Catalytic glycosylation for minimally protected donors and acceptors.

Oligosaccharides have myriad functions throughout biological processes1,2. Chemical synthesis of these structurally complex molecules facilitates investigation of their functions. With a dense concentration of stereocentres and hydroxyl groups, oligosaccharide assembly through O-glycosylation requires simultaneous control of site, stereo- and chemoselectivities3,4. Chemists have traditionally relied on protecting group manipulations for this purpose5-8, adding considerable synthetic work. Here we report a glycosylation platform that enables selective coupling between unprotected or minimally protected donor and acceptor sugars, producing 1,2-cis-O-glycosides in a catalyst-controlled, site-selective manner. Radical-based activation9 of allyl glycosyl sulfones forms glycosyl bromides. A designed aminoboronic acid catalyst brings this reactive intermediate close to an acceptor through a network of non-covalent hydrogen bonding and reversible covalent B-O bonding interactions, allowing precise glycosyl transfer. The site of glycosylation can be switched with different aminoboronic acid catalysts by affecting their interaction modes with substrates. The method accommodates a wide range of sugar types, amenable to the preparation of naturally occurring sugar chains and pentasaccharides containing 11 free hydroxyls. Experimental and computational studies provide insights into the origin of selectivity outcomes.

Photoinduced copper-catalysed asymmetric amidation via ligand cooperativity.

The substitution of an alkyl electrophile by a nucleophile is a foundational reaction in organic chemistry that enables the efficient and convergent synthesis of organic molecules. Although there has been substantial recent progress in exploiting transition-metal catalysis to expand the scope of nucleophilic substitution reactions to include carbon nucleophiles1-4, there has been limited progress in corresponding reactions with nitrogen nucleophiles5-8. For many substitution reactions, the bond construction itself is not the only challenge, as there is a need to control stereochemistry at the same time. Here we describe a method for the enantioconvergent substitution of unactivated racemic alkyl electrophiles by a ubiquitous nitrogen-containing functional group, an amide. Our method uses a photoinduced catalyst system based on copper, an Earth-abundant metal. This process for asymmetric N-alkylation relies on three distinct ligands-a bisphosphine, a phenoxide and a chiral diamine. The ligands assemble in situ to form two distinct catalysts that act cooperatively: a copper/bisphosphine/phenoxide complex that serves as a photocatalyst, and a chiral copper/diamine complex that catalyses enantioselective C-N bond formation. Our study thus expands enantioselective N-substitution by alkyl electrophiles beyond activated electrophiles (those bearing at least one sp- or sp2-hybridized substituent on the carbon undergoing substitution)8-13 to include unactivated electrophiles.

Metallaphotoredox-enabled deoxygenative arylation of alcohols.

Metal-catalysed cross-couplings are a mainstay of organic synthesis and are widely used for the formation of C-C bonds, particularly in the production of unsaturated scaffolds1. However, alkyl cross-couplings using native sp3-hybridized functional groups such as alcohols remain relatively underdeveloped2. In particular, a robust and general method for the direct deoxygenative coupling of alcohols would have major implications for the field of organic synthesis. A general method for the direct deoxygenative cross-coupling of free alcohols must overcome several challenges, most notably the in situ cleavage of strong C-O bonds3, but would allow access to the vast collection of commercially available, structurally diverse alcohols as coupling partners4. We report herein a metallaphotoredox-based cross-coupling platform in which free alcohols are activated in situ by N-heterocyclic carbene salts for carbon-carbon bond formation with aryl halide coupling partners. This method is mild, robust, selective and most importantly, capable of accommodating a wide range of primary, secondary and tertiary alcohols as well as pharmaceutically relevant aryl and heteroaryl bromides and chlorides. The power of the transformation has been demonstrated in a number of complex settings, including the late-stage functionalization of Taxol and a modular synthesis of Januvia, an antidiabetic medication. This technology represents a general strategy for the merger of in situ alcohol activation with transition metal catalysis.

A submillimeter bundled microtubular flow battery cell with ultrahigh volumetric power density.

Flow batteries are a promising energy storage solution. However, the footprint and capital cost need further reduction for flow batteries to be commercially viable. The flow cell, where electron exchange takes place, is a central component of flow batteries. Improving the volumetric power density of the flow cell (W/Lcell) can reduce the size and cost of flow batteries. While significant progress has been made on flow battery redox, electrode, and membrane materials to improve energy density and durability, conventional flow batteries based on the planar cell configuration exhibit a large cell size with multiple bulky accessories such as flow distributors, resulting in low volumetric power density. Here, we introduce a submillimeter bundled microtubular (SBMT) flow battery cell configuration that significantly improves volumetric power density by reducing the membrane-to-membrane distance by almost 100 times and eliminating the bulky flow distributors completely. Using zinc-iodide chemistry as a demonstration, our SBMT cell shows peak charge and discharge power densities of 1,322 W/Lcell and 306.1 W/Lcell, respectively, compared with average charge and discharge power densities of <60 W/Lcell and 45 W/Lcell, respectively, of conventional planar flow battery cells. The battery cycled for more than 220 h corresponding to >2,500 cycles at off-peak conditions. Furthermore, the SBMT cell has been demonstrated to be compatible with zinc-bromide, quinone-bromide, and all-vanadium chemistries. The SBMT flow cell represents a device-level innovation to enhance the volumetric power of flow batteries and potentially reduce the size and cost of the cells and the entire flow battery.

Coupling and regulation mechanisms of the flavin-dependent halogenase PyrH observed by infrared difference spectroscopy.

Flavin-dependent halogenases are central enzymes in the production of halogenated secondary metabolites in various organisms and they constitute highly promising biocatalysts for regioselective halogenation. The mechanism of these monooxygenases includes formation of hypohalous acid from a reaction of fully reduced flavin with oxygen and halide. The hypohalous acid then diffuses via a tunnel to the substrate-binding site for halogenation of tryptophan and other substrates. Oxidized flavin needs to be reduced for regeneration of the enzyme, which can be performed in vitro by a photoreduction with blue light. Here, we employed this photoreduction to study characteristic structural changes associated with the transition from oxidized to fully reduced flavin in PyrH from Streptomyces rugosporus as a model for tryptophan-5-halogenases. The effect of the presence of bromide and chloride or the absence of any halides on the UV-vis spectrum of the enzyme demonstrated a halide-dependent structure of the flavin-binding pocket. Light-induced FTIR difference spectroscopy was applied and the signals assigned by selective isotope labeling of the protein moiety. The identified structural changes in α-helix and ß-sheet elements were strongly dependent on the presence of bromide, chloride, the substrate tryptophan, and the product 5-chloro-tryptophan, respectively. We identified a clear allosteric coupling in solution at ambient conditions between cofactor-binding site and substrate-binding site that is active in both directions, despite their separation by a tunnel. We suggest that this coupling constitutes a fine-tuned mechanism for the promotion of the enzymatic reaction of flavin-dependent halogenases in dependence of halide and substrate availability.

Cu-Catalyzed Amination of Base-Sensitive Aryl Bromides and the Chemoselective N- and O-Arylation of Amino Alcohols.

We report a general and functional-group-tolerant method for the Cu-catalyzed amination of base-sensitive aryl bromides including substrates possessing acidic functional groups and small five-membered heteroarenes. The results presented herein substantially expand the scope of Cu-catalyzed C-N coupling reactions. The combination of L8, an anionic N1,N2-diarylbenzene-1,2-diamine ligand, along with the mild base NaOTMS leads to the formation of a stable yet reactive catalyst that resists deactivation from coordination to heterocycles or charged intermediates. This system enables the use of low catalyst and ligand loadings. Exploiting the differences in nucleophile deprotonation in C-O and C-N coupling reactions catalyzed by Cu·L8 we developed a method to chemoselectively N- and O-arylate a variety of amino alcohol substrates. Employing NaOt-Bu as the base resulted exclusively in C-O coupling when the amino alcohols featured primary alcohols and more hindered amines or aniline groups. Utilizing NaOTMS enabled the ability to override the steric-based selectivity of these reactions completely and exclusively promoted C-N coupling regardless of the structure of the amino alcohol. The ability to invert the observed chemoselectivity is distinct from previously described methods that require protecting group manipulations or rely entirely on steric effects to control reactivity. These results substantially improve the scope of Cu-catalyzed C-N coupling reactions using N1,N2-diarylbenzene-1,2-diamine ligands and introduce a new chemoselective method to arylate amino alcohols.

Characterization of Parallel-Stranded DNA Duplexes by Surface-Enhanced Raman Spectroscopy and Bromide-Modified Gold Nanoparticles.

The parallel double-stranded DNA (dsDNA) demonstrates potential utility in molecular biology, diagnosis, therapy, and molecular assembly. However, techniques for the characterization of parallel dsDNA are limited. Here, we demonstrate that a series of intensive characteristic Raman bands of three parallel dsDNAs, which are stabilized by reverse Hoogsteen A+·A+ base pairs or hemiprotonated C+·C, G·G minor groove edge, Hoogsteen A·A base pairs, or Hoogsteen T·A, C+·G base pairs, have been observed by surface-enhanced Raman spectroscopy (SERS) when the gold nanoparticles modified by bromine and magnesium ions (Au BMNPs) were used as substrates. The featured bands can not only accurately discriminate parallel dsDNA from antiparallel one but also identify the strand orientation within dsDNA. The proposed approach will have a significant impact on DNA analysis, especially in the detection and differentiation of various DNA conformations.

Methylation of Phenyl Rings in Ester-Stabilized Phosphorus Ylides Vastly Enhances Their Protonophoric Activity.

We have recently discovered that ester-stabilized phosphorus ylides, resulting from deprotonation of a phosphonium salt such as [Ph3PCH2COOR], can transfer protons across artificial and biological membranes. To create more effective cationic protonophores, we synthesized similar phosphonium salts with one ((heptyloxycarbonylmethyl)(p-tolyl)bromide) or two ((butyloxycarbonylmethyl)(3,5-xylyl)osphonium bromide) methyl substituents in the phenyl groups. The methylation enormously augmented both protonophoric activity of the ylides on planar bilayer lipid membrane (BLM) and uncoupling of mammalian mitochondria, which correlated with strongly accelerated flip-flop of their cationic precursors across the BLM.

Active-bromide and surfactant synergy for enhanced microfouling control.

Biofilms are structured microbial communities encased in a matrix of self-produced extracellular polymeric substance (EPS) and pose significant challenges in various industrial cooling systems. A nuclear power plant uses a biocide active-bromide for control of biological growth in its condenser cooling system. This study is aimed at evaluating the anti-bacterial and anti-biofilm efficacy of active-bromide against planktonic and biofilm-forming bacteria that are commonly encountered in seawater cooling systems. The results demonstrated that active-bromide at the concentration used at the power plant (1 ppm) exhibited minimal killing activity against Pseudomonas aeruginosa planktonic cells. The bacterial cell surface hydrophobicity assay using Staphylococcus aureus and P. aeruginosa indicated that Triton-X 100 significantly decreased the hydrophobicity of planktonic cells, enhancing the susceptibility of the cells to active-bromide. Biofilm inhibition assays revealed limited efficacy of active-bromide at 1 ppm concentration, but significant inhibition at 5 ppm and 10 ppm. However, the addition of a surfactant, Triton-X 100, in combination with 1 ppm active-bromide displayed a synergistic effect, leading to significant biofilm dispersal of pre-formed P. aeruginosa biofilms. This observation was substantiated by epifluorescence microscopy using a live/dead bacterial assay that showed the combination treatment resulted in extensive cell death within the biofilm, as indicated by a marked increase in red fluorescence, compared to treatments with either agent alone. These findings suggest that active bromide alone may be insufficient for microfouling control in the seawater-based condenser cooling system of the power plant. Including a biocompatible surfactant that disrupts established biofilms (microfouling) can significantly improve the efficacy of active bromide treatment.

Simultaneous Oxidation of Bromide and Dissolution of Manganese Oxide Induced by Freezing.

This study demonstrates that the oxidation of bromide by birnessite (δ-MnO2) results in the concurrent production of soluble manganese (Mn(II)) and reactive bromine (RBr) species in frozen solutions, a process not observed in aqueous solutions. This enhanced oxidation in ice is attributed to the concentration of protons, birnessite, or bromide in the ice grain boundary region. Furthermore, different types of commercial manganese oxides can also oxidize bromide to RBr and release Mn(II) in ice. The presence of fulvic acid (FA) further increases the simultaneous production of RBr and Mn(II) in ice, accompanying the formation of organobromine compounds (OBCs). In frozen δ-MnO2/Br-/FA system, a significant increase in OBCs, mainly highly unsaturated and phenolic compounds, was detected using Fourier transform ion cyclotron resonance mass spectrometry. A marked contrast was observed in the number of OBCs formed in frozen solutions (853 and 415 OBCs at initial pH 3.0 and 5.8, respectively) compared to their aqueous counterparts (11 and 23 OBCs). These findings introduce a new pathway for the formation of RBr, Mn(II), and OBCs in ice, highlighting the need for further research on the environmental fate of bromide and manganese.

Harnessing bromide ions to boost peroxymonosulfate for reactive yellow 145 dye degradation.

Bromide (Br-) was found in the fresh waters at concentrations from 0.1 to 1 mg/L and can be used to activate peroxymonosulfate (PMS) as a widely used chemical oxidation agent. In the present study, the reaction between PMS and Br- ions (PMS/Br- process) for the effective degradation of reactive yellow 145 (RY-145) dye was investigated by changing operational parameters vis solution pH, dosage of Br- ions and PMS, RY-145 concentration, and reaction time. Based on the results, the simultaneous presence of PMS and Br- ions in the solution led to efficient degradation of RY-145 with a synergistic index of 11.89. The degradation efficiency of RY-145 was decreased in severe basic pH and the presence of CO32- ions as a coexisting anion. Likewise, 4 mg/L of humic acid (HA), used as a classic scavenger, led to a 26.53% decrease in the RY-145 degradation efficiency. The free bromine (HOBr/OBr-), superoxide radical (●O2-), and singlet oxygen (1O2) was the dominant oxidation agents in RY-145 degradation, which confirmed the nonradical degradation pathway. In addition, PMS/Br- process showed excellent ability in mineralizing RY-145 in different aqueous solutions (total organic carbon (TOC) decreased 86.39% in deionized water and 78.23% in tap water). Although pollutants such as azo dyes can be effectively removed in the PMS/Br- process, the formation of byproducts should be strategically controlled and special attention should be paid when the PMS-based advance oxidation process is applied to treat Br- containing solutions.

Rational design and construction of direct Z-scheme ternary heterojunction photocatalyst AgBr/CoWO4/Ag for efficient environmental remediation.

The indiscriminate discharge of micropollutants (e.g., dyes, antibiotics, industrial additives, etc.) represents a significant risk to human health, and the removal of these substances from water bodies has become a prominent area of research within the field of environmental remediation. A simple hydrothermal-precipitation-photoreduction method was employed to synthesize novel Z-scheme heterojunction photocatalysts of AgBr/CoWO4/Ag. The catalysts demonstrated remarkable degradation capabilities with regard to a range of micropollutants present in wastewater. Of the catalysts tested, 5AgBr/CoWO4/Ag exhibited the highest degradation rates, reaching 98.58% for Rhodamine B, 86.82% for tetracycline hydrochloride, and 95.60% for 2-mercaptobenzothiazole within 60 min. In particular, the reaction kinetic rate of 5AgBr/CoWO4/Ag towards Rhodamine B degradation (k2 = 0.26278 L mg-1·min-1) is 9 times that of AgBr (k2 = 0.02953 L mg-1·min-1) and 113 times that of CoWO4 (k2 = 0.00233 L mg-1·min-1), which serves to highlight the exceptional photocatalytic activity of the material. The experimental data and subsequent analysis indicated that the enhanced photocatalytic performance can be attributed to two factors: firstly, the electron mediation by Ag nanoparticles leading to improved charge separation efficiency, and secondly, the formation of Z-scheme heterojunctions between AgBr and CoWO4. The cyclic tests provided confirmation of the excellent stability and recyclability of the AgBr/CoWO4/Ag photocatalysts. It is anticipated that this study will facilitate the development of novel methods for the degradation of refractory micropollutants and provide insights into environmental remediation, thereby contributing to the sustainable development of society.

Bi2S3/Ti3C2-TPP nano-heterostructures induced by near-infrared for photodynamic therapy combined with photothermal therapy on hypoxic tumors.

BACKGROUND: Photodynamic therapy (PDT) efficacy of bismuth sulfide (Bi2S3) semiconductor has been severely restricted by its electron-hole pairs (e--h+) separation inefficiency and oxygen (O2) deficiency in tumors, which greatly hinders reactive oxygen species (ROS) generation and further clinical application of Bi2S3 nanoparticles (NPs) in biomedicine. RESULTS: Herein, novel Bi2S3/titanium carbide (Ti3C2) two-dimensional nano-heterostructures (NHs) are designed to realize multimode PDT of synchronous O2 self-supply and ROS generation combined with highly efficient photothermal tumor elimination for hypoxic tumor therapy. Bi2S3/Ti3C2 NHs were synthesized via the in situ synthesis method starting from Ti3C2 nanosheets (NSs), a classical type of MXene nanostructure. Compared to simple Bi2S3 NPs, Bi2S3/Ti3C2 NHs significantly extend the absorption to the near-infrared (NIR) region and enhance the photocatalytic activity owing to the improved photogenerated carrier separation, where the hole on the valence band (VB) of Bi2S3 can react with water to supply O2 for the electron on the Ti3C2 NSs to generate ·O2- and ·OH through electron transfer. Furthermore, they also achieve 1O2 generation through energy transfer due to O2 self-supply. After the modification of triphenylphosphium bromide (TPP) on Bi2S3/Ti3C2 NHs, systematic in vitro and in vivo evaluations were conducted, revealing that the synergistic-therapeutic outcome of this nanoplatform enables complete eradication of the U251 tumors without recurrence by NIR laser irradiation, and it can be used for computed tomography (CT) imaging because of the strong X-ray attenuation ability. CONCLUSION: This work expands the phototherapeutic effect of Bi2S3-based nanoplatforms, providing a new strategy for hypoxic tumor theranostics.

Improved photoluminescence stability and defect passivation in SbBr3 post-treated CsPbBr3 quantum dots under ambient conditions.

Inorganic cesium lead halide perovskites have evoked wide popularity because of their excellent optoelectronic properties, high photoluminescence (PL) quantum yield (PLQY), and narrowband emission. Here, cesium lead bromide (CsPbBr3 ) quantum dots (QDs) were synthesized via the ligand-assisted re-precipitation method. Post-synthesis treatment of CsPbBr3 QDs using antimony tribromide improved the PL stability and optoelectronic properties of the QDs. In addition, the PLQY of the post-treated sample was enhanced to 91% via post-treatment, and the luminescence observed was maintained for 8 days. The post-synthesis treatment ensured defect passivation and improved the stability of CsPbBr3 perovskite QDs. High-resolution transmission electron microscopy revealed the presence of more ordered, uniform-sized CsPbBr3 QDs after post-synthesis treatment, and the uniformity of the sample improved as the day passed. The formation of a mixed crystal phase was observed from X-ray diffraction in both as-synthesized, as well as post-treated QDs samples with the possibility of a polycrystalline nature in the post-treated CsPbBr3 QDs as per the selected area electron diffraction pattern. The X-ray photoelectron spectroscopy spectra confirmed the presence of antimony and the possibility of defect passivation in the post-treated samples. These QDs can act as potential candidates in various optoelectronic applications such as photodetectors and light-emitting diodes due to their high PLQY and longer lifetime.

Evaluation of in vitro SARS-CoV-2 inactivation by a new quaternary ammonium compound: Bromiphen bromide.

The pneumonia (COVID-19) outbreak caused by the novel coronavirus named severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), which unpredictably exploded in late December of 2019 has stressed the importance of being able to control potential pathogens with the aim of limiting their spread. Although vaccines are well known as a powerful tool for ensuring public health and controlling the pandemic, disinfection and hygiene habits remain crucial to prevent infection from spreading and maintain the barrier, especially when the microorganism can persist and survive on textiles, surfaces, and medical devices. During the coronavirus disease pandemic, around half of the disinfectants authorized by the US Environmental Protection Agency contained quaternary ammonium compounds (QACs); their effectiveness had not been proven. Herein, the in vitro SARS-CoV-2 inactivation by p-bromodomiphen bromide, namely bromiphen (BRO), a new, potent, and fast-acting QAC is reported. This study demonstrates that BRO, with a dose as low as 0.02%, can completely inhibit SARS-CoV-2 replication in just 30 s. Its virucidal activity was 10- and 100-fold more robust compared to other commercially available QACs, namely domiphen bromide and benzalkonium chloride. The critical micellar concentration and the molecular lipophilicity potential surface area support the relevance of the lipophilic nature of these molecules for their activity.

Effect of Fillers Modification with ILs on Fillers Textural Properties: Thermal Properties of SBR Composites.

In this work, we present the effect of graphene nanoplatelets (GnPs) modification with ionic liquids (ILs). The textural properties of graphene nanoplatelets (GnPs) used as styrene-butadiene rubber's filler and the thermal properties of the composites obtained with the use of the mentioned fillers were investigated. GnPs were modified with 1-butylpyridinium bromide (BPyBr) and 4-methyl-1-butylpyridinium bromide (BmPyBr) through two different ways. One strategy has been to deposit the filler modifier from the solution. The second one involved the modification of the filler with ionic liquids in bulk during the preparation of elastomer blends. Settlement of the proposed ionic liquids onto the GnPs' surface led to significant changes in the textural characteristics. BPyBr has restricted the filler's microporosity, whereas BmPyBr has caused the formation of a more opened filler structure without the increase in its average pore size. GnPs modified with ILs led to reducing the temperature of vulcanization of SBR compounds and affected the thermal stability of the composites.

Formation and toxicity alteration of halonitromethanes from Chlorella vulgaris during UV/chloramination process involving bromide ion.

Frequent algal blooms cause algal cells and their algal organic matter (AOM) to become critical precursors of disinfection by-products (DBPs) during water treatment. The presence of bromide ion (Br-) in water has been demonstrated to affect the formation laws and species distribution of DBPs. However, few researchers have addressed the formation and toxicity alteration of halonitromethanes (HNMs) from algae during disinfection in the presence of Br-. Therefore, in this work, Chlorella vulgaris was selected as a representative algal precursor to investigate the formation and toxicity alteration of HNMs during UV/chloramination involving Br-. The results showed that the formation concentration of HNMs increased and then decreased during UV/chloramination. The intracellular organic matter of Chlorella vulgaris was more susceptible to form HNMs than the extracellular organic matter. When the Br-: Cl2 mass ratio was raised from 0.004 to 0.08, the peak of HNMs total concentration increased 33.99%, and the cytotoxicity index and genotoxicity index of HNMs increased 67.94% and 22.80%. Besides, the formation concentration and toxicity of HNMs increased with increasing Chlorella vulgaris concentration but decreased with increasing solution pH. Possible formation pathways of HNMs from Chlorella vulgaris during UV/chloramination involving Br- were proposed based on the alteration of nitrogen species and fluorescence spectrum analysis. Furthermore, the formation laws of HNMs from Chlorella vulgaris in real water samples were similar to those in deionized water samples. This study contributes to a better comprehension of HNMs formation from Chlorella vulgaris and provides valuable information for water managers to reduce hazards associated with the formation of HNMs.

Bromide induced the formation of brominated halonitromethanes from aspartic acid in the UV/chlorine disinfection process.

Brominated halonitromethanes (Br-HNMs) are generated in water disinfection processes and present high toxicity to human health. This work used aspartic acid (ASP) as the precursor to reveal that bromide (Br-) induced the production of Br-HNMs in the UV/chlorine disinfection process. Consequently, six Br-HNMs were identified, and their yields presented an increasing and then declining evolution over the reaction time from 0 to 15 min. Also, the total Br-HNMs yield reached the maximum of 251.1 µg L-1 at 5 min and then declined to 107.1 µg L-1. The total Br-HNMs yield increased from 2.40 to 251.14 µg L-1 with the increase of Cl2:Br- ratios from 0.25 to 3.0 by increasing free chlorine dosage with a fixed Br- concentration, and it increased from 207.59 to 251.14 µg L-1 and then decreased to 93.44 µg L-1 with the increase of Cl2:Br- ratio from 1.0 to 3.6 by increasing Br- concentration with a fixed free chlorine dosage. Besides, the total Br-HNMs yield reached the highest value (251.14 µg L-1) at pH 7.0 and the lowest value (74.20 µg L-1) at pH 8.0. Subsequently, the possible reaction mechanism of Br-HNMs generated from ASP was deduced, and the changes in toxicity of Br-HNMs also followed an increasing and then declining trend, closely relating to Br-HNMs yields and Br- utilization. This work explored and illustrated the yields, influence factors, reaction mechanisms, and toxicity of Br-HNMs formed from Br- containing ASP water during UV/chlorine disinfection, which might help to control Br-HNMs formation.

[A case of chronic bromide intoxication due to continuous use of a commercially available analgesic in a patient diagnosed with pseudohyperchloremia].

An 87-year-old woman was admitted to our hospital with general fatigue, anorexia, nausea, and chest pain, and was diagnosed with Takotsubo cardiomyopathy and a stomal ulcer. Pseudohyperchloremia and a negative anion gap were detected in laboratory tests. She was continuously taking commercially available analgesics, including bromvalerylurea. On the 11th day of hospitalization, her bromide concentration was high (331.2 mg/L). She was readmitted with fatigue and anorexia one and a half years after her last hospitalization. On admission, her serum chloride and bromide levels were also high. Despite being instructed to stop taking analgesics after the first hospitalization, she was unable to stop taking the medication. It took more than two years for her blood bromide concentration to decrease and the withdrawal of the medication to be confirmed. Clinicians should consider bromide intoxication in patients with unclear neuropsychiatric symptoms and high chloride levels.

Direct Deaminative Functionalization.

Selective functional group interconversions in complex molecular settings underpin many of the challenges facing modern organic synthesis. Currently, a privileged subset of functional groups dominates this landscape, while others, despite their abundance, are sorely underdeveloped. Amines epitomize this dichotomy; they are abundant but otherwise intransigent toward direct interconversion. Here, we report an approach that enables the direct conversion of amines to bromides, chlorides, iodides, phosphates, thioethers, and alcohols, the heart of which is a deaminative carbon-centered radical formation process using an anomeric amide reagent. Experimental and computational mechanistic studies demonstrate that successful deaminative functionalization relies not only on outcompeting the H-atom transfer to the incipient radical but also on the generation of polarity-matched, productive chain-carrying radicals that continue to react efficiently. The overall implications of this technology for interconverting amine libraries were evaluated via high-throughput parallel synthesis and applied in the development of one-pot diversification protocols.