Healthy Vaccinee Bias and MenB-FHbp Vaccine Effectiveness Against Gonorrhea.

Observational studies demonstrated 30% to 40% effectiveness of outer-membrane vesicle (OMV) meningococcal serogroup B vaccines against gonorrhea. To explore whether healthy vaccinee bias influenced such findings, we examined the effectiveness of MenB-FHbp, a non-OMV vaccine that is not protective against gonorrhea. MenB-FHbp was ineffective against gonorrhea.

Demographic and Clinical Characteristics of Mpox in Persons Who Had Previously Received 1 Dose of JYNNEOS Vaccine and in Unvaccinated Persons - 29 U.S. Jurisdictions, May 22-September 3, 2022.

As of November 14, 2022, monkeypox (mpox) cases had been reported from more than 110 countries, including 29,133 cases in the United States.* Among U.S.

Molecularly Functionalized Electrodes for Efficient Electrochemical Water Remediation.

The development and investigation of materials that leverage unique interfacial effects on electronic structure and redox chemistry are likely to play an outstanding role in advanced technologies for wastewater treatment. Here, the use of surface functionalization of metal oxides with a Ru poly(pyridyl) complex was reported as a way to create hybrid assemblies with optimized electrochemical performance for water remediation, superior to those that could be achieved with the molecular catalyst or metal-oxide electrodes used individually. Mechanistic analysis demonstrated that the molecularly functionalized electrodes could suppress the formation of hydroxyl radicals (i.

Surface immobilized copper(I) diimine photosensitizers as molecular probes for elucidating the effects of confinement at interfaces for solar energy conversion.

Heteroleptic copper(i) bis(phenanthroline) complexes with surface anchoring carboxylate groups have been synthesized and immobilized on nanoporous metal oxide substrates. The species investigated are responsive to the external environment and this work provides a new strategy to control charge transfer processes for efficient solar energy conversion.

Stabilization of Ruthenium(II) Polypyridyl Chromophores on Mesoporous TiO Electrodes: Surface Reductive Electropolymerization and Silane Chemistry.

Stabilization is a critical issue in the long term operation of dye-sensitized photoelectrosynthesis cells (DSPECs) for water splitting or CO reduction. The cells require a stable binding of the robust molecular chromophores, catalysts, and chromophore/catalyst assemblies on metal oxide semiconductor electrodes under the corresponding (photoelectro)chemical conditions. Here, an efficient stabilization strategy is presented based on functionalization of FTOTiO (mesoporous, nanostructured TiO deposited on fluorine-doped tin oxide (FTO) glass) electrodes with a vinylsilane followed by surface reductive electropolymerization of a vinyl-derivatized Ru(II) polypyridyl chromophore.

Light-driven water oxidation by a dye-sensitized photoanode with a chromophore/catalyst assembly on a mesoporous double-shell electrode.

A mesoporous atomic layer deposition (ALD) double-shell electrode, AlO (insulating core)//ALD ZnO|ALD TiO, on a fluorine-doped tin oxide (FTO) conducting substrate was explored for a photoanode assembly, FTO//AlO (insulating core)//ALD ZnO|ALD TiO|-chromophore-catalyst, for light-driven water oxidation. Photocurrent densities at photoanodes based on mesoporous ALD double-shell (ALD ZnO|ALD TiO|) and ALD single-shell (ALD ZnO|, ALD TiO|) electrodes were investigated for O evaluation by a generator-collector dual working electrode configuration. The high photocurrent densities obtained based on the mesoporous ALD ZnO|ALD TiO photoanode for O evolution arise from a significant barrier to back electron transfer (BET) by the optimized tunneling barrier in the structure with the built-in electric field at the ALD ZnO|ALD TiO interface.

Stable Molecular Surface Modification of Nanostructured, Mesoporous Metal Oxide Photoanodes by Silane and Click Chemistry.

Binding functional molecules to nanostructured mesoporous metal oxide surfaces provides a way to derivatize metal oxide semiconductors for applications in dye-sensitized photoelectrosynthesis cells (DSPECs). The commonly used anchoring groups, phosphonates and carboxylates, are unstable as surface links to oxide surfaces at neutral and high pH, leading to rapid desorption of appended molecules. A synthetically versatile molecular attachment strategy based on initial surface modification with a silyl azide followed by click chemistry is described here.

A Molecular Silane-Derivatized Ru(II) Catalyst for Photoelectrochemical Water Oxidation.

Photoanodes in dye-sensitized photoelectrosynthesis cells integrate molecular chromophore/catalyst assemblies on mesoporous n-type metal oxide electrodes for light-driven water oxidation. One limitation for sustainable photoanodes is the stability of chromophore/catalyst assembly on electrode surfaces for long periods. Progress has been made in stabilizing chromophores based on atomic layer deposition, polymer dip coating, C-C cross-coupling by electropolymerization, and silane surface binding, but little progress has been made on catalyst stabilization.

Stabilized photoanodes for water oxidation by integration of organic dyes, water oxidation catalysts, and electron-transfer mediators.

Stabilized photoanodes for light-driven water oxidation have been prepared on nanoparticle core/shell electrodes with surface-stabilized donor-acceptor chromophores, a water oxidation catalyst, and an electron-transfer mediator. For the electrode, fluorine-doped tin oxide FTO|SnO/TiO|-Org1-|1.1 nm AlO|-RuP-WOC (water oxidation catalyst) with Org1 (1-cyano-2-(4-(diphenylamino)phenyl)vinyl)phosphonic acid), the mediator RuP ([Ru(4,4-(POH)-2,2-bipyridine)(2,2-bipyridine)]), and the WOC, Ru(bda)(py(CH)P(OH)) (bda is 2,2-bipyridine-6,6-dicarboxylate with x = 3 or 10), solar excitation resulted in photocurrents of ∼500 µA/cm and quantitative O evolution at pH 4.

Completing a Charge Transport Chain for Artificial Photosynthesis.

A ruthenium polypyridyl chromophore with electronically isolated triarylamine substituents has been synthesized that models the role of tyrosine in the electron transport chain in photosystem II. When bound to the surface of a TiO electrode, electron injection from a Ru(II) Metal-to-Ligand Charge Transfer (MLCT) excited state occurs from the complex to the electrode to give Ru(III). Subsequent rapid electron transfer from the pendant triarylamine to Ru(III) occurs with an observed rate constant of ∼10 s, which is limited by the rate of electron injection into the semiconductor.

Interfacial Deposition of Ru(II) Bipyridine-Dicarboxylate Complexes by Ligand Substitution for Applications in Water Oxidation Catalysis.

Water oxidation is a critical step in artificial photosynthesis and provides the protons and electrons used in reduction reactions to make solar fuels. Significant advances have been made in the area of molecular water oxidation catalysts with a notable breakthrough in the development of Ru(II) complexes that use a planar "bda" ligand (bda is 2,2'-bipyridine-6,6'-dicarboxylate). These Ru(II)(bda) complexes show lower overpotentials for driving water oxidation making them ideal for light-driven applications with a suitable chromophore.

Water Photo-oxidation Initiated by Surface-Bound Organic Chromophores.

Organic chromophores can be synthesized by established methods and offer an opportunity to expand overall solar spectrum utilization for dye-sensitized photoelectrosynthesis cells. However, there are complications in the use of organic chromophores arising from the instability of their oxidized forms, the inability of their oxidized forms to activate a water oxidation catalyst, or the absence of a sufficiently reducing excited state for electron injection into appropriate semiconductors. Three new triarylamine donor-acceptor organic dyes have been investigated here for visible-light-driven water oxidation.

Place Still Matters: Racial/Ethnic and Geographic Disparities in HIV Transmission and Disease Burden.

Neighborhood-level structural interventions are needed to address HIV/AIDS in highly affected areas. To develop these interventions, we need a better understanding of contextual factors that drive the pandemic. We used multinomial logistic regression models to examine the relationship between census tract of current residence and mode of HIV transmission among HIV-positive cases.

Plasmon-enhanced light-driven water oxidation by a dye-sensitized photoanode.

Dye-sensitized photoelectrosynthesis cells (DSPECs) provide a flexible approach for solar water splitting based on the integration of molecular light absorption and catalysis on oxide electrodes. Recent advances in this area, including the use of core/shell oxide interfacial structures and surface stabilization by atomic layer deposition, have led to improved charge-separation lifetimes and the ability to obtain substantially improved photocurrent densities. Here, we investigate the introduction of Ag nanoparticles into the core/shell structure and report that they greatly enhance light-driven water oxidation at a DSPEC photoanode.

Layer-by-Layer Molecular Assemblies for Dye-Sensitized Photoelectrosynthesis Cells Prepared by Atomic Layer Deposition.

In a dye sensitized photoelectrosynthesis cell (DSPEC), the relative orientation of the catalyst and chromophore plays an important role in determining the device efficiency. Here we introduce a new, robust atomic layer deposition (ALD) procedure for the preparation of molecular chromophore-catalyst assemblies on wide bandgap semiconductors. In this procedure, solution deposited, phosphonate derivatized metal complexes on metal oxide surfaces are treated with reactive metal reagents in the gas phase by ALD to form an outer metal ion bridging group, which can bind a second phosphonate containing species from solution to establish a R-PO-O-M-O-PO-R type surface assembly.

Antiretroviral Prescription and Viral Suppression in a Representative Sample of HIV-Infected Persons in Care in 4 Large Metropolitan Areas of the United States, Medical Monitoring Project, 2011-2013.

Background: Comparisons of antiretroviral therapy (ART) prescription and viral suppression among people in HIV care across US metropolitan areas are limited. Medical Monitoring Project, 2011-2013, data were used to describe and compare associations between sociodemographics and ART prescription and viral suppression for persons receiving HIV care.

Setting: Chicago, Los Angeles County (LAC), Philadelphia, and San Francisco in the United States.

Cationic Copper Hydride Clusters Arising from Oxidation of (PhP)CuH.

Transfer of the first electron from (PhP)CuH to Cp*Fe is fast (k > 10 L·mol·s). Transfer of a second electron to the same oxidant has a much lower thermodynamic driving force and is considerably slower, with k = 9.29(4) × 10 L·mol·s.

Fluoropolymer-Stabilized Chromophore-Catalyst Assemblies in Aqueous Buffer Solutions for Water-Oxidation Catalysis.

Here, the application of the fluorinated polymer [Dupont AF, a copolymer of 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole and tetrafluoroethylene] is described in stabilizing phosphonate-derivatized molecular assemblies on oxide electrodes. In the procedure, the polymer was dip-coated onto the surfaces of oxide electrodes with pre-bound, phosphonate-derivatized chromophores and assemblies, including assemblies for water oxidation. The results of the experiments showed a high degree of stabilization by the added polymer and a demonstration of its use in stabilizing surface-bound assemblies for water-oxidation catalysis.

Viral Loads Among HIV-Infected Persons Diagnosed With Primary and Secondary Syphilis in 4 US Cities: New York City, Philadelphia, PA, Washington, DC, and Phoenix, AZ.

Background: Incident syphilis among HIV-infected persons indicates the ongoing behavioral risk for HIV transmission. Detectable viral loads (VLs) among coinfected cases may amplify this risk.

Methods: Primary and secondary cases reported during 2009-2010 from 4 US sites were crossmatched with local HIV surveillance registries to identify syphilis case-persons infected with HIV before or shortly after the syphilis diagnosis.

Individual and community factors associated with geographic clusters of poor HIV care retention and poor viral suppression.

Background: Previous analyses identified specific geographic areas in Philadelphia (hotspots) associated with negative outcomes along the HIV care continuum. We examined individual and community factors associated with residing in these hotspots.

Methods: Retrospective cohort of 1404 persons newly diagnosed with HIV in 2008-2009 followed for 24 months after linkage to care.

Location of HIV diagnosis impacts linkage to medical care.

: We evaluated 1359 adults newly diagnosed with HIV in Philadelphia in 2010-2011 to determine if diagnosis site (medical clinic, inpatient setting, counseling and testing center (CTC), and correctional facility) impacted time to linkage to care (difference between date of diagnosis and first CD4/viral load). A total of 1093 patients (80%) linked to care: 86% diagnosed in medical clinics, 75% in inpatient settings, 62% in CTCs, and 44% in correctional facilities. Adjusting for other factors, diagnosis in inpatient settings, CTCs, and correctional facilities resulted in a 33% (adjusted hazard ratio = 0.

Comparison of geographic methods to assess travel patterns of persons diagnosed with HIV in Philadelphia: how close is close enough?

Travel distance to medical care has been assessed using a variety of geographic methods. Network analyses are less common, but may generate more accurate estimates of travel costs. We compared straight-line distances and driving distance, as well as average drive time and travel time on a public transit network for 1789 persons diagnosed with HIV between 2010 and 2012 to identify differences overall, and by distinct geographic areas of Philadelphia.