Deep Cracking of Bulky Hydrocarbons into Light Products via Tandem Catalysis over Uniform Interconnected ZSM-5@AlSBA-15 Composites.

Deep cracking of bulky hydrocarbons on zeolite-containing catalysts into light products with high activity, desired selectivity, and long-term stability is demanded but challenging. Herein, the efficient deep cracking of 1,3,5-triisopropylbenzene (TIPB) on intimate ZSM-5@AlSBA-15 composites via tandem catalysis is demonstrated. The rapid aerosol-confined assembly enables the synthesis of the composites composed of a continuous AlSBA-15 matrix decorated with isolated ZSM-5 nanoparticles. The two components at various ZSM-5/AlSBA-15 mass ratios are uniformly mixed with chemically bonded pore walls, interconnected pores, and eliminated external surfaces of nanosized ZSM-5. The typical composite with a ZSM-5/AlSBA-15 mass ratio of 0.25 shows superior performance in TIPB cracking with outstanding activity (≈100% conversion) and deep cracking selectivity (mass of propylene + benzene > 60%) maintained for a long time (> 6 h) under a high TIPB flux (2 mL h-1 ), far better (several to tens of times higher) than the single-component and physically mixed catalysts and superior to literature results. The high performance is attributed to the cooperative tandem catalytic process, that is, selective and timely pre-cracking of TIPB to isopropylbenzene (IPB) in AlSBA-15 and subsequently timely diffusion and deep cracking of IPB in nanosized ZSM-5.

Direct-to-Consumer Telemedicine Practices in the Health and Fertility of Men: A Systematic Review of the Literature.

PURPOSE: Men are increasingly turning toward online direct-to-consumer (DTC) men's health platforms to fulfill their health needs. Research surrounding these platforms is lacking and the motivations and predictors underlying this online health-seeking behavior is largely unknown. This review scopes the existing literature concerning DTC men's health and identifies factors influencing engagement, as well as health outcomes of this platform. MATERIALS AND METHODS: A structured search was performed following PRISMA guidelines. CINAHL via EBSCO, Embase, MEDLINE via Ovid, PsycINFO, PubMed and Web of Science were searched. RESULTS: Peer-reviewed quantitative and qualitative studies with a focus on demographics and characteristics of those using DTC men's health platforms, as well as studies related to patient outcomes using such platforms, were included. Ten of the 3,003 studies identified met the inclusion and exclusion criteria. Four cross-sectional descriptive studies evaluated the motivations behind men's engagement with DTC platforms. Convenience, embarrassment and health motivation were identified as predominant factors associated with DTC platform use. The review identified a lack of qualitative studies, and major limitations were noted in the quantitative studies that impacted the accuracy of findings. Six further quantitative studies explored the quality of care provided by DTC platforms. DTC platforms were found to have a varying level of adherence to established clinical guidelines, but appeared to provide satisfactory patient outcomes with low levels of patient-reported side effects and adverse events. CONCLUSIONS: There is a lack of research within the DTC men's health space given the infancy of the field. Important predictors and motivations underlying men's choices in accessing these platforms have been noted across several studies. However, further studies need to be conducted to investigate the psychosocial underpinnings of this behavior. Studies across a wider variety of male health conditions treated by these platforms will also help to provide insights to guide patient-centered care within the DTC landscape.

Psychological, social, and sexual challenges affecting men receiving male infertility treatment: a systematic review and implications for clinical care.

In recent years, social research surrounding the consequences of infertility has increasingly focused on the male perspective; however, a gap exists in the understanding of men's experiences of male infertility treatment. This review aims to synthesize the existing evidence concerning the psychological, social, and sexual burden of male infertility treatment on men, as well as patient needs during clinical care. A systematic search identified 12 studies that are diverse in design, setting, and methods. Psychological evaluations have found that urological surgery may have a lasting impact on infertility-specific stress, and treatment failure can lead to feelings of depression, grief, and inadequacy. Men tended to have an avoidant coping mechanism throughout fertility treatment, and their self-esteem, relationship quality, and sexual functions can be tied to outcomes of treatment. Partner bonds can be strengthened by mutual support and enhanced communication; couple separation, however, has been noted as a predominant reason for discontinuing male infertility treatment and may be associated with difficult circumstances surrounding severe male infertility. Surgical treatments can affect the sexual functioning of infertile men; however, the impact of testicular sperm extraction outcomes appears to be psychologically driven whereas the improvements after microsurgical varicocelectomy are only evident in hypogonadal men. Clinically, there is a need for better inclusion, communication, education, and resource provision, to address reported issues of marginalization and uncertainty in men. Routine psychosocial screening in cases of severe male infertility and follow-up in cases of surgical treatment failure are likely beneficial.

Spray freeze dried niclosamide nanocrystals embedded dry powder for high dose pulmonary delivery.

Based on the drug repositioning strategy, niclosamide (NCL) has shown potential applications for treating COVID-19. However, the development of new formulations for effective NCL delivery is still challenging. Herein, NCL-embedded dry powder for inhalation (NeDPI) was fabricated by a novel spray freeze drying technology. The addition of Tween-80 together with 1,2-Distearoyl-sn-glycero-3-phosphocholine showed the synergistic effects on improving both the dispersibility of primary NCL nanocrystals suspended in the feed liquid and the spherical structure integrity of the spray freeze dried (SFD) microparticle. The SFD microparticle size, morphology, crystal properties, flowability and aerosol performance were systematically investigated by regulating the feed liquid composition and freezing temperature. The addition of leucine as the aerosol enhancer promoted the microparticle sphericity with greatly improved flowability. The optimal sample (SF- 80D-N20L2D2T1) showed the highest fine particle fraction of ∼47.83%, equivalently over 3.8 mg NCL that could reach the deep lung when inhaling 10 mg dry powders.

Aerosol Spray Drying Guided Synthesis of Ultrasmall Alloyed Bimetallic Nanoparticles Supported on Silica for Catalytic Semihydrogenation.

Supported bimetallic nanoparticles (NPs) with ultrasmall sizes and homogeneous alloying are attractive for catalysis. However, facile synthesis of this type of material remains very challenging. Here, the aerosol drying impregnation method for rapid, scalable, and general synthesis of silica-supported bimetallic NPs is proposed. The method relies on aerosol spray drying to promote the mixing and dispersing of binary metal precursors on SiO2 . It is capable of controlling the composition and size of bimetallic NPs and avoids the use of expensive metal complex salts and complicated experiment procedures. Twelve permutations combining a noble metal (Pd, Ru, and Pt) and a base one (Fe, Co, Ni, and Cu) with ultrasmall sizes (1.4-2.2 nm in average size), uniform dispersion, and good alloying are synthesized. Interesting activity and selectivity trends in catalytic semihydrogenation of phenylacetylene over the supported Pd-based NPs can be observed. The silica-supported PdNi NPs deliver both high activity and styrene selectivity. Spectroscopic and density functional theory calculation results reveal the improved chemoselectivity originated from the suitably down-shifted d-band center of the PdNi NPs inducing an increased energy barrier for overhydrogenation and a weakened styrene adsorption.

Micro-fluidic Spray Freeze Dried Ciprofloxacin Hydrochloride-Embedded Dry Powder for Inhalation.

Active pharmaceutical ingredient (API)-embedded dry powder for inhalation (AeDPI) is highly desirable for pulmonary delivery of high-dose drug. Herein, a series of spray freeze-dried (SFD) ciprofloxacin hydrochloride (CH)-embedded dry powders were fabricated via a self-designed micro-fluidic spray freeze tower (MFSFT) capable of tuning freezing temperature of cooling air as the refrigerant medium. The effects of total solid content (TSC), mass ratio of CH to L-leucine (Leu) as the aerosol dispersion enhancer, and the freezing temperature on particle morphology, size, density, moisture content, crystal properties, flowability, and aerodynamic performance were investigated. It was found that the Leu content and freezing temperature had considerable influence on the fine particle fraction (FPF) of the SFD microparticles. The optimal formulation (CH/Leu = 7:3, TSC = 2%w/w) prepared at - 40°C exhibited remarkable effective drug deposition (~ 33.38%), good aerodynamic performance (~ 47.69% FPF), and excellent storage stability with ultralow hygroscopicity (~ 1.93%). This work demonstrated the promising feasibility of using the MFSFT instead of conventional liquid nitrogen assisted method in the research and development of high-dose AeDPI.

Oxygen vacancies and interfacial iron sites in hierarchical BiOCl nanosheet microflowers cooperatively promoting photo-Fenton.

Controllable active site construction, crystal structure regulation and efficient charge separation are core issues in heterogeneous photo-Fenton. Herein, abundant oxygen vacancies and well-dispersed interfacial iron sites are simultaneously constructed in hierarchical nanosheet-assembled BiOCl microflowers. The composites exhibit superior performance in photo-Fenton oxidation of carbamazepine (10 mg L-1) with a low H2O2 concentration (1.3 mM). The high performance highly depends on the synergistic effects between oxygen vacancies and iron species. Rather than modulating the valence band, the involvements of oxygen vacancies and iron species could modify the conduction band of BiOCl. The presence of oxygen vacancies promotes the migration of photo-generated electrons and accelerates the redox cycling of ≡Fe(III)/≡Fe(II) to boost the activation of H2O2 to generate hydroxyl radicals, and oxygen vacancies can be well preserved after cyclic use. This work provides understanding on efficient utilization of oxygen vacancies and interfacial iron sites to assist photo-Fenton and the underlying electron transfer mechanism.

Spray Dried Levodopa-Doped Powder Potentially for Intranasal Delivery.

This work was aimed to develop levodopa (L-dopa) nasal powder to achieve controllable drug release and high nasal deposition efficiency. A series of uniform microparticles, composed of amorphous L-dopa and excipients of hydroxypropyl methyl cellulose (HPMC), polyvinylpyrrolidone (PVP), or hydroxypropyl-ß-cyclodextrin (CD), were fabricated by a self-designed micro-fluidic spray dryer. The effects of excipient type and drug/excipient mass ratio on the particle size, morphology, density, and crystal property, as well as the in vitro performance of drug release, mucoadhesion, and nasal deposition, were investigated. Increased amounts of added excipient, regardless of its type, could accelerate the L-dopa release to different extent. The addition of CD showed the most obvious effect, i.e., ~83% of L-dopa released in 60 min for SD-L1CD2, compared to 37% for raw L-dopa. HPMC could more apparently improve the particle mucoadhesion than PVP and CD, with respective adhesive forces of ~269, 111, and 26 nN for SD-L1H2, -L1P2, and -L1CD2. Nevertheless, the deposition fractions in the olfactory region for such samples were almost the same (~14%), probably ascribable to their quite similar particle aerodynamic diameter (~30 µm). This work demonstrates a feasible methodology for the development of nasal powder.

Spray dried hydroxyapatite-based supraparticles with uniform and controllable size and morphology.

This work aims to prepare uniform spray dried hydroxyapatite-based (SD HAP-based) supraparticles with controllable morphology via micro-fluidic spray drying. Sodium polyacrylate (PAAS) and sodium chloride (NaCl) were used to prepare the precursor suspensions by regulating the inter-particle repulsive forces and electrostatic shielding effect, respectively. The particle size (D50) and zeta potential of the suspension were highly associated with the mass ratio of HAP to PAAS (mH/mP) and the NaCl concentration (CNaCl), which further had significant effect on the permeability (k) of the droplet shell formed during spray drying and ultimately the supraparticle morphology. D50 ˂ 2 µm and absolute zeta potential ˃ 20 mV, obtained when mH/mP ˂ 100 under low CNaCl, rendered ultralow k and consequently deformed supraparticles; Whereas D50 ˃ 2 µm and absolute zeta potential ˂ 20 mV, achieved by decreasing PAAS amount, i.e. mH/mP ≥ 100 or improving CNaCl to efficiently screen surface net charge of HAP, high k and spherical supraparticles were thus preferentially formed.

Microdroplet confined assembly enabling the scalable synthesis of titania supported ultrasmall low-valent copper catalysts for efficient photocatalytic activation of peroxymonosulfate.

The synthesis of highly dispersed low-valent copper catalysts is very challenging because they are prone to oxidation and sintering. Herein, scalable synthesis of ultrafine Cu(0)/Cu(i) catalysts supported on mesoporous titania microspheres is enabled by a one-step microdroplet confined assembly method. The extremely fast solute assembly in the microdroplet induces excellent metal precursor dispersion, reduces sol-gel crosslinking, and creates wrinkled microspheres with surface crusts and hollow cavities. This structural architecture allows the generation of an inner reductive gas environment during calcination in air to reduce Cu(ii) and create oxygen vacancy (OV) sites in titania. The obtained catalysts exhibit excellent performance in the photocatalytic activation of peroxymonosulfate (PMS) for pollutant degradation. The Cu(0) species with a surface plasmon resonance effect and OV-rich anatase facilitate efficient solar light utilization and charge separation. The intimate interface between Cu(i)/Cu(0) and anatase enables fast electron transfer and timely copper redox cycling to promote the activation of PMS.

Study on the Stability, Evolution of Physicochemical Properties, and Postsynthesis of Metal-Organic Frameworks in Bubbled Aqueous Ozone Solution.

Metal-organic frameworks (MOFs) are highly promising in many areas. Their application and postsynthesis under strong oxidative environments are emerging. However, the stability, physicochemical property evolution, and possible postmodification and postsynthesis of MOFs in strong oxidative solutions are largely unknown. In this paper, the behaviors of a series of MOFs in bubbled aqueous ozone (O3) solutions are studied. The chosen MOFs are categorized into trimesic type including MIL-101(Fe) and MIL-96(Al); terephthalic type including MOF-74(Co), UiO-66(Zr), MIL-53(Al), and MIL-101(Cr); and imidazole type including ZIF-67(Co) and ZIF-8(Zn), based on the ligand structure. The intrinsic stability and evolution of the physicochemical properties of these MOFs during aqueous O3 treatment are elucidated using structural, morphological, textural, thermal, and spectroscopic analyses. Several stable, metastable, and instable MOFs are identified. The critical parameters that determine the stability and capability for postsynthesis of these MOFs in aqueous O3 solutions are discussed. The stability follows the general order of trimesic-type > terephthalic-type ≫ imidazole-type MOFs because of the distinct antioxidation capability of the ligands. The effects of the ligand, metal cation, and their coordination number on stability are discussed. MIL-100(Fe), MIL-96(Al), and MOF-74(Co) are stable in aqueous O3. UiO-66(Zr), MIL-53(Al), and MIL-101(Cr) are metastable that their porosity, particle size, and crystallinity can be postmodified. ZIF-67(Co) and ZIF-8(Zn) are instable and can be gradually and completely disassembled. Their particle size and morphology and surface groups can be tuned by controlling the treatment time. Postsynthesis of metal hydroxides from ZIF-67(Co) and gradual release of dissolved zinc ion from ZIF-8(Zn) are achievable. The stable MIL-96(Al) shows promising performance in catalytic ozonation for degrading 4-nitrophenol, and the α-Co(OH)2 derived from treating ZIF-67(Co) shows highly promising performance in the electrocatalytic oxygen evolution reaction (OER).

Sintering- and oxidation-resistant ultrasmall Cu(I)/(II) oxides supported on defect-rich mesoporous alumina microspheres boosting catalytic ozonation.

Supported copper oxides with well-dispersed metal species, small size, tunable valence and high stability are highly desirable in catalysis. Herein, novel copper oxide (CuOx) catalysts supported on defect-rich mesoporous alumina microspheres are developed using a spray-drying-assisted evaporation induced self-assembly method. The catalysts possess a special structure composed of a mesoporous outer layer, a mesoporous-nanosphere-stacked under layer and a hollow cavity. Because of this special structure and the defective nature of the alumina support, the CuOx catalysts are ultrasmall in size (1 ~ 3 nm), bivalent with a very high Cu+/Cu2+ ratio (0.7), and highly stable against sintering and oxidation at high temperatures (up to 800 °C), while the wet impregnation method results in CuOx catalysts with much larger sizes (~15 nm) and lower the Cu+/Cu2+ ratios (~0.29). The catalyst formation mechanism through the spray drying method is proposed and discussed. The catalysts show remarkable performance in catalytic ozonation of phenol wastewaters. With high-concentration phenol (250 ppm) as the model organic pollutant, the optimized catalyst delivers promising catalytic performance with 100% phenol removal and 53% TOC removal in 60 min, and a high cyclic stability. Superoxide anion free radicals (⋅O2-), singlet oxygen (1O2) and hydroxyl radicals (⋅OH) are the predominant reactive species. A detailed structure-performance study reveals the surface hydroxyl groups and Cu+/Cu2+ redox couples play cooperatively to accelerate O3 decomposition generating reactive radicals. The plausible catalytic O3 decomposition mechanism is proposed and discussed with supportive evidences.

Immune Monitoring Reveals Fusion Peptide Priming to Imprint Cross-Clade HIV-Neutralizing Responses with a Characteristic Early B Cell Signature.

The HIV fusion peptide (FP) is a promising vaccine target. FP-directed monoclonal antibodies from vaccinated macaques have been identified that neutralize up to ∼60% of HIV strains; these vaccinations, however, have involved ∼1 year with an extended neutralization-eclipse phase without measurable serum neutralization. Here, in 32 macaques, we test seven vaccination regimens, each comprising multiple immunizations of FP-carrier conjugates and HIV envelope (Env) trimers. Comparisons of vaccine regimens reveal FP-carrier conjugates to imprint cross-clade neutralizing responses and a cocktail of FP conjugate and Env trimer to elicit the earliest broad responses. We identify a signature, appearing as early as week 6 and involving the frequency of B cells recognizing both FP and Env trimer, predictive of vaccine-elicited breadth ∼1 year later. Immune monitoring of B cells in response to vaccination can thus enable vaccine insights even in the absence of serum neutralization, here identifying FP imprinting, cocktail approach, and early signature as means to improve FP-directed vaccine responses.

Scalable Synthesis of Uniform Mesoporous Aluminosilicate Microspheres with Controllable Size and Morphology and High Hydrothermal Stability for Efficient Acid Catalysis.

Mesoporous aluminosilicates are promising solid acid catalysts. They are also excellent supports for transition metal catalysts for various catalytic applications. Synthesis of mesoporous aluminosilicates with controllable particle size, morphology, and structure, as well as adjustable acidity and high hydrothermal stability, is very desirable. In this work, we demonstrate the scalable synthesis of Al-SBA-15 microspheres with controllable physicochemical properties by using the microfluidic jet-spray-drying technology. The productivity is up to ∼30 g of dried particles per nozzle per hour. The Al-SBA-15 microspheres possess uniform controllable micron sizes (27.5-70.2 µm), variable surface morphologies, excellent hydrothermal stability (in pure steam at 800 °C), high surface areas (385-464 m2/g), ordered mesopore sizes (5.4-5.8 nm), and desirable acid properties. The dependence of various properties, including particle size, morphology, porosity, pore size, acidity, and hydrothermal stability, of the obtained Al-SBA-15 microspheres on experimental parameters including precursor composition (Si/Al ratio and solid content) and processing conditions (drying and calcination temperatures) is established. A unique morphology transition from smooth to wrinkled microsphere triggered by control of the Si/Al ratio and solid content is observed. The particle formation and morphology-evolution mechanism are discussed. The Al-SBA-15 microspheres exhibit high acid catalytic performance for aldol-condensation reaction between benzaldehyde and ethyl alcohol with a high benzaldehyde conversion (∼56.3%), a fast pseudo-first-order reaction rate (∼0.1344 h-1), and a high cyclic stability, superior to the commercial zeolite acid (H-ZSM-5). Several influencing factors on the catalytic performance of the obtained Al-SBA-15 microspheres are also studied.

Development of a 3Mut-Apex-Stabilized Envelope Trimer That Expands HIV-1 Neutralization Breadth When Used To Boost Fusion Peptide-Directed Vaccine-Elicited Responses.

HIV-1 envelope (Env) trimers, stabilized in a prefusion-closed conformation, can elicit humoral responses capable of neutralizing HIV-1 strains closely matched in sequence to the immunizing strain. One strategy to increase elicited neutralization breadth involves vaccine priming of immune responses against a target site of vulnerability, followed by vaccine boosting of these responses with prefusion-closed Env trimers. This strategy has succeeded at the fusion peptide (FP) site of vulnerability in eliciting cross-clade neutralizing responses in standard vaccine-test animals. However, the breadth and potency of the elicited responses have been less than optimal. Here, we identify three mutations (3mut), Met302, Leu320, and Pro329, that stabilize the apex of the Env trimer in a prefusion-closed conformation and show antigenically, structurally, and immunogenically that combining 3mut with other approaches (e.g., repair and stabilize and glycine-helix breaking) yields well-behaved clade C-Env trimers capable of boosting the breadth of FP-directed responses. Crystal structures of these trimers confirmed prefusion-closed apexes stabilized by hydrophobic patches contributed by Met302 and Leu320, with Pro329 assuming canonically restricted dihedral angles. We substituted the N-terminal eight residues of FP (FP8, residues 512 to 519) of these trimers with the second most prevalent FP8 sequence (FP8v2, AVGLGAVF) and observed a 3mut-stabilized consensus clade C-Env trimer with FP8v2 to boost the breadth elicited in guinea pigs of FP-directed responses induced by immunogens containing the most prevalent FP8 sequence (FP8v1, AVGIGAVF). Overall, 3mut can stabilize the Env trimer apex, and the resultant apex-stabilized Env trimers can be used to expand the neutralization breadth elicited against the FP site of vulnerability.IMPORTANCE A major hurdle to the development of an effective HIV-1 vaccine is the elicitation of serum responses capable of neutralizing circulating strains of HIV, which are extraordinarily diverse in sequence and often highly neutralization resistant. Recently, we showed how sera with 20 to 30% neutralization breadth could, nevertheless, be elicited in standard vaccine test animals by priming with the most prevalent N-terminal 8 residues of the HIV-1 fusion peptide (FP8), followed by boosting with a stabilized BG505-envelope (Env) trimer. Here, we show that subsequent boosting with a 3mut-apex-stabilized consensus C-Env trimer, modified to have the second most prevalent FP8 sequence, elicits higher neutralization breadth than that induced by continued boosting with the stabilized BG505-Env trimer. With increased neutralizing breadth elicited by boosting with a heterologous trimer containing the second most prevalent FP8 sequence, the fusion peptide-directed immune-focusing approach moves a step closer toward realizing an effective HIV-1 vaccine regimen.

A Bimetallic Fe-Mn Oxide-Activated Oxone for In Situ Chemical Oxidation (ISCO) of Trichloroethylene in Groundwater: Efficiency, Sustained Activity, and Mechanism Investigation.

Bimetallic Fe-Mn oxide (BFMO) has been regarded as a promising activator of peroxysulfate (PS), the sustained activity and durability of BFMO for long-term activation of PS in situ, however, is unclear for groundwater remediation. A BFMO (i.e., Mn1.5FeO6.35) was prepared and explored for PS-based in situ chemical oxidation (ISCO) of trichloroethylene (TCE) in sand columns with simulated/actual groundwater (SGW/AGW). The sustained activity of BFMO, oxidant utilization efficiency, and postreaction characterization were particularly investigated. Electron spin resonance (ESR) and radical scavenging tests implied that sulfate radicals (SO4•-) and hydroxyl radicals (HO•) played major roles in degrading TCE, whereas singlet oxygen (1O2) contributed less to TCE degradation by BFMO-activated Oxone. Fast degradation and almost complete dechlorination of TCE in AGW were obtained, with reaction stoichiometry efficiencies (RSE) of ΔTCE/ΔOxone at 3-5%, much higher than those reported RSE values in H2O2-based ISCO (≤0.28%). HCO3- did not show detrimental effect on TCE degradation, and effects of natural organic matters (NOM) were negligible at high Oxone dosage. Postreaction characterizations displayed that the BFMO was remarkably stable with sustained activity for Oxone activation after 115 days of continuous-flow test, which therefore can be promising catalyst for Oxone-based ISCO for TCE-contaminated groundwater remediation.

Spray-drying water-based assembly of hierarchical and ordered mesoporous silica microparticles with enhanced pore accessibility for efficient bio-adsorption.

The fast and scalable spray-drying-assisted evaporation-induced self-assembly (EISA) synthesis of hierarchically porous SBA-15-type silica microparticles from a water-based system is demonstrated. The SBA-15-type silica microparticles has bowl-like shapes, uniform micro-sizes (∼90 µm), large ordered mesopores (∼9.5 nm), hierarchical meso-/macropores (20-100 nm) and open surfaces. In the synthesis, soft- and hard-templating approaches are combined in a single rapid drying process with a non-ionic tri-block copolymer (F127) and a water-insoluble polymer colloid (Eudragit RS, 120 nm) as the co-templates. The RS polymer colloid plays three important roles. First, the RS nanoparticles can be partially dissolved by in-situ generated ethanol to form RS polymer chains. The RS chains swell and modulate the hydrophilic-hydrophobic balance of F127 micelles to allow the formation of an ordered mesostructure with large mesopore sizes. Without RS, only worm-like mesostructure with much smaller mesopore sizes can be formed. Second, part of the RS nanoparticles plays a role in templating the hierarchical pores distributed throughout the microparticles. Third, part of the RS polymer forms surface "skins" and "bumps", which can be removed by calcination to enable a more open surface structure to overcome the low pore accessibility issue of spray-dried porous microparticles. The obtained materials have high surface areas (315-510 m2 g-1) and large pore volumes (0.64-1.0 cm3 g-1), which are dependent on RS concentration, HCl concentration, silica precursor hydrolysis time and drying temperature. The representative materials are promising for the adsorption of lysozyme. The adsorption occurs at a >three-fold faster rate, in a five-fold larger capacity (an increase from 20 to 100 mg g-1) and without pore blockage compared with the adsorption of lysozyme onto spray-dried microparticles of similar physicochemical properties obtained without the use of RS.

Variability in Hospital Admission Rates for Neonates With Fever in North Carolina.

Background. Despite multiple guidelines recommending admission, there is significant variation among emergency departments (EDs) regarding disposition of neonates presenting with fever. We performed a statewide epidemiologic analysis to identify characteristics that may influence patient disposition in such cases within North Carolina. Methods. This study is a retrospective cohort study of infants 1 to 28 days old with a diagnosis of fever presenting to North Carolina EDs from October 1, 2010, to September 30, 2015, using data from the NC DETECT (North Carolina Disease Event Tracking and Epidemiologic Collection Tool) database. We analyzed various patient epidemiology characteristics and their associations with patients being admitted or discharged from the emergency room setting. Results. Of 2745 unique patient visits for neonatal fever, 1173 (42.7%) were discharged from the ED, while 1572 (57.3%) were either admitted or transferred for presumed admission. Age, sex, region within North Carolina, and the presence of a pediatric service did not significantly influence disposition. An abnormal documented ED temperature was associated with higher likelihood of admission (P < .01). The size of the hospital was also found to be significant when comparing large with small hospitals (P < .01). Government-funded insurance was associated with lower likelihood of admission (P < .01). Conclusions. A high number of neonates diagnosed with fever were discharged home, inconsistent with current recommendations. An association with a government-funded insurance represents a possible health care disparity. Further studies are warranted to further understand these variations in practice.

Antibody Lineages with Vaccine-Induced Antigen-Binding Hotspots Develop Broad HIV Neutralization.

The vaccine-mediated elicitation of antibodies (Abs) capable of neutralizing diverse HIV-1 strains has been a long-standing goal. To understand how broadly neutralizing antibodies (bNAbs) can be elicited, we identified, characterized, and tracked five neutralizing Ab lineages targeting the HIV-1-fusion peptide (FP) in vaccinated macaques over time. Genetic and structural analyses revealed two of these lineages to belong to a reproducible class capable of neutralizing up to 59% of 208 diverse viral strains. B cell analysis indicated each of the five lineages to have been initiated and expanded by FP-carrier priming, with envelope (Env)-trimer boosts inducing cross-reactive neutralization. These Abs had binding-energy hotspots focused on FP, whereas several FP-directed Abs induced by immunization with Env trimer-only were less FP-focused and less broadly neutralizing. Priming with a conserved subregion, such as FP, can thus induce Abs with binding-energy hotspots coincident with the target subregion and capable of broad neutralization.

Facile synthesis of alkaline-earth metal manganites for the efficient degradation of phenolic compounds via catalytic ozonation and evaluation of the reaction mechanism.

In this paper, we demonstrate the facile and general synthesis of alkaline-earth metal manganites, denoted as A(Mg, Ca, Ba)MnxOy, for efficient degradation of high-concentration phenolic compounds via catalytic ozonation. The representative CaMnxOy oxides show a hierarchical spherical structure constructed by crystalline nanorods and numerous macropores. They possess mixed Mn4+/Mn3+ chemical valences and abundant surface hydroxyl (OH) groups. The ozone (O3) decomposition rate on the CaMnxOy catalysts is greatly accelerated and follows the first-order law. These catalysts are promising for the degradation of phenolic compounds via catalytic ozonation, exhibiting rapid pseudofirst-order degradation kinetics, a high total organic carbon (TOC) removal efficiency and an excellent stability. Under optimized conditions (a low O3 dosage of 1.5 mg/min and a catalyst dosage of 7.5 g/L), for the treatment of concentrated phenol (50-240 mg/L), the CaMnxOy catalysts show 100% degradation and 50-70% mineralization within 1.0 h. The Ca2+ ions are essential to create redox Mn4+/Mn3+ couples and to significantly reduce manganese leaching. High surface ratios of Mn4+/Mn3+ and OH/lattice oxygen (Olat) are beneficial for enhancing the catalytic performance. Superoxide anion free radicals (O2-) and singlet oxygen (1O2) are the predominant reactive species for the oxidation degradation. The O2- reaction pathway is proposed. Specifically, the surface OH sites activate O3, displaying highly enhanced decomposition rates. The generated O2- and 1O2 play a role in oxidation. The redox Mn4+/Mn3+ and the Olat/oxygen vacancy (Olat/Ovac) couples play important roles in electron transfer. The proposed mechanism is supported by active site probing, radical scavenging, spectroscopic studies, and the results in the degradation of substituted phenols.