Dual Emission with Efficient Phosphorescence Promoted by Intermolecular Halogen Interactions in Luminescent Tetranuclear Zinc(II) Clusters.

The development of Zn-based phosphorescent materials, associated with a ligand-centered (LC) transition, is extremely limited. Herein, we demonstrated dual emissions including fluorescence and phosphorescence in luminescent tetranuclear Zn(II) clusters [Zn4LI4(µ3-OMe)2X2] (HLI = methyl-5-iode-3-methoxysalicylate; X = I, Br, Cl), incorporating iodine-substituted ligands. Single-crystal X-ray structural analyses and variable-temperature emission spectra studies revealed the presence of iodine substitutions, and intermolecular halogen interactions produced the internal/external heavy-atom effects and yielded strong green phosphorescence with a long emission lifetime (λmax = 510-522 nm, Φem = 0.28-0.47, τav = 0.78-0.95 ms, at 77 K). This work provided a new example that the introduction of halogen interactions is an advantageous approach for inducing phosphorescence in fluorescent metal complexes.

Development of Fournier's gangrene after chemotherapy for the recurrence of testicular cancer despite the absence of anorectal lesions: A case report.

BACKGROUND: Fournier's gangrene usually occurs when a specific bacterium intrudes into soft tissue, causing a wound or tumor. We encountered a patient with Fournier's gangrene due to severe myelosuppression after chemotherapy, despite the absence of an initial lesion on the anus and rectum. CASE PRESENTATION: A 54-year-old man with a left testicular cancer recurrence had undergone chemotherapy. He had asymptomatic hepatitis and high hepatitis B virus DNA levels, which were normalized by administering tenofovir alafenamide fumarate. Twelve days after the start of chemotherapy, he complained of severe pain around the anus. The following day, he went into septic shock. Visual inspection showed dark purple skin discoloration on the left side of the anus. Laboratory data revealed severe neutropenia. Computed tomography showed a high density of soft tissue on the left side of the anus and gas bubbles in the left femoral ring. We diagnosed the patient with Fournier's gangrene due to a severe immunosuppressive state resulting from chemotherapy. We emergently removed necrotic tissue to the fullest extent possible. However, because the patient was in severe sepsis status, careful management in the intensive care unit was required for 32 days. After the first emergency operation, we performed several additional excisions. Finally, 391 days after the initial surgery, the patient was discharged from our hospital. The tumor has not recurred, and he is under outpatient observation in the urology department. CONCLUSION: Fournier's gangrene should be considered in patients who are in a severe myelosuppressive state due to chemotherapy, have normal hepatitis B virus DNA levels but high hepatitis B surface antigen after tenofovir administration, complain of severe pain in the perianal area, and have a dark purple skin discoloration around the anus, despite having no initial anorectal lesions.

Solvent vapour-responsive structural transformations in molecular crystals composed of a luminescent mononuclear aluminium(III) complex.

Investigations into the construction of functional molecular crystals and their external stimuli-induced structural transformations represent compelling research topics, particularly for the advancement of sensors and memory devices. However, reports on the development of molecular crystals constructed from discrete mononuclear complex units and exhibiting structural transformations via the adsorption/desorption of guest molecules are scarce. In this study, we synthesised three molecular crystals composed of [Al(sap)(acac)(H2O)]·(solvent) (H2sap = 2-salicylideneaminophenol, acac = acetylacetonate, solvent = Me2CO (Al·Me2CO), MeCN (Al·MeCN), or DMSO (Al·DMSO)), and demonstrated solvent vapour-responsive reversible crystal-to-crystal structural transformations in Al·Me2CO and Al·MeCN. For Al·DMSO, exposure to DMSO vapour led to the formation of DMSO-coordinated compound [Al(sap)(acac)(DMSO)], indicating an irreversible structural transformation. This solvent vapour-responsive system incorporates a luminescent mononuclear aluminium(III) complex (λmax = 539-552 nm, Φem = 0.07-0.27) as the molecular building unit for the porous-like framework. Therefore, we synthesised a new functional molecular material and a potential molecular building unit that facilitates guest fixation through hydrogen-bonding.

Nitrous Oxide Emission in Response to pH from Degrading Palsa Mire Peat Due to Permafrost Thawing.

N2O, a greenhouse gas, is increasingly emitted from degrading permafrost mounds of palsa mires because of the global warming effects on microbial activity. In the present study, we hypothesized that N2O emission could be affected by a change in pH conditions because the collapse of acidic palsa mounds (pH 3.4-4.6) may result in contact with minerogenic ground water (pH 4.8-6.3), thereby increasing the pH. We compared the effects of pH change on N2O emission from cultures inoculated with peat suspensions. Peat samples were collected on a transect from a still intact high part to the collapsing edge of a degrading palsa mound in northwestern Finland, assuming the microbial communities could be different. We adjusted the pH of peat suspensions prepared from a collapsing palsa mound and compared the N2O emission in a pH gradient from 4.5 to 8.5. The collapsing edge had the highest N2O emission from the peat suspensions among all points on the transect under natural acidic conditions (pH 4.5). The N2O emission was reduced with a moderate rise in pH (pH 5.0-6.0) by approximately 85% compared with natural acidic level (pH 4.5). The bacterial communities in acidic cultures differed considerably from those in alkaline cultures. When pH was adjusted to alkaline conditions, N2O-emitting bacteria different from those present in acidic conditions appeared to emit N2O. The bacterial communities could be characterized by changing pH conditions after thawing and collapse of permafrost have contrasting impacts on N2O production that calls for further attention in future studies.

An Unknown Non-denitrifier Bacterium Isolated from Soil Actively Reduces Nitrous Oxide under High pH Conditions.

A nitrous oxide (N2O)-consuming bacterium isolated from farmland soil actively consumed N2O under high pH conditions. An acetylene inhibition assay did not show the denitrification of N2 to N2O by this bacterium. When N2O was injected as the only nitrogen source, this bacterium did not assimilate N2O. A polymerase chain reaction demonstrated that this bacterium did not have the typical nosZ gene. This bacterium belonged to Chitinophagaceae, but did not belong to known families that include bacteria with the atypical nosZ. This is the first study to show that a non-denitrifier actively reduces N2O, even under high pH conditions.

Age-related circadian disorganization caused by sympathetic dysfunction in peripheral clock regulation.

The ability of the circadian clock to adapt to environmental changes is critical for maintaining homeostasis, preventing disease, and limiting the detrimental effects of aging. To date, little is known about age-related changes in the entrainment of peripheral clocks to external cues. We therefore evaluated the ability of the peripheral clocks of the kidney, liver, and submandibular gland to be entrained by external stimuli including light, food, stress, and exercise in young versus aged mice using in vivo bioluminescence monitoring. Despite a decline in locomotor activity, peripheral clocks in aged mice exhibited normal oscillation amplitudes under light-dark, constant darkness, and simulated jet lag conditions, with some abnormal phase alterations. However, age-related impairments were observed in peripheral clock entrainment to stress and exercise stimuli. Conversely, age-related enhancements were observed in peripheral clock entrainment to food stimuli and in the display of food anticipatory behaviors. Finally, we evaluated the hypothesis that deficits in sympathetic input from the central clock located in the suprachiasmatic nucleus of the hypothalamus were in part responsible for age-related differences in the entrainment. Aged animals showed an attenuated entrainment response to noradrenergic stimulation as well as decreased adrenergic receptor mRNA expression in target peripheral organs. Taken together, the present findings indicate that age-related circadian disorganization in entrainment to light, stress, and exercise is due to sympathetic dysfunctions in peripheral organs, while meal timing produces effective entrainment of aged peripheral circadian clocks.