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1. J ‐modulated ¹⁹ F‐ and ¹ H‐detected dual‐optimized inverted ¹ J _CC 1,n‐ADEQUATE: A universal ADEQUATE experiment

   https://doi.org/10.1002/mrc.5324  

   Crouch, Ronald C; Pelmuş, Marius; Raab, Jeffrey G; Tischenko, Evgeny; Frey, Michael; Wang, Yunyi; Reibarkh, Mikhail; Williamson, R Thomas; Martin, Gary E (March 2023, Magnetic Resonance in Chemistry)

   Abstract The recently reported¹⁹F‐detected dual‐optimized inverted¹J_CC1,n‐ADEQUATE experiment and the previously reported¹H‐detected version have been modified to incorporateJ‐modulation, making it feasible to acquire all 1,1‐ and 1,n‐ADEQUATE correlations as well as¹J_CCandⁿJ_CChomonuclear scalar couplings in a single experiment. The experiments are demonstrated usingN,N‐dimethylamino‐2,5,6‐trifluoro‐3,4‐phthalonitrile andN,N‐dimethylamino‐3,4‐phthalonitrile. 

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2. Condensin I ^DC , H4K20me1, and perinuclear tethering maintain X chromosome repression in C. elegans

   https://doi.org/10.1101/2024.04.05.588224  

   Trombley, Jessica; Rakozy, Audry I; Jash, Eshna; Csankovszki, Györgyi (April 2024, bioRxiv)

   Abstract Dosage compensation inCaenorhabditis elegansequalizes X-linked gene expression between XX hermaphrodites and XO males. The process depends on a condensin- containing dosage compensation complex (DCC), which binds the X chromosomes in hermaphrodites to repress gene expression. Condensin I^DCand an additional five DCC components must be present on the X during early embryogenesis in hermaphrodites to establish dosage compensation. However, whether the DCC’s continued presence is required to maintain the repressed state once established is unknown. Beyond the role of condensin I^DCin X chromosome compaction, additional mechanisms contribute to X- linked gene repression. DPY-21, a non-condensin I^DCDCC component, is an H4K20me2/3 demethylase whose activity enriches the repressive histone mark, H4 lysine 20 monomethylation, on the X chromosomes. In addition, CEC-4 tethers H3K9me3-rich chromosomal regions to the nuclear lamina, which also contributes to X- linked gene repression. To investigate the necessity of condensin I^DCduring the larval and adult stages of hermaphrodites, we used the auxin-inducible degradation system to deplete the condensin I^DCsubunit DPY-27. While DPY-27 depletion in the embryonic stages resulted in lethality, DPY-27 depleted larvae and adults survive. In these DPY-27 depleted strains, condensin I^DCwas no longer associated with the X chromosome, the X became decondensed, and the H4K20me1 mark was gradually lost, leading to X-linked gene derepression. These results suggest that the stable maintenance of dosage compensation requires the continued presence of condensin I^DC. A loss-of-function mutation incec-4, in addition to the depletion of DPY-27 or the genetic mutation ofdpy- 21, led to even more significant increases in X-linked gene expression, suggesting that tethering heterochromatic regions to the nuclear lamina helps stabilize repression mediated by condensin I^DCand H4K20me1. Author SummaryIn some organisms, whether an individual becomes male, female, or hermaphrodite is determined by the number of their sex chromosomes. In the nematodeCaenorhabditis elegans, males have one X chromosome, whereas hermaphrodites have two X chromosomes. This difference in the number of X chromosomes is crucial for deciding whether an individual becomes a hermaphrodite or a male. However, having two X chromosomes can lead to problems because it results in different gene expression levels, resulting in hermaphrodite lethality. To solve this issue, many organisms undergo a process called dosage compensation. Dosage compensation inC. elegansis achieved by a group of proteins known as the dosage compensation complex (DCC), which includes a protein called DPY-27. The function of DPY-27 is essential during early embryonic development. This study shows that in contrast to early embryonic development, larvae and adults can still survive when DPY-27 is missing. In these worms, all known mechanisms involved in dosage compensation are disrupted and the X is no longer repressed. Our results suggest that the maintenance of dosage compensation in nematodes is an active process, and that it is essential for survival when the organism is developing, but once fully developed, the process becomes dispensable. 

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3. The Neumann function and the L ^p Neumann problem in chord-arc domains

   https://doi.org/10.1515/ans-2023-0171  

   Hofmann, Steve; Sparrius, Derek (February 2025, Advanced Nonlinear Studies)

   Abstract We construct the Neumann function in a 1-sided chord-arc domain (i.e., a uniform domain with an Ahlfors regular boundary), and establish size and Hölder continuity estimates up to the boundary. We then obtain a Kenig-Pipher type theorem, in whichL^psolvability of the Neumann problem is shown to yield solvability inL^qfor 1 <q<p, and in the Hardy spaceH¹, in 2-sided chord-arc domains, under suitable background hypotheses. 

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4. Facile Conversion of syn ‐[Fe ^IV (O)(TMC)] ²⁺ into the anti Isomer via Meunier's Oxo–Hydroxo Tautomerism Mechanism

   https://doi.org/10.1002/anie.201811454  

   Prakash, Jai; Sheng, Yuan; Draksharapu, Apparao; Klein, Johannes E. M. N.; Cramer, Christopher J.; Que, Jr., Lawrence (January 2019, Angewandte Chemie International Edition)

   Abstract Thesynandantiisomers of [Fe^IV(O)(TMC)]²⁺(TMC=tetramethylcyclam) represent the first isolated pair of synthetic non‐heme oxoiron(IV) complexes with identical ligand topology, differing only in the position of the oxo unit bound to the iron center. Both isomers have previously been characterized. Reported here is that thesynisomer [Fe^IV(O_syn)(TMC)(NCMe)]²⁺(2) converts into itsantiform [Fe^IV(O_anti)(TMC)(NCMe)]²⁺(1) in MeCN, an isomerization facilitated by water and monitored most readily by¹H NMR and Raman spectroscopy. Indeed, when H₂¹⁸O is introduced to2, the nascent1becomes¹⁸O‐labeled. These results provide compelling evidence for a mechanism involving direct binding of a water moleculetransto the oxo atom in2with subsequent oxo–hydroxo tautomerism for its incorporation as the oxo atom of1. The nonplanar nature of the TMC supporting ligand makes this isomerization an irreversible transformation, unlike for their planar heme counterparts. 

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5. Photochemistry of N ‐Phenyl Dibenzothiophene Sulfoximine ^†

   https://doi.org/10.1111/php.13456  

   Isor, Ankita; Hommelsheim, Renè; Cone, Grant W.; Frings, Marcus; Petroff, II, John T.; Bolm, Carsten; McCulla, Ryan D. (June 2021, Photochemistry and Photobiology)

   Abstract Sulfoximines are popular scaffolds in drug discovery due to their hydrogen bonding properties and chemical stability. In recent years, the role of reactive intermediates such as nitrenes has been studied in the synthesis and degradation of sulfoximines. In this work, the photochemistry ofN‐phenyl dibenzothiophene sulfoximine [5‐(phenylimino)‐5H‐5λ⁴‐dibenzo[b,d]thiopheneS‐oxide] was analyzed. The structure resembles a combination ofN‐phenyl iminodibenzothiophene and dibenzothiopheneS‐oxide, which generate nitrene and O(³P) upon UV‐A irradiation, respectively. The photochemistry ofN‐phenyl dibenzothiophene sulfoximine was explored by monitoring the formation of azobenzene, a photoproduct of triplet nitrene, using direct irradiation and sensitized experiments. The reactivity profile was further studied through direct irradiation experiments in the presence of diethylamine (DEA) as a nucleophile. The studies demonstrated thatN‐phenyl dibenzothiophene sulfoximine underwent S–N photocleavage to release singlet phenyl nitrene which formed a mixture of azepines in the presence of DEA and generated moderate amounts of azobenzene in the absence of DEA to indicate formation of triplet phenyl nitrene. 

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