically stable rigid poly(l-lactic acid) (PLLA) and a few different molecular weights of polydimethylsiloxane (PDMS) to increase the O2 and CO2 permeabilities of PLLA films and make them acceptable for packaging highly respirable products. The effect of PDMS on the morphology, mechanical properties, and gas permeability of PLDx L was investigated. Copolymers showed approximately 10 times the fracture strain and 1.7 times the CO2 and O2 permeabilities of neat PLLA. Additionally, PLDx L maintained an increased CO2 /O2 perm-selectivity consistent between 5 and 40°C. Passive modified atmosphere packaging of Brassica chinensis L was developed to assess the membrane's impact on headspace gas inside the package. The results showed that poly(amide)/poly(ethylene) packaging with 48 cm2 PLD1.8 L membrane as a breathing window can provide 50 g B. chinensis L. with a healthy atmosphere of 3%-8% O2 and 5%-8% CO2 between 6 and 22 days. Vegetables packaged in PLD1.8 L had the lower respiration rate, lower nitrite contents, and less proliferation of microorganisms. Moreover, a suitable atmosphere kept vegetables with higher ascorbic acid and a good appearance after more than 2 weeks of storage at 5°C. PRACTICAL APPLICATION: The permeability of the PLLA-based membrane can be adjusted for the breathable window membrane of sealed fresh products. In the future, several types of film could be developed to match the respiratory and metabolic characteristics of different kinds of products. Such PLLA-based specialized membranes can refine the fresh-keeping function and be more attractive to the customer.

[Clinical effect observation of biodegradable conduit small gap tublization repairing peripheral nerve injury].

OBJECTIVE: To observe the clinical effect of biodegradable conduit small gap tublization to repair peripheral nerve injury. METHODS: In the study, 30 cases of fresh peripheral nerve injury in the upper extremities were recruited. After formally informed and obtaining the consent, the recruited patients were divided into the degradable chitin conduit tublization group (experimental group: 15 cases) and traditional epineurial neurorrhaphy group (control group: 15 cases). Their nerve functional recovery conditions were clinically observed according to the standard score methods provided by SHEN Ning-jiang and British Medical Research Council. The excellent and good rates of the overall nerve functional recovery were calculated. The electrophysiologic study was carried out after 6 months. RESULTS: Of the total 30 cases, 28 were followed up, and there were 14 cases in the degradable chitin conduit tublization group and traditional epineurial neurorrhaphy group. The operation procedure was very simple, and the mean suture time [(8.0±0.8) min] was 20% shorter than that of the traditional epineurial neurorrhaphy group [(10.0±0.6) min]. All the wounds in the degradable chitin conduit tublization group healed as expected without rejection, hypersensitive reaction or anomalous draining. Electrophysiology examination results after 6 months displayed that the sensory nerves conduction velocity recovery rate was 77.37% of the normal value, and motor nerve conduction velocity recovery rate was 70.09% in the degradable chitin conduit tublization group. The sensory nerves conduction velocity recovery rate was 61.69% of the normal value, and motor nerve conduction velocity recovery rate was 56.15% in the traditional epineurial neurorrhaphy group. The exact propability methods was applied in the comparison of sensory and motor nerve conduction velocity recovery rate, and there was no statistically significant of two groups(sensory nerve conduction velocity recovery rate P=0.678;motor nerve conduction velocity recovery rate P=0.695). The combinated functional recovery excellent and good rates after repair in the degradable chitin conduit tublization group were 78.57%, while 28.57% in the traditional epineurial neurorrhaphy group. The Fisher's exact probabilistic method was applied in the comparison of combinated functional recovery excellent and good rates, and there was statistically significant of two groups(P=0.021). CONCLUSION: The operation procedure of the degradable chitin conduit tublization is very simple and the clinical recovery effect is much better than that of the traditional epineurial neurorrhaphy. The biodegradable conduit small gap tublization methods to repair peripheral nerve injury has the possibility to substitute the traditional epineurial neurorrhaphy.

Analysis of the Effect of Antibiotic Bone Cement in the Treatment of Diabetic Foot Ulcer through Tibia Transverse Transport.

OBJECTIVE: To explore the efficacy of antibiotic bone cement (ABC) combined with the modified tibial transverse transport (mTTT) on the treatment of severe diabetic foot with infection. METHODS: A retrospective cohort study was conducted of 243 patients with TEXAS grade 3/4 stage D diabetic foot ulcers from December 2016 to December 2019. A total of 115 patients treated with mTTT were classified as the mTTT group (78 male and 37 female, mean age: 70.4 ± 6 years) and 128 patients who were treated with ABC combined with mTTT were in the ABC + mTTT group (89 male and 39 female, mean age: 68.9 ± 8 years). Follow-up records during treatment and 6 months after surgery were collected, including the time required for white blood cells (WBC) and C-reactive protein (CRP) to return to normal range, wound healing time, pain visual analog scale (VAS), ankle-brachial index (ABI), foot skin temperature, transcutaneous oxygen pressure measurement (TcPO2 ), complications, and other indicators. Normally distributed data were compared using the independent sample t-test, non-normally distributed data were analyzed by one-way ANOVA analysis of variance. RESULTS: There were 128 cases in the ABC + mTTT group (89 male and 39 female, mean age: 68.9 ± 8 years) treated with ABC and mTTT, and 115 cases in the TTT group (78 male and 37 female, mean age: 70.4 ± 6 years) treated with mTTT alone. The time required for WBC and CRP to return to the normal range and wound healing time in the ABC + mTTT group were significantly shorter than those in the mTTT group (12.9 ± 4.6 vs. 22.6 ± 1.6 days, t = 3.979, p < 0.001; 25.3 ± 1.3 vs. 31.3 ± 2.3 days, t = 4.261, p = 0.001; 11.9 ± 3.8 vs. 15.9 ± 3.9 days, t = 4.539, p < 0.001). There were no significant intergroup differences in the foot skin temperature, VAS score, ABI, and TcPO2 (t = 0.349, 0.542, 0.765, 0.693 while all p > 0.05). CONCLUSION: Although the application of ABC with mTTT for treatment of diabetic foot ulcers did not affect the wound healing time and ankle blood supply in the mid-term, it could control ulcer infection faster and accelerate wound healing.

Biocompatible Polyurethane Conduit Grafted with Vascular Endothelial Growth Factor-Loaded Hydrogel Repairs the Peripheral Nerve Defect in Rats.

Artificial nerve guidance conduits (NGCs) can be potentially used to address the problems of peripheral nerve defects. The biomaterial polyurethane (PU) has already been used to construct NGCs. However, the use of a combination of PU-based NGCs and other bioactive cues, such as extracellular matrix proteins and growth factors, has not been reported yet. A PU conduit grafted with a vascular endothelial growth factor (VEGF)-loaded hydrogel (abbreviated as PU/Gel/VEGF conduit) is fabricated. The leachate generated during the use of the PU/Gel/VEGF conduit could facilitate the proliferation, migration, and expression of the neural marker S100ß in RSC96 cells (in vitro). The walking track and target muscle are analyzed, and it is observed that PU/Gel/VEGF conduits promote the functional recovery of the injured side. Various histological staining analyses are carried out, and the results reveal that the PU/Gel/VEGF conduit effectively improves the extent of nerve regeneration achieved. The number of blood vessels developed during the regeneration of the axons in the PU/Gel/VEGF group (attributable to the pro-angiogenic effect of the functional NGC) is higher than the number of blood vessels developed in the PU/Gel conduit. Overall, the results indicate that PU/Gel/VEGF conduits could promote the process of peripheral nerve regeneration.

Improvement of bio-based polyurethane and its optimal application in controlled release fertilizer.

In the past decades, polyurethane has emerged as a new material that has been widely developed and applied in coated controlled release fertilizers (CRFs). Particularly in recent years, the excessive consumption of petroleum resources and increasing demand for sustainable development have resulted in considerable interest in bio-based polyurethane coated controlled-release fertilizers. This review article focuses on the application and progress of environmentally friendly bio-based materials in the polyurethane-coated CRF industry. We also explore prospects for the green and sustainable development of coated CRFs. Using animal and plant oils, starch, lignin, and cellulose as raw materials, polyols can be produced by physical, chemical, and biological means to replace petroleum-based materials and polyurethane film coating for CRFs can be prepared. Various modifications can also improve the hydrophobicity and degradability of polyurethane film. A growing body of research on bio-based polyurethane has revealed its great potential in the production and application of coated CRFs. The purpose of this review is to highlight the practicality of bio-based materials in the application of polyurethane-coated CRFs and to clarify their current limitations.

A hollow Co3-xCuxS4 with glutathione depleting and photothermal properties for synergistic dual-enhanced chemodynamic/photothermal cancer therapy.

Chemodynamic therapy has become an emerging cancer treatment strategy, in which tumor cells are killed through toxic reactive oxygen species (ROS), especially hydroxyl radicals (˙OH) produced by the Fenton reaction. Nevertheless, low ROS generation efficiency and ROS depletion by cellular antioxidant systems are still the main obstacles in chemodynamic therapy. In the present work, we propose a dually enhanced chemodynamic therapy obtained by inhibiting ˙OH consumption and promoting ˙OH production based on the administration of bimetallic sulfide Co3-xCuxS4 nanoparticles functionalized by polyethylene glycol. These bimetallic nanoparticles display glutathione depleting and photothermal properties. The nanoparticles are gradually degraded in a tumor microenvironment, resulting in Co2+ and Cu2+ release. The released Co2+ triggers a Fenton-like reaction that turns endogenous hydrogen peroxide into highly toxic ˙OH. In the cellular environment, Cu2+ ions are reduced to Cu+ by endogenous GSH, which decreases the intracellular antioxidant capacity and additionally up-regulates ˙OH production via the Cu+-induced Fenton-like reaction. Moreover, under near-infrared light irradiation, the bimetallic nanoparticles display a photothermal conversion efficacy of 46.7%, which not only improves chemodynamic therapy via boosting a Fenton-like reaction but results in photothermal therapy through hyperthermia. Both in vitro cancer cell killing and in vivo tumor ablation experiments show that the bimetallic nanoparticles display outstanding therapeutic efficacy and negligible systemic toxicity, indicating their anticancer potential.

Nitrogen-doped porous carbon fiber with enriched Fe2N sites: Synthesis and application as efficient electrocatalyst for oxygen reduction reaction in microbial fuel cells.

Low-cost, stable and highly efficient oxygen reduction reactions (ORR) electrocatalysts are of great significance for microbial fuel cells to break the limit of the air cathode. The expensive noble metal catalysts are easy to be contaminated due to biofouling, which could damage the catalytic activity significantly. Among the reported non-noble metal catalysts, FeCN materials are promising substitutes that have comparable catalytic activity with Pt/C. In this article, a facile process to obtain N-doped porous carbon fibers (NPCF) with abundant Fe2N moieties from iron based metal organic framework (MOF(Fe)) embedded electrospun fibers has been developed. The fiber structure promotes the in situ conversion of Fe2N sites in embedded MOF(Fe) during pyrolysis under NH3 atmosphere. The abundant Fe2N sites, presence of pyrrolic nitrogen and hierarchical porous structure of obtained Fe2N/NPCF make it possess excellent electrocatalytic activity to ORR with comparable performance (E1/2 = 0.8648 V) and superior long term stability to commercial 20 wt% Pt/C. This work expends the toolbox for design of high performance cathodic catalysts for MFCs and also provides original insights in Fe-N active sites construction for FeNC ORR catalysts.

Structure-activity examination of poly(glycoamidoguanidine)s: glycopolycations containing guanidine units for nucleic acid delivery.

In this study we synthesized a new series of polymers known as poly(glycoamidoguanidine)s (PGAGs). These new polymer structures were synthesized by copolymerizing a carbohydrate monomer (diester; galatarate or tartarate) with a diamine incorporating guanidine or methylguanidine as a charge center to create a polyamide backbone. These materials were strategically designed and compared to our previously studied DNA delivery vehicles, poly(glycoamidoamine)s (PGAAs), which contain secondary amines as the charge groups along the polymer backbone to examine the effect of charge center type on the cellular delivery efficiency of plasmid DNA (pDNA). The guanidine moieties within the PGAGs facilitate electrostatic binding with the negatively charged phosphate backbone of plasmid DNA (pDNA). Stable polymer-pDNA complexes (polyplexes) with sizes in the range of 60-200 nm are formed at polymer/pDNA charge ratios (N/P) of 5 and above. When the PGAGs are complexed with Cy5-labeled pDNA (Cy5-pDNA) at N/P ratios of 10 and 25, between 80 and 95% of HeLa cells were positive for Cy5 fluorescence, indicating effective cellular internalization of the polyplexes. The toxicity of both PGAA and PGAG polyplexes was studied via MTT assays, and over 95% cell survival was observed at N/P ratios of 5, 10, 15, 20, 25, and 30 in HeLa cells. Transgene expression was examined via luciferase assays at various N/P ratios in the absence and presence of serum. In the absence of serum, the PGAG polyplexes revealed similar transgene expression when compared to polyplexes formed with their analogous PGAA structures. In the presence of serum, one analog (Gg) consisting of galactarate copolymerized with the guanidine monomer yielded gene expression similar to the positive control, Glycofect Transfection Reagent. This new series of guanidine-containing oligomers are promising as a new design strategy to incorporate an alternative charge center type within the backbone of glycopolymer-based nucleic acid delivery vehicles.

Type III Resistant Starch Prepared from Debranched Starch: Structural Changes under Simulated Saliva, Gastric, and Intestinal Conditions and the Impact on Short-Chain Fatty Acid Production.

Type III resistant starch (RS3) has high resistance to enzymatic digestibility and benefits colonic bacteria by producing short-chain fatty acids (SCFAs) via fermentation. Studies have delineated RS preparation and the description of RS fractions with different types of starch, but the digestion process has received little attention. The molecular and crystalline structure changes, thermal properties, and SCFA content of RS3 obtained from debranched starch were investigated in simulated salivary, gastric, and intestinal digestion systems. The average degree of polymerization and the melting enthalpy change of the digested RS3 residues increased; a high molecular order was reflected by the higher relative crystallinity. Fine structural changes suggested that enzyme-resistant starch might form during digestion by the rearrangement of short amylose chains into enzyme-resistant structures with higher relative crystallinity. After fermentation of human feces, RS3 increased the SCFA content, especially of butyric acid, indicating that this recrystallized RS3 could be a new prebiotic product.

Bottlebrush Polymer-Conjugated Melittin Exhibits Enhanced Antitumor Activity and Better Safety Profile.

Despite potency against a variety of cancers in preclinical systems, melittin (MEL), a major peptide in bee venom, exhibits non-specific toxicity, severe hemolytic activity, and poor pharmacological properties. Therefore, its advancement in the clinical translation system has been limited to early-stage trials. Herein, we report a biohybrid involving a bottlebrush-architectured poly(ethylene glycol) (PEG) and MEL. Termed pacMEL, the conjugate consists of a high-density PEG arrangement, which provides MEL with steric inhibition against protein access, while the high molecular weight of pacMEL substantially enhances plasma pharmacokinetics with a ∼10-fold increase in the area under the curve (AUC∞) compared to free MEL. pacMEL also significantly reduces hepatic damage and unwanted innate immune response and all but eliminated hemolytic activities of MEL. Importantly, pacMEL passively accumulates at subcutaneously inoculated tumor sites and exhibits stronger tumor-suppressive activity than molecular MEL. Collectively, pacMEL makes MEL a safer and more appealing drug candidate.