Correlation between positron annihilation lifetime and photoluminescence measurements for calcined Hydroxyapatite.

Hydroxyapatite (HAp) Ca10(PO4)6(OH)2 is a compound that has stable chemical properties, composition, and an affinity for human bone. As a result, it can be used in odontology, cancer treatment, and orthopedic grafts to repair damaged bone. To produce calcined HAp at 600 °C with different pH values, a wet chemical precipitation method was employed. All synthesized HAp samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), photoluminescence (PL), Zeta potential, and positron annihilation lifetime spectroscopy (PALS). The XRD results revealed that all calcined HAp samples were formed in a hexagonal structure with a preferred (002) orientation at different pH values. The crystal size of the samples was determined using the Scherrer equation, which ranged from 16 to 25 nm. The SEM and TEM results showed that the morphology of the samples varied from nanorods to nanospheres and rice-like structures depending on the pH value of the sample. The PL measurements indicated that the blue and green emission peaks of HAp were due to defects (bulk, surface, and interface) in the samples, which created additional energy levels within the band gap. According to Zeta potential measurements, the charge carrier changed from a positive to negative value, ranging from 3.94 mV to - 2.95 mV. PALS was used to understand the relationship between the defects and the photoluminescence (PL) properties of HAp. Our results suggest that HAp nanoparticles have excellent potential for developing non-toxic biomedical and optical devices for phototherapy.

Constructing B─N─P Bonds in Ultrathin Holey g-C3N4 for Regulating the Local Chemical Environment in Photocatalytic CO2 Reduction to CO.

The lack of intrinsic active sites for photocatalytic CO2 reduction reaction (CO2RR) and fast recombination rate of charge carriers are the main obstacles to achieving high photocatalytic activity. In this work, a novel phosphorus and boron binary-doped graphitic carbon nitride, highly porous material that exhibits powerful photocatalytic CO2 reduction activity, specifically toward selective CO generation, is disclosed. The coexistence of Lewis-acidic and Lewis-basic sites plays a key role in tuning the electronic structure, promoting charge distribution, extending light-harvesting ability, and promoting dissociation of excitons into active carriers. Porosity and dual dopants create local chemical environments that activate the pyridinic nitrogen atom between the phosphorus and boron atoms on the exposed surface, enabling it to function as an active site for CO2RR. The P-N-B triad is found to lower the activation barrier for reduction of CO2 by stabilizing the COOH reaction intermediate and altering the rate-determining step. As a result, CO yield increased to 22.45 µmol g-1 h-1 under visible light irradiation, which is ≈12 times larger than that of pristine graphitic carbon nitride. This study provides insights into the mechanism of charge carrier dynamics and active site determination, contributing to the understanding of the photocatalytic CO2RR mechanism.

Synergistic Electronic Interaction of Nitrogen Coordinated Fe-Sn Double-Atom Sites: An Efficient Electrocatalyst for Oxygen Reduction Reaction.

Double-atom site catalysts (DASs) have emerged as a recent trend in the oxygen reduction reaction (ORR), thereby modifying the intermediate adsorption energies and increasing the activity. However, the lack of an efficient dual atom site to improve activity and durability has limited these catalysts from widespread application. Herein, the nitrogen-coordinated iron and tin-based DASs (Fe-Sn-N/C) catalyst are synthesized for ORR. This catalyst has a high activity with ORR half-wave potentials (E1/2 ) of 0.92 V in alkaline, which is higher than those of the state-of-the-art Pt/C (E1/2  = 0.83 V), Fe-N/C (E1/2  = 0.83 V), and Sn-N/C (E1/2  = 0.77 V). Scanning electron transmission microscopy analysis confirmed the atomically distributed Fe and Sn sites on the N-doped carbon network. X-ray absorption spectroscopy analysis revealed the charge transfer between Fe and Sn. Both experimental and theoretical results indicate that the Sn with Fe-NC (Fe-Sn-N/C) induces charge redistribution, weakening the binding strength of oxygenated intermediates and leading to improved ORR activity. This study provides the synergistic effects of DASs catalysts and addresses the impacts of P-block elements on d-block transition metals in ORR.

Neurogenic Appendicitis: A Reappraisal of the Clinicopathological Features and Pathogenesis.

In 1921; Masson and Maresch first coined the term "neurogenic appendicitis (NA)" to describe "neuroma-like" lesions in the appendix. To date, our knowledge about NA is limited; therefore, we conducted a comprehensive analysis of the literature (1921 to 2020) to examine the clinicopathological features of NA. We also addressed the pathophysiology of acute abdominal pain and fibrosis in this entity. We performed a meta-analysis study by searching the PubMed database, using several keywords, such as: "appendix," "neurogenic," "obliterative," "neuroma," "fibrous obliteration," "appendicopathy," and "appendicitis." Our study revealed that patients with NA usually present clinically with features of acute appendicitis, bud2t they have grossly unremarkable appendices. Histologically, the central appendiceal neuroma was the most common histological variant of NA, followed by the submucosal and intramucosal variants. To conclude, NA represents a form of neuroinflammation. The possibility of NA should be considered in patients with clinical features of acute appendicitis who intraoperatively show a grossly unremarkable appendix. Neuroinflammation and neuropeptides play roles in the development of pain and fibrosis in NA.

Impact of Fennel Essential Oil as an Antibiotic Alternative in Rabbit Diet on Antioxidant Enzymes Levels, Growth Performance, and Meat Quality.

In the current study, fennel essential oil was used as an antibiotic alternative compared to gentamycin for enhancing the expression of apoptosis genes and antioxidant enzymes in weaned rabbits as well as meat quality and growth performance. The gene expression of the cell lymphoma 2 (BAX and BCL2), caspase3 (CASP3), and glutathione peroxidase (GPX1) were estimated in the liver tissue using qRT-PCR. A total of 45 Moshtohor weaned male rabbits aged four weeks were randomly allocated to control, T1, and T2 treatment groups; each consisted of 15 weaned male rabbits with five replicates. Rabbits in the T1 and T2 groups were orally supplied with 1 mL fennel oil and 1 mL gentamycin, respectively. Weaned rabbits under different treatments showed increased body weight (BW) at 8 and 12 weeks of age and average daily gain (ADG) at 4-8 and 4-12 weeks of age compared to the control group. Compared to the controls, the weaned rabbits supplemented with fennel oil and gentamycin had lower total cholesterol, triglyceride, and MDA. In addition, villus length, mRNA of BAX, BCL2, Casp3, and GPX were increased in the different treatments compared to the control. Furthermore, the meat of these rabbits was less tender, had a lower aerobic plate count (APC), pH, and was brighter and redder in color than the control. Under the conditions of the present study, the supplementation of weaned Moshtohor rabbits with fennel oil as a natural alternative for gentamycin enhanced feed conversion and daily gain through enhancing villus length and mucus thickness. Additionally, fennel essential oil reduces oxidative stress by increasing the antioxidant enzymes.

Nano-Porous-Silicon Powder as an Environmental Friend.

Nano-porous silicon (NPS) powder synthesis is performed by means of a combination of the ultra-sonication technique and the alkali chemical etching process, starting with a commercial silicon powder. Various characterization techniques {X-ray powder diffraction, transmission electron microscopy, Fourier Transform Infrared spectrum, and positron annihilation lifetime spectroscopy} are used for the description of the product's properties. The NPS product is a new environmentally friendly material used as an adsorbent agent for the acidic azo-dye, Congo red dye. The structural and free volume changes in NPS powder are probed using positron annihilation lifetime (PALS) and positron annihilation Doppler broadening (PADB) techniques. In addition, the mean free volume (VF), as well as fractional free volume (Fv), are also studied via the PALS results. Additionally, the PADB provides a clear relationship between the core and valence electrons changes, and, in addition, the number of defect types present in the synthesized samples. The most effective parameter that affects the dye removal process is the contact time value; the best time for dye removal is 5 min. Additionally, the best value of the CR adsorption capacity by NPS powder is 2665.3 mg/g at 100 mg/L as the initial CR concentration, with an adsorption time of 30 min, without no impact from temperature and pH. So, 5 min is the enough time for the elimination of 82.12% of the 30 mg/L initial concentration of CR. This study expresses the new discovery of a cheap and safe material, in addition to being environmentally friendly, without resorting to any chemical additives or heat treatments.

The Effect of Foliar and Ground-Applied Essential Nutrients on Huanglongbing-Affected Mature Citrus Trees.

The fate of foliar and ground-applied essential nutrients is the least studied topic under citrus greening or Huanglongbing (HLB)-affected citrus, which is inherently suffering from severe root decline because of HLB-associated problems. The objective of this study was to evaluate if ground-applied coupled with foliar spray of essential nutrients can reverse the decline in tree growth and understand the fate of the nutrients in the soil-root-tree interfaces. The treatments were arranged in a split-split plot design in which nitrogen (N) was ground-applied in 20 splits biweekly and Mn, Zn, and B were foliar and /or ground-applied in three splits following the spring, summer, and late summer flush seasons. Soil nutrients in three depths (0-15, 15-30, and 30-45 cm), root, and leaf nutrient concentrations of the essential nutrients, leaf area index (LAI), and tree canopy volume (TCV) data were studied twice (spring and summer) for two years. A significantly higher soil NH4-N and NO3-N concentrations were detected in the topsoil depth than the two lower soil depths (15-30 and 30-45 cm) indicating lesser nutrient leaching as trees received moderate (224 kg ha-1) N rate. Except for soil zinc (Zn) concentration, all the nutrient concentrations were significantly higher in the topsoil (0-15 cm), compared with two lower soil depths indicating that Zn was intricate by changes in soil environmental conditions, root acquisition, and/or leaching to lower soil depth. Leaf N concentration significantly increased over time following seasonal environmental fluctuations, tree growth, and development. Thus, leaf N concentration remained above the optimum nutrient range implying lower N requirement under irrigation scheduling with SmartIrrigation, an App used to determine the daily irrigation duration to meet tree water requirement and split fertigation techniques. Root Manganese (Mn) and Zn concentrations were significantly higher in the root tissues of the treated than the control trees and translocated to the leaves accordingly. Meanwhile, a significantly higher LAI for trees budded on Swingle (Swc) rootstock however, larger TCV for trees budded on Volkameriana (Volk) rootstocks. The trees had significantly larger TCV when the trees received a moderate N rate during early study years and under foliar 9 kg ha-1 coupled with the ground 9 kg ha-1 Mn and Zn treatments during the late study years. Therefore, split ground application of 224 kg ha-1 of N, foliar applied 9 kg ha-1 coupled with ground-applied 9 kg ha-1 Mn and Zn were the suggested rates to sustain the essential leaf nutrient concentration within the optimum ranges and improve the deterioration of vegetative growth associated with HLB-induced problems of citrus trees.

Alleviation of carbon tetrachloride-induced hepatocellular damage and oxidative stress in rats by Anabaena oryzae phycocyanin.

Phycocyanin isolated from Anabaena biomass was in-vitro assayed for its antioxidant activity against DPPH (2,2-diphenyl-1-picrylhydrazyl) and ABTS [2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)] free radical, revealing maximum activities amounting to 77 and 80% at 1,000 µg/ml and SC50 values about 96 and 111 µg/ml, respectively. A biological experiment was conducted, involving 40 male Wistar Albino rats, divided into five groups. Group I received only the basal diet as a normal control, while groups II, III, IV, and V were administrated intraperitoneal (IP) injection of a single dose of CCl4 (50% in corn oil) at 0.5 ml/kg body weight. Subsequently, groups II, III, IV, and V received phycocyanin at 0.0, 25, 50, and 100 mg/kg body weight/day. CCl4 induced considerable increases (p < .05) in the levels of serum ALT, AST, urea and creatinine, total lipid, and triglycerides coupled with significant reductions (p < .05) in serum antioxidant enzymes and some liver histopathological deformations compared to the negative control (group 1). Administration of Anabaena oryzae phycocyanin can counteract these CCl4 -induced changes. PRACTICAL APPLICATIONS: Phycocyanin isolated from Anabaena has beneficial effects such as the antioxidant, antibacterial, anticancer, and hepatoprotective effect. Phycocyanin may play a key role in alleviating oxidative stress, artificially induced by carbon tetrachloride in Albino rats, to ultimately determine its capacity to serve as a natural antioxidant for food and health applications.

Antigen delivery format variation and formulation stability through use of a hybrid vector.

A hybrid biological-biomaterial antigen delivery vector comprised of a polymeric shell encapsulating an Escherichia coli core was previously developed for in situ antigen production and subsequent delivery. Due to the engineering capacity of the bacterial core, the hybrid vector provides unique opportunities for immunogenicity optimization through varying cellular localization (cytoplasm, periplasm, cellular surface) and type (protein or DNA) of antigen. In this work, three protein-based hybrid vector formats were compared in which the pneumococcal surface protein A (PspA) was localized to the cytoplasm, surface, and periplasmic space of the bacterial core for vaccination against pneumococcal disease. Furthermore, we tested the hybrid vector's capacity as a DNA vaccine against Streptococcus pneumoniae by introducing a plasmid into the bacterial core to facilitate PspA expression in antigen presenting cells (APCs). Through testing these various formulations, we determined that cytoplasmic accumulation of PspA elicited the strongest immune response (antibody production and protection against bacterial challenge) and enabled complete protection at substantially lower doses when compared to vaccination with PspA + adjuvant. We also improved the storage stability of the hybrid vector to retain complete activity after 1 month at 4 °C using an approach in which hybrid vectors suspended in a microbial freeze drying buffer were desiccated. These results demonstrate the flexibility and robustness of the hybrid vector formulation, which has the potential to be a potent vaccine against S. pneumoniae.

Atolypenes, Tricyclic Bacterial Sesterterpenes Discovered Using a Multiplexed In Vitro Cas9-TAR Gene Cluster Refactoring Approach.

Most natural product biosynthetic gene clusters identified in bacterial genomic and metagenomic sequencing efforts are silent under laboratory growth conditions. Here, we describe a scalable biosynthetic gene cluster activation method wherein the gene clusters are disassembled at interoperonic regions in vitro using CRISPR/Cas9 and then reassembled with PCR-amplified, short DNAs, carrying synthetic promoters, using transformation assisted recombination (TAR) in yeast. This simple, cost-effective, and scalable method allows for the simultaneous generation of combinatorial libraries of refactored gene clusters, eliminating the need to understand the transcriptional hierarchy of the silent genes. In two test cases, this in vitro disassembly-TAR reassembly method was used to create collections of promoter-replaced gene clusters that were tested in parallel to identify versions that enabled secondary metabolite production. Activation of the atolypene ( ato) gene cluster led to the characterization of two unprecedented bacterial cyclic sesterterpenes, atolypene A (1) and B (2), which are moderately cytotoxic to human cancer cell lines. This streamlined in vitro disassembly- in vivo reassembly method offers a simplified approach for silent gene cluster refactoring that should facilitate the discovery of natural products from silent gene clusters cloned from either metagenomes or cultured bacteria.

Increased production of yersiniabactin and an anthranilate analog through media optimization.

Yersiniabactin (Ybt) is a mixed nonribosomal peptide-polyketide natural product that binds a wide range of metals with the potential to impact processes requiring metal retrieval and removal. In this work, we substantially improved upon the heterologous production of Ybt and an associated anthranilate analog through systematic screening and optimization of culture medium components. Specifically, a Plackett-Burman design-of-experiments methodology was used to screen 22 components and to determine those contributing most to siderophore production. L-cysteine, L-serine, glucose, and casamino acids significantly contributed to the production of both compounds. Using this approach together with metabolic engineering of the base biosynthetic process, Ybt and the anthranilate analog titers were increased to 867 ± 121 mg/L and 16.6 ± 0.3 mg/L, respectively, an increase of ∼38 and ∼79-fold relative to production in M9 medium. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:1193-1200, 2017.

E. coli metabolic engineering for gram scale production of a plant-based anti-inflammatory agent.

In this report, the heterologous production of salicylate (SA) is the basis for metabolic extension to salicylate 2-O-ß-d-glucoside (SAG), a natural product implicated in plant-based defense mechanisms. Production was optimized through a combination of metabolic engineering, gene expression variation, and co-culture design. When combined, SA and SAG production titers reached ~0.9g/L and ~2.5g/L, respectively. The SAG compound was then tested for anti-inflammatory properties relative to SA and acetylsalicylate (aspirin). Results indicate comparable activity between SAG and aspirin in reducing nitric oxide (NO) and reactive oxygen species (ROS) from macrophage cells while no discernable negative effects on cellular viability were observed.

Improved heterologous production of the nonribosomal peptide-polyketide siderophore yersiniabactin through metabolic engineering and induction optimization.

Biosynthesis of complex natural products like polyketides and nonribosomal peptides using Escherichia coli as a heterologous host provides an opportunity to access these molecules. The value in doing so stems from the fact that many compounds hold some therapeutic or other beneficial property and their original production hosts are intractable for a variety of reasons. In this work, metabolic engineering and induction variable optimization were used to increase production of the polyketide-nonribosomal peptide compound yersiniabactin, a siderophore that has been utilized to selectively remove metals from various solid and aqueous samples. Specifically, several precursor substrate support pathways were altered through gene expression and exogenous supplementation in order to boost production of the final compound. The gene expression induction process was also analyzed to identify the temperatures and inducer concentrations resulting in highest final production levels. When combined, yersiniabactin production was extended to ∼175 mg L-1 . © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1412-1417, 2016.

In situ pneumococcal vaccine production and delivery through a hybrid biological-biomaterial vector.

The type and potency of an immune response provoked during vaccination will determine ultimate success in disease prevention. The basis for this response will be the design and implementation of antigen presentation to the immune system. Whereas direct antigen administration will elicit some form of immunological response, a more sophisticated approach would couple the antigen of interest to a vector capable of broad delivery formats and designed for heightened response. New antigens associated with pneumococcal disease virulence were used to test the delivery and adjuvant capabilities of a hybrid biological-biomaterial vector consisting of a bacterial core electrostatically coated with a cationic polymer. The hybrid design provides (i) passive and active targeting of antigen-presenting cells, (ii) natural and multicomponent adjuvant properties, (iii) dual intracellular delivery mechanisms, and (iv) a simple formulation mechanism. In addition, the hybrid format enables device-specific, or in situ, antigen production and consolidation via localization within the bacterial component of the vector. This capability eliminates the need for dedicated antigen production and purification before vaccination efforts while leveraging the aforementioned features of the overall delivery device. We present the first disease-specific utilization of the vector toward pneumococcal disease highlighted by improved immune responses and protective capabilities when tested against traditional vaccine formulations and a range of clinically relevant Streptococcus pneumoniae strains. More broadly, the results point to similar levels of success with other diseases that would benefit from the production, delivery, and efficacy capabilities offered by the hybrid vector.

Sensitivity improvement of reflective tilted FBGs.

Tilted fiber Bragg gratings are used as energy couplers in which the core mode and cladding modes can be coupled together. Cladding modes have extensive importance in sensing applications due to their sensitive characteristics to the surrounding refractive index. The cladding modes are investigated theoretically by studying a three-layer model of optical fibers, whereas the core mode is investigated by studying a two-layer model of optical fibers. The analysis reveals that to increase the coupling of the energy transferred from the core mode to cladding modes, the cladding radius needs to be decreased. Such behavior is illustrated through studying the change in the electric field distribution and is used to improve the sensitivity of the sensing refractive index of the surrounding medium.

Recent progress in therapeutic natural product biosynthesis using Escherichia coli.

E. coli has become a common host for the heterologous biosynthesis of natural products that demonstrate therapeutic value but suffer from access challenges posed by native production hosts. This review will highlight recent examples of heterologous products produced using E. coli. An emphasis will be placed on tools at the cellular and process levels to enable, improve, and alter production efforts. At the cellular scale, summaries of the process to enable heterologous biosynthesis will be supplemented with strategies (synthetic biology and metabolic engineering) to improve production levels. Process engineering strategies such as precursor-directed biosynthesis will also be highlighted in analog formation cases. In summary, the article will provide a recent overview of heterologous production efforts using E. coli and the relationship of the products produced to therapeutic applications.

Molecular variation of the nonribosomal peptide-polyketide siderophore yersiniabactin through biosynthetic and metabolic engineering.

The production of the mixed nonribosomal peptide-polyketide natural product yersiniabactin (Ybt) has been established using E. coli as a heterologous host. In this study, precursor-directed biosynthesis was used to generate five new analogs of Ybt, demonstrating the flexibility of the heterologous system and the biosynthetic process in allowing compound diversity. A combination of biosynthetic and cellular engineering was then used to influence the production metrics of the resulting analogs. First, the cellular levels and activity of FadL, a hydrocarbon transport protein, were tested for subsequent influence upon exogenous precursor uptake and Ybt analog production with a positive correlation observed between FadL over-production and analog formation. Next, a Ybt biosynthetic editing enzyme was removed from the heterologous system which decreased native compound production but increased analog formation. A final series of experiments enhanced endogenous anthranilate towards complete pathway formation of the associated analog which showed a selective ability to bind gold.

Total Biosynthesis and Diverse Applications of the Nonribosomal Peptide-Polyketide Siderophore Yersiniabactin.

Yersiniabactin (Ybt) is a mixed nonribosomal peptide-polyketide natural product natively produced by the pathogen Yersinia pestis. The compound enables iron scavenging capabilities upon host infection and is biosynthesized by a nonribosomal peptide synthetase featuring a polyketide synthase module. This pathway has been engineered for expression and biosynthesis using Escherichia coli as a heterologous host. In the current work, the biosynthetic process for Ybt formation was improved through the incorporation of a dedicated step to eliminate the need for exogenous salicylate provision. When this improvement was made, the compound was tested in parallel applications that highlight the metal-chelating nature of the compound. In the first application, Ybt was assessed as a rust remover, demonstrating a capacity of ∼40% compared to a commercial removal agent and ∼20% relative to total removal capacity. The second application tested Ybt in removing copper from a variety of nonbiological and biological solution mixtures. Success across a variety of media indicates potential utility in diverse scenarios that include environmental and biomedical settings.

A prospective randomized multicenter study to evaluate the best day for embryo transfer: does the outcome justify prolonged embryo culture?

PURPOSE: This study aimed to evaluate the best day for embryo transfer in a prospective unrestricted randomized multicenter trial. METHODS: Data were collected on a preformed Excel-sheet which contained random numbers from 1 to 5 for each subsequent patient as a preprogrammed day for embryo transfer. Information was requested on patient's age, indication for sterility treatment, stimulation protocol used, numbers of oocytes retrieved, fertilized oocytes, cryopreserved embryos, and cell stage of embryos transferred. RESULTS: A total of 329 embryo transfers were performed, resulting in 106 clinical pregnancies (32.2%). Pregnancy rates achieved were 20.0% on day 1, 30.4% on days 2 and 3, and 50.0% on days 4 and 5 (p = 0.03). CONCLUSIONS: Within the scope of the present randomized multicenter trial, embryo transfers performed on days 4 and 5 enhanced the pregnancy rate significantly, compared to those of days 1, 2, and 3.