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Cellulose nanomaterial (CNM) and polyethylenimine (PEI) composites have attracted growing attention due to their multifunctional characteristics, which have been applied in different fields. In this work, soybean hulls were valorized into carboxyl cellulose nanofibrils (COOH-CNFs), and composited into hydrogels with PEI by combining them with cationic chelating and physical adsorption strategies. Cellulose nanofibrils (CNFs) were produced from soybean hulls prior to oxidation by a TEMPO mediated reaction to obtain COOH–CNFs; then drops of zinc chloride were added to 1.5% aqueous COOH–CNF dispersions, which were left for 24 h to form COOH-CNF hydrogels. Finally, the hydrogels were functionalized using different concentration of PEI solutions over a range of pH values. Elemental analysis results showed that 20% aq. PEI at pH 11.6 is the optimum condition to synthesize the COOH–CNF/PEI hydrogels. Additionally, the adsorption efficiency for the removal of anionic methyl blue dyes and Cu(II) ions from water was tested, reaching 82.6% and 69.8%, respectively, after 24 h. These results demonstrate the great potential of COOH–CNF/PEI hydrogels as adsorbent materials for water remediation. Graphical abstract

Here, we report the synthesis of robust hybrid iodinated silica-lipid nanoemulsions (HSLNEs) for use as a contrast agent for ultrasound and X-ray applications. We engineered iodinated silica nanoparticles (SNPs), lipid nanoemulsions, and a series of HSLNEs by a low-energy spontaneous nanoemulsification process. The formation of a silica shell requires sonication to hydrolyze and polymerize/condensate the iodomethyltrimethoxysilane at the oil/water interface of the nanoemulsion droplets. The resulting nanoemulsions (NEs) exhibited a homogeneous spherical morphology under transmission electron microscopy. The particles had diameters ranging from 20 to 120 nm with both negative and positive surface charges in the absence and presence of cetyltrimethylammonium bromide (CTAB), respectively. Unlike CTAB-coated nanoformulations, the CTAB-free NEs showed excellent biocompatibility in murine RAW macrophages and human U87-MG cell lines in vitro. The maximum tolerated dose assessment was evaluated to verify their safety profiles in vivo. In vitro X-ray and ultrasound imaging and in vivo computed tomography were used to monitor both iodinated SNPs and HSLNEs, validating their significant contrast-enhancing properties and suggesting their potential as dual-modality clinical agents in the future.

Infections of Toxoplasma gondii can cause severe and sometimes fatal diseases in immunocompromised individuals. The de novo heme biosynthesis pathway is required for intracellular growth and pathogenesis, making it an appealing therapeutic target. We synthesized a small library of derivatives of the herbicide oxadiazon, a known inhibitor of the penultimate reaction within the heme biosynthesis pathway in plants, catalyzed by protoporphyrinogen oxidase (PPO). Seven of the 18 analogs exhibit potent intracellular growth inhibition of wild-type T. gondii (IC(50) = 1 to 2.4 μM). An assay of the compounds against Toxoplasma PPO knockout and complementation strains confirmed the mode of action to be due to the potent inhibition of PPO. The most potent compounds have no detectable cytotoxicity against human foreskin fibroblast cells up to 100 μM. This study suggests that oxadiazon derivatives may represent a new molecular scaffold for the effective treatment of T. gondii infections.

A versatile biosensing platform based on a single electrode electrochemical system, paper-based devices and glow sticks.

Hydrogels are promising candidates for wound healing bandages because they can mimic the native skin microenvironment. Additionally, there is increasing growth in the use of naturally derived materials and plant-based biomaterials to produce healthcare products with healing purposes because of their biocompatibility and biodegradation properties. In this study, cellulose extracted from biodiverse sources in Ecuador was used as the raw material for the fabrication of hydrogels with enhanced antifouling properties. Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM) were used to characterize the cellulose and hydrogels.

Various noninvasive imaging techniques are used to produce deep-tissue and high-resolution images for biomedical research and clinical purposes. Organic and inorganic bioimaging agents have been developed to enhance the resolution and contrast intensity. This paper describes the synthesis of polytetrafluoroethylene-like nanoparticles (PTFE≈ NPs), their characterization, biological activity, and bioimaging properties. Transmission electron microscopy (TEM) images showed the shape and the size of the as-obtained small and ultrasmall PTFE≈ NPs. Fourier transform infrared spectroscopy (FTIR) confirmed the PTFE-like character of the samples. X-ray diffraction (XRD) enabled the determination of the crystallization system, cell lattice, and index of crystallinity of the material in addition to the presence of titania (TiO2) as the contamination. These findings were corroborated by X-ray photoelectron spectroscopy (XPS) that identifies the chemical states of the elements present in the samples along with their atomic percentages allowing the determination of both the purity index of the sample and the nature of the impurities. Additionally, diffuse reflectance ultraviolet-visible spectroscopy (UV-vis) was used to further assess the optical properties of the materials. Importantly, PTFE≈ NPs showed significant in vitro and in vivo biocompatibility. Lastly, PTFE≈ NPs were tested for their ultrasound and X-ray contrast properties. Our encouraging preliminary results open new avenues for PTFE-like nanomaterials as a suitable multifunctional contrast agent for biomedical imaging applications. Combined with suitable surface chemistry and morphology design, these findings shed light to new opportunities offered by PTFE nanoparticles in the ever-booming biomedical field.

The structures of seven compounds based on guanidinium cations, isolated sulfate anions, and additional organic cations and solvent molecules are reported. All seven compounds, (C(NH2)3)2(SO4) (1), (C(NH2)3)3(C5H6N)(SO4)2 (2), (C(NH2)3)3(C5H6N)(SO4)2·H2O (3), (C(NH2)3)3(C5H6N)(SO4)2·CH3OH (4), (C(NH2)3)11(C5H6N)(SO4)6·2.5C2H5OH (5), (C(NH2)3)3(C6H16N)(SO4)2 (6), and (C(NH2)3)2(C20H26N2O2)(SO4)2 (7) crystallize without a center of symmetry, and are built of related motifs of six-membered rings via hydrogen bonding of three guanidinium cations and three sulfate anions. These six-membered rings form extended sheets and frameworks through additional hydrogen bonding interactions. The presence of additional cations and solvent molecules in varying ratios add structural diversity by modifying the guanidinium sulfate frameworks, but retaining the acentricity of the structures. The study reveals a remarkable tendency for these guanidinium sulfate frameworks to crystallize without a center of symmetry, and furthermore, in polar or chiral space groups. This provides a potential pathway for the use of hydrogen bonding interactions to design structures having interesting physical or nonlinear optical properties.

Lipid nanoemulsions (LNEs) are promising nanocarriers for delivering high payloads of lipophilic molecules. Nonetheless, the dynamic nature at their aqueous interfaces results in poor surface chemistry and thus ligand functionalization can be challenging. Herein, two independent strategies, postconjugation and preconjugation, were explored to prepare LNEs grafted covalently with model ligands, fluorescein dye and RGD peptide, respectively. Fluorescein was successfully conjugated with high grafting efficiency to an amine-functionalized lipid nanoemulsion (NH

Electrophilic halofunctionalization reactions have undergone a resurgence sparked by recent discoveries in the field of catalytic asymmetric halocyclizations. To build mechanistic understanding of these asymmetric transformations, a toolbox of analytical methods has been deployed, addressing the roles of catalyst, electrophile (halenium donor), and nucleophile in determining rates and stereopreferences. The test reaction, (DHQD)2PHAL-catalyzed chlorocyclization of 4-arylpent-4-enoic acid with 1,3-dichloro-5,5-dimethylhydantoin (DCDMH), is revealed to be first order in catalyst and chlorenium ion donor and zero order in alkenoic acid substrate under synthetically relevant conditions. The simplest interpretation is that rapid substrate-catalyst binding precedes rate-limiting chlorenium attack, controlling the face selectivity of both chlorine attack and lactone closure. ROESY and DFT studies, aided by crystal structures of carboxylic acids bound by the catalyst, point to a plausible resting state of the catalyst-substrate complex predisposed for asymmetric chlorolactonization. As revealed by our earlier labeling studies, these findings suggest modes of binding in the (DHQD)2PHAL chiral pocket that explain the system's remarkable control over rate- and enantioselection-determining events. Though a comprehensive modeling analysis is beyond the scope of the present work, quantum chemical analysis of the fragments' interactions and candidate reaction paths point to a one-step concerted process, with the nucleophile playing a critical role in activating the olefin for concomitant electrophilic attack.

Periodic mesoporous organosilica nanoparticles (PMO SiNPs) were developed for the targeted capture of specific volatile organic compounds (VOCs). The removal kinetics for adsorbing VOCs were fast and the maximum removal could be achieved within less than 30 min. PMO SiNPs removed >99% of VOCs at a low sorbent dose (i.e. >0.5 mL analyte per g PMO SiNPs). They also showed good recyclability and maintained reasonable removal efficiencies after five cycles (i.e. 77% and 65% for hexanal and butyric acid vapors, respectively).

Aldehydes are commonly encountered Volatile Organic Compounds (VOCs) released to the atmosphere from a variety of anthropogenic sources. Based on the increasing interest in developing sustainable and environmentally friendly materials for the decontamination of VOCs, cellulose particles have emerged as one possible candidate, but there is a lack of understanding of the physicochemical properties affecting the adsorption of VOCs, and the effect of the extraction source on these intrinsic features. The present study was focused on the evaluation of unmodified cellulose particles extracted from biodiverse sources in Ecuador as potential VOC decontaminants. Modifications of the natural fibers with polyethylenimine (PEI) coating were performed to enhance the adsorption effectiveness. Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Brunauer–Emmett–Teller (BET) measurements, and scanning electron microscopy (SEM) methods were used to characterize the physicochemical properties of the isolates. Gas chromatography assays demonstrated that unmodified cellulose can adsorb an aldehyde VOC, hexanal, reaching up to a 56.42 ± 7.30% reduction. Electrostatic coating of the cellulose particles with small quantities of PEI enhanced the VOC remediation capacities (i.e. 98.12 ± 1.18%). Results demonstrated that the biodiverse plant source of the cellulose isolate can affect the gas capturing properties, and that these particles can be an environmentally friendly solution for effective adsorption of VOC pollutants.

A novel technique for the absolute stereochemical determination of alcohols has been developed that uses crystallization of guanidinium salts of organosulfates. The simple one-pot, two-step process leverages facile formation of guandinium organosulfate single crystals for the straightforward determination of the absolute stereochemistry of enantiopure alcohols by means of X-ray crystallography. The strong hydrogen bonding network drives the stability of the crystal lattice and allows for a diverse range of organic alcohol substrates to be analyzed.

Strategies for the synthesis of a new class of porous and nonporous biodegradable microparticles (MPs) based on poly(D,L-lactic acid)-poly(ethylene glycol)-COOH (PDLLA-PEG-COOH) or poly(D,L-lactide-co-glycolide) (PLGA) copolymers have been investigated. Further, these MPs were coated with polyethylenimine (PEI) in order to compare the performance of the naked and PEI-capped MPs for the gas phase capture of model aldehyde VOCs, hexanal and octanal. The removal efficiencies of the different MP formulations ranged from 50% reduction to 97% reduction of VOC vapors. By coupling the intrinsic gas adsorption properties of the parent, naked MPs with the potential for covalent capture by means of PEI-surface coating, we have generated new materials exhibiting a dual modality for VOC capture. These materials represent a new matrix for the remediation of VOCs based on renewable, sustainable polymers.

The α-oxidized thioimidates are useful bidentate ligands and are important motifs in pharmaceuticals, pesticides, and fungicides. Despite their broad utility, a direct route for their synthesis has been elusive. Herein, we describe a one-step synthesis of N,N-dicarbamoyl 2-iminothioimidates from easily accessible thioacetylenes and commercially available azodicarboxylates (20 examples, ≤99% yield). Additionally, the mechanism of the transformation was extensively explored by variable-temperature NMR, in situ IR, and quantum mechanical simulations. These experiments suggest that the reaction commences with a highly asynchronous [2 + 2] cycloaddition, which leads to a four-membered diazacyclobutene intermediate with a barrier consistent with the observed reaction rate. This intermediate was then isolated for subsequent kinetic measurements, which yielded an experimental barrier within 1 kcal/mol of the calculated barrier for a subsequent 4π electrocyclic ring opening leading to the observed iminothioimidate products. This method represents the first direct route to α-oxidized thioimidates from readily accessible starting materials.

Persistent Organic Pollutants (POPs) have become a very serious issue for the environment because of their toxicity, resistance to conventional degradation mechanisms, and capacity to bioconcentrate, bioaccumulate and biomagnify. In this review article, the safety, regulatory, and remediation aspects of POPs including aromatic, chlorinated, pesticides, brominated, and fluorinated compounds, are discussed. Industrial and agricultural activities are identified as the main sources of these harmful chemicals, which are released to air, soil and water, impacting on social and economic development of society at a global scale. The main types of POPs are presented, illustrating their effects on wildlife and human beings, as well as the ways in which they contaminate the food chain. Some of the most promising and innovative technologies developed for the removal of POPs from water are discussed, contrasting their advantages and disadvantages with those of more conventional treatment processes. The promising methods presented in this work include bioremediation, advanced oxidation, ionizing radiation, and nanotechnology. Finally, some alternatives to define more efficient approaches to overcome the impacts that POPs cause in the hydric sources are pointed out. These alternatives include the formulation of policies, regulations and custom-made legislation for controlling the use of these pollutants.

A series of amine-functionalized cellulose nanocrystal materials were successfully synthesized, characterized, and evaluated for the remediation of pesticide contaminants from organic and aqueous media. Their ability to degrade malathion in organic systems has been examined, resulting in up to 100% degradation of the compound into detectable lower molecular weight by-products. A poly(ethylenimine) cellulose nanocrystal (CNC-PEI) material was also capable of degrading aqueous solutions of malathion, deltamethrin, and permethrin with 100%, 95%, and 78% degradation, respectively. Thus, these materials can potentially serve as a new and viable remediation technique based on their ability to effectively degrade various pesticides. The reusability of the CNC-PEI was also explored. The CNC-PEI material maintained its ability to degrade malathion throughout two wash and re-use cycles.

We describe the inhibition of the starch utilization system (Sus) belonging to various strains of Bacteroides dorei in a non-lethal manner using the small molecule probe, acarbose. Concentrations of acarbose as low as 5 μM significantly impede the growth of B. dorei and increase the doubling time of cultures. The successful inhibition of this species of Bacteroides is relevant to several disease states including type I diabetes mellitus. This method continues to explore a new, potential route to intervene in illnesses associated with aberrant changes in the composition of the human gut microbiota through the strategic manipulation of its constituents.

The synthesis and application of gold nanoparticles (AuNPs) have attracted much attention due to their interesting optical and chemical properties, as well as their utility in imaging, therapeutics, sensors, electronics, and catalysis. AuNPs are synthesized using multiple approaches, followed by chemical modification or encapsulation, to enhance their colloidal stability, biocompatibility, and targeting. Here, we report the one-step synthesis of gold–polyester nanoparticles for use as an imaging agent. The AuNPs were prepared inside polymeric NPs by means of ultraviolet irradiation of a gold salt in the presence of Irgacure I-2959 photoinitiator. We monitored the kinetic growth and nucleation of AuNPs (in vitro and ex vivo) over time using spectral analysis. Moreover, we investigated the cytotoxicity, localized plasmonic surface resonance (LSPR), and cellular imaging capabilities of the Au–polyester nanoparticles. The resulting Au–polyester NPs were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), dynamic light scattering (DLS), and transmission electron microscopy (TEM) to probe their chemical structure, size, zeta potential (ζ), and morphology, respectively. Furthermore, in vitro experiments showed that the NP formulation is stable over time and exhibits negligible toxicity against 3T3 fibroblast and U-87 MG glioblastoma cells. The results also demonstrated that the Au–polyester NPs exhibit excellent cellular imaging properties. This one-step strategy goes beyond current syntheses of gold–polyester nanoparticles because it can be used to synthesize the imaging agent in situ (i.e., in living cells) in lieu of conventional ex situ approaches.

Electrophilic halofunctionalization reactions have undergone a resurgence sparked by recent discoveries in the field of catalytic asymmetric halocyclizations. To build mechanistic understanding of these asymmetric transformations, a toolbox of analytical methods has been deployed, addressing the roles of catalyst, electrophile (halenium donor), and nucleophile in determining rates and stereopreferences. The test reaction, (DHQD)

A formal [2 + 2] cycloaddition of 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) with electron-rich alkynyl sulfides and selenides is described. These investigations provide a convenient method to access diazacyclobutenes in good yield while tolerating a relatively broad substrate scope of thio-acetylenes. This method provides ready access to a unique and hitherto rarely accessible class of heterocycles. A combination of dynamic NMR, X-ray crystallography, and computation sheds light on the potential aromaticity of the scaffold.

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in many consumer products and present serious environmental challenges due to their persistent nature. Currently, conventional water treatment methods fail to remove PFAS, and other newly proposed materials/techniques face challenges when employed under realistic conditions. This study reports on poly(ethylenimine)-functionalized cellulose microcrystals (PEI-f-CMC) that showed a near-instant and high removal of PFAS under concentrations relevant to their actual occurrence in the natural environment (i.e.

Human African trypanosomiasis is a disease of sub-Saharan Africa, where millions are at risk for the illness. The disease, commonly referred to as African sleeping sickness, is caused by an infection by the eukaryotic pathogen, Trypanosoma brucei. Previously, a target-based high throughput screen revealed ebselen (EbSe), and its sulfur analog, EbS, to be potent in vitro inhibitors of the T. brucei hexokinase 1 (TbHK1). These molecules also exhibited potent trypanocidal activity in vivo. In this manuscript, we synthesized a series of sixteen EbSe and EbS derivatives bearing electron-withdrawing carboxylic acid and methyl ester functional groups, and evaluated the influence of these substituents on the biological efficacy of the parent scaffold. With the exception of one methyl ester derivative, these modifications ablated or blunted the potent TbHK1 inhibition of the parent scaffold. Nonetheless, a few of the methyl ester derivatives still exhibited trypanocidal effects with single-digit micromolar or high nanomolar EC50 values.

Heme, an iron-enclosed organic ring, is essential for virtually all living organisms by serving as a prosthetic group in proteins that function in diverse cellular activities ranging from diatomic gas transport and detection to mitochondrial respiration to detoxification. Cellular heme levels in microbial pathogens can be a composite of endogenous de novo synthesis or exogenous uptake of heme or heme synthesis intermediates1,2. Intracellular pathogenic microbes switch routes for heme supply when heme availability in their replicative environment fluctuates through infections2. Here, we show that the Toxoplasma gondii, an obligate intracellular human pathogen, encodes a functional heme biosynthesis pathway. A chloroplast-derived organelle, termed apicoplast, is involved in the heme production. Genetic and chemical manipulation revealed that de novo heme production is essential for T. gondii intracellular growth and pathogenesis. Surprisingly, the herbicide oxadiazon significantly impaired Toxoplasma growth, consistent with phylogenetic analyses that show T. gondii protoporphyrinogen oxidase is more closely related to plants than mammals. We further improve upon this inhibition by 15-to 25-fold with two oxadiazon derivatives, providing therapeutic proof that Toxoplasma heme biosynthesis is a druggable target. As T. gondii has been used to model other apicomplexan parasites3, our study underscores the utility of targeting heme biosynthesis in other pathogenic apicomplexans.

The α-oxidized thioimidates are useful bidentate ligands and are important motifs in pharmaceuticals, pesticides, and fungicides. Despite their broad utility, a direct route for their synthesis has been elusive. Herein, we describe a one-step synthesis of

We describe the inhibition of the starch utilization system (Sus) belonging to various strains of Bacteroides dorei in a non-lethal manner using the small molecule probe, acarbose. Concentrations of acarbose as low as 5 μM significantly impede the growth of B. dorei and increase the doubling time of cultures. The successful inhibition of this species of Bacteroides is relevant to several disease states including type I diabetes mellitus. This method continues to explore a new, potential route to intervene in illnesses associated with aberrant changes in the composition of the human gut microbiota through the strategic manipulation of its constituents.

Rendering is a global industry that recycles by-products resulting from butchering operations, which process billions of animals per year. About 50% of the weight of livestock is not consumed by humans and must be processed by rendering operations, which cook and separate the material into its protein and fat components. These products serve as a sustainable food source for livestock, feedstocks for oleochemicals, and raw material for biodiesel refineries. Due to the scale and nature of the raw materials and the cooking process, rendering operations emit a significant, but as yet poorly quantified, VOC load. Assessing this VOC load is important in order to calibrate the industry’s contribution to global VOC emissions, and to help address nuisance odor problems. We conducted VOC air sampling of two facilities in California, USA during the winter and summer seasons. VOC and reduced sulfur analyses were conducted using 8 h ambient air samples. Analyses for amines, ammonia, aldehydes/ketones, and volatile fatty acids were conducted using sampling pumps. These analyses detected 43 compounds at the facilities, and the number and concentration of detectable compounds were seasonally dependent. The compounds present at the highest concentrations included: ammonia (1600–2800 ppb, i.e., winter–summer levels), acetic acid (80–320 ppb, along with twelve other fatty acids ranging from ~0.5–140 ppb), acetone (55–241 ppb, along with nine other aldehyde/ketone products ranging from 0.4–60 ppb), and ethanol (15–81 ppb). These constituents have low odor thresholds and thus contribute to nuisance odor problems. Further, the overall VOC contribution arising from rendering facilities on a global scale is as yet very poorly characterized. This analysis will be useful to guide the development of new odor abatement strategies and strategies for the reduction of VOC emissions associated with this critical industry.

A new drug delivery strategy was investigated for the development of potent anti-parasitic compounds against Trypanosoma brucei, the causative agent of African sleeping sickness. Thus, potent in vitro hexokinase inhibitors were rendered cytotoxic by appending a tripeptide peroxosomal targeting sequence that facilitated delivery of the molecular cargo to the appropriate organelle in the parasite.

To address a need for highly X-ray opaque biodegradable materials, a series of poly(e-caprolactone) derivatives were prepared using oxime post-polymerization modification to conjugate two different iodinated hydroxylamines. These materials were synthesized with up to 32 wt. % iodine content and demonstrated improved X-ray contrast relative to both the ketone precursors and previously reported monoiodinated materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016

We devised a half-day laboratory exercise for a group of 10th grade homeschooled students enrolled in an honors-level high school general chemistry course organized by a collective of homeschooling families associated with local Christian churches. Anecdotal evidence suggested that the students met the learning objectives of the exercise. The influence of the exercise on the students’ perception of laboratory experimentation was assessed quantitatively by means of a brief pre- and post-encounter Likert-scale survey.

Heme, an iron-containing organic ring, is essential for virtually all living organisms by serving as a prosthetic group in proteins that function in diverse cellular activities ranging from diatomic gas transport and sensing, to mitochondrial respiration, to detoxification. Cellular heme levels in microbial pathogens can be a composite of endogenous de novo synthesis or exogenous uptake of heme or heme synthesis intermediates. Intracellular pathogenic microbes switch routes for heme supply when heme availability fluctuates in their replicative environment throughout infection. Here, we show that Toxoplasma gondii, an obligate intracellular human pathogen, encodes a functional heme biosynthesis pathway. A chloroplast-derived organelle, termed apicoplast, is involved in heme production. Genetic and chemical manipulation revealed that de novo heme production is essential for T. gondii intracellular growth and pathogenesis. Surprisingly, the herbicide oxadiazon significantly impaired Toxoplasma growth, consistent with phylogenetic analyses that show T. gondii protoporphyrinogen oxidase is more closely related to plants than mammals. This inhibition can be enhanced by 15- to 25-fold with two oxadiazon derivatives, lending therapeutic proof that Toxoplasma heme biosynthesis is a druggable target. As T. gondii has been used to model other apicomplexan parasites, our study underscores the utility of targeting heme biosynthesis in other pathogenic apicomplexans, such as Plasmodium spp., Cystoisospora, Eimeria, Neospora, and Sarcocystis., Author summary Toxoplasma gondii infects essentially all warm-blooded animals due to its broad species and tissue tropism. Almost one-third of the human population carry Toxoplasma infection, which can cause severe morbidity and mortality in immunocompromised individuals. The current antibiotics against Toxoplasma trigger strong side effects in some groups of patients and have limited efficacy on congenital toxoplasmosis. Thus, an urgent need for novel therapeutics exist. Here, we show that Toxoplasma gondii actively produces heme, a key nutrient for many subcellular activities, via its plant-like heme biosynthesis pathway for intracellular growth and acute virulence. We found that several herbicidal heme biosynthesis inhibitors and their derivatives show inhibitory effects against intracellular Toxoplasma growth. Our findings provide evidence that disrupting heme production in Toxoplasma could be an effective therapeutic strategy to control infection.

Polyethylenimine (PEI) functionalized kaolinite clay was successfully prepared, characterized, and assessed for the remediation of volatile organic compounds (VOCs) comprising the aldehyde, carboxylic acid, and disulfide functional group classes. A gas chromatographic vapor capture assay evaluated the capability of unmodified and modified clay material to capture representative aldehyde, carboxylic acid, and disulfide VOCs in a laboratory setting. Unmodified kaolinite (Kao) clay was moderately or poorly effective at remediating these VOCs, while the poly(amine) functionalized Kao was capable of capturing VOCs in the vapor phase with reductions up to 100%. Sample cartridge tubes were packed with PEI-functionalized clay in order to assess their ability to reduce the detectable volatile fatty acid load at an open-air rendering plant in a relevant field test for applying these materials in a packed-bed scrubber application. The PEI-Kao packed cartridges were capable of significantly reducing the detectable concentration of volatile fatty acid effluent from the rendering operation. These volatile fatty acids are major contributors to nuisance odors associated with rendering.

A new approach for the nonmicrobicidal phenotypic manipulation of prominent gastrointestinal microbes is presented. Low micromolar concentrations of a chemical probe, acarbose, can selectively inhibit the Starch Utilization System and ablate the ability of Bacteroides thetaiotaomicron and B. fragilis strains to metabolize potato starch and pullulan. This strategy has potential therapeutic relevance for the selective modulation of the GI microbiota in a nonmicrobicidal manner.

While many known methods for oxidation mediated by polyoxometalates (POMs) employ environmentally friendly co-oxidants, they tend to employ large catalyst loadings (e.g. 40 mol%) and costly high reaction temperatures (~90–135 °C) that potentially contribute to the degradation of the catalyst and reduce their effectiveness. Herein, we present some initial results demonstrating a room temperature catalytic oxidation using the reduced salt-inclusion polyoxometalate, Cs5(V14As8O42Cl), that contains polyoxovanadate (POV) clusters as an efficient catalyst (e.g., 2 mol%) in the transformation of secondary alcohols to their corresponding ketones in very good to quantitative yields. Further, the catalyst can be suspended on celite and recycled.

A full account of our recently communicated method for the V 2 O 5 mediated bromolactonization of alkenoic acids is presented. Here we describe the extensive evaluation of the metal oxide catalyst, terminal oxidant, halide source, solvent system, and reaction temperature that resulted in optimal conditions employing 0.05 equiv V 2 O 5 , 3 equiv urea-hydrogen peroxide complex (UHP), and 3 equiv of NH 4 Br in an acetone:H 2 O (6:1) solvent system at room temperature. Additionally, we have expanded the substrate scope of the reaction with the aim of evaluating the functional group tolerance of the transformation. Further, we present preliminary data of a related halogenation of β-diketones with our optimal conditions. Finally, we probed the role of urea in the transformation.

A remarkable solvent-controlled enantiodivergence is seen in the hydroquinidine 1,4-phthalazinediyl diether ((DHQD)2PHAL)-catalyzed chlorocyclization of unsaturated carbamates. Eyring plot analyses of this previously unreported reaction are used to probe and compare the R- and S-selective pathways. In the CHCl3/hexanes solvent system, the pro-R process shows a surprising increase in selectivity with increasing temperature. These studies point to a strongly solvent-dependent entropy-enthalpy balance between the pro-R and pro-S pathways.

A series of 37 peptides containing an iodo-aryl amide active site were generated by means of both solid phase and conventional synthesis. These peptides were screened for asymmetric induction in the bromolactonization of 4-phenyl-4-pentenoic acid based on the generation of chiral bromoiodinane bromenium sources. The study culminated in the discovery of a tri-peptide iodo-aryl amide that effected the desired bromolactonization in quantitative conversion with 24% ee. The experiments disclosed herein provided valuable insight that ultimately facilitated the development of more synthetically useful enantioselective halocyclization methodology.

The successful marriage of structural features from our 2-aminoimidazole and menthyl carbamate classes of anti-biofilm agents has resulted in the development of a novel hybrid scaffold of biofilm modulators. The compounds were evaluated against a panel of four bacterial strains for anti-biofilm and anti-microbial activity.

N-Acylated N-chlorohydantoins are shown to be competent chlorenium sources in the (DHQD)(2)PHAL-mediated asymmetric chlorolactonization. The derivatives demonstrate the exact role of the N1 and N3 chlorine atoms in the parent dichlorohydantoins with the N1 chlorine serving as an inductive activator and the N3 chlorine being delivered to the substrate. The putative associated catalyst/chlorine source complex was experimentally demonstrated through a series of matched/mismatched experiments employing chiral N-chlorinated hydantoins.

An efficient protocol for the bromolactonization of alkenoic acids is presented that obviates the use of molecular bromine or exogenous bromenium sources. Vanadium (V) oxide catalyzes the in situ oxidation of bromide salts to bromenium (Br + ) in a process mediated by urea–hydrogen peroxide complex. Initial mechanistic investigations indicate that the presence of urea does not accelerate the halolactonization reaction.