Chronic pneumonia due to Klebsiella oxytoca mimicking pulmonary tuberculosis

Klebsiella species infrequently cause acute community acquired pneumonia (CAP). The chronic form of the disease caused by K. pneumoniae (Friedlander’s bacillus) was occasionally seen in the pre-antibiotic era. K. oxytoca is a singularly uncommon cause of CAP. The chronic form of the disease caused by K. oxytoca has been documented only once before. A 50-year-old immunocompetent male smoker presented with haemoptysis for 12 months. Imaging demonstrated a cavitary lesion in the right upper lobe with emphysematous changes. Sputum stains and cultures for Mycobacterium tuberculosis were negative. However, three sputum samples for aerobic culture as well as bronchial aspirate cultured pure growth of K. oxytoca. A diagnosis of chronic pneumonia due to K. oxytoca was established and with appropriate therapy, the patient was largely asymptomatic. The remarkable clinical and radiological similarity to pulmonary tuberculosis can result in patients with chronic Klebsiella pneumonia erroneously receiving anti-tuberculous therapy

Frailty and chronic kidney disease: associations and implications

ABSTRACT Introduction: Frailty and its association with chronic kidney disease (CKD) has been established previously. The present study examined this association further by studying the distribution of frailty among groups defined by different stages of the disease. It also identified associated health deficits and explored their association with estimated glomerular filtration rate (eGFR) and urine albumin creatinine ratio (UACR). Methods: A cross-sectional survey was conducted on 90 non-dialysis dependent CKD Stage 1–4 patients, recruited in three stratified groups of 30 participants each based on the stage of disease. Frailty was assessed using Fried’s frailty criteria and associated health deficits were recorded using a pre-determined list. Depression was screened using a 4-point depression scale. Results: 21.1% of the participants were frail and 43.3% were pre-frail. The proportion of frailty in CKD groups A (Stages 1 and 2), B (Stage 3a), and C (Stages 3b and 4) was 10%, 13.3%, and 40%, respectively. The association of health deficits including co-morbidities, physical parameters, mental status, daily activities, etc. with UACR, eGFR, and CKD stages was not statistically significant. Nearly one in two frail participants was depressed compared with 14% among non-frail participants. Conclusion: The skewed distribution of 21% frail subjects identified in our study indicates an association between frailty and advancing kidney disease. Frail individuals had a lower eGFR, higher UACR, were more likely to be depressed, and had higher count of health deficits and poorer performance on Barthel Index of Activities of Daily Living and WHOQOL. Early identification of depression would improve care in these patients

Trapping an Elusive Fe(IV)-Superoxo Intermediate Inside a Self-Assembled Nanocage in Water at Room Temperature

Molecular cavities that mimic natural metalloenzymes have shown the potential to trap elusive reaction intermediates. Here, we demonstrate the formation of a rare yet stable Fe(IV)-superoxo intermediate at room temperature subsequent to dioxygen binding at the Fe(III) site of a (Et4N)2[FeIII(Cl)(bTAML)] complex confined inside the hydrophobic interior of a water-soluble Pd6L412+ nanocage. Using a combination of electron paramagnetic resonance, Mössbauer, Raman/IR vibrational, X-ray absorption, and emission spectroscopies, we demonstrate that the cage-encapsulated complex has a Fe(IV) oxidation state characterized by a stable S = 1/2 spin state and a short Fe-O bond distance of ∼1.70 Å. We find that the O2 reaction in confinement is reversible, while the formed Fe(IV)-superoxo complex readily reacts when presented with substrates having weak C-H bonds, highlighting the lability of the O-O bond. We envision that such optimally trapped high-valent superoxos can show new classes of reactivities catalyzing both oxygen atom transfer and C-H bond activation reactions.J.D. thanks TIFR and the Department of Atomic Energy (DAE), Government of India,for funds under Project no. 12- R&D-TFR-5.10-0100. S.S.G.acknowledges SERB, New Delhi (Grant no. EMR/2017/003258), for funding, and P.D. thanks CSIR for the fellowship.D.M. acknowledges support from the Spanish Ministerio de Ciencia, Innovacion y Universidades grant (PID2019-111086RA-I00, TED2021-132757B-I00, CNS2023-145046,and PID2022-143013OB-I00), PIE grant from CSIC- ICMM(20226AT001), and the Ramón y Cajal Fellowship(RYC2020-029863-I). We acknowledge SOLEIL for the provision of synchrotron radiation facilities under proposalno. 20210639 at the SAMBA beamline and thank Dr. GautierLandrot for assistance at the beamline. S.A.V.J. and S.D.acknowledge the Max Planck Society for support. We thank Dr. Sergey Peredkov for the XES measurements. The Fe KβXES measurements were carried out at the PINK beamline atthe BESSY II electron storage ring operated by the Helmholtz-Zentrum Berlin für Materialien und Energie. S.S.G. thanks Dr.Michael T. Green (UC Irvine) for the suggestion of the NOexperimentPeer reviewe

Trapping an Elusive Fe(IV)-Superoxo Intermediate Inside a Self-Assembled Nanocage at Room Temperature

Natural metalloenzymes stabilize reactive intermediates through specific metal-substrate interactions in protein confinement. Using the structural blueprint of enzyme pockets it is possible to trap elusive intermediates inside molecular cavities. Here we demonstrate room temperature trapping of a rare yet stable Fe(IV)-superoxo [FeIV(O2)-bTAML] intermediate subsequent to dioxygen binding at the Fe(III) site of a (Et4N)2[FeIII(Cl)(bTAML)] catalyst confined inside the hydrophobic interior of a water-soluble Pd6L412+ nanocage. <br /

Photoinduced Charge Transfer State Probes the Dynamic Water Interaction with Metal–Organic Nanocages

Kinetic stabilization of reactive photointermediates inside nanocages is conjectured to arise through a subtle interplay of cavity-induced hydrophobicity, cage electrostatics, and solvent-mediated interactions. Herein we enunciate the dynamic role of the water shell around an electron-deficient Pd₆L₄¹²⁺ nanohost by optically triggering the emergent host–guest charge transfer (CT) band arising from incarcerated guest 9-anthracenealdehyde (9-AA). Using time-resolved spectroscopy complemented with resonance Raman, we determine two temporal regimes of aqueous solvation, i.e. ∼120 fs and ∼4 ps, around the host–guest complex. Solvent-isotope dependent lifetime changes of the emissive twisted intramolecular charge transfer state for “caged” 9-AA unravel a slower ∼1.65 ns water interaction through the exposed −CHO group. Our work provides the first comprehensive physical glimpse of all excited state water-mediated interactions and thus motivates rational design of new reactions that would use the aqueous shell for supramolecular photochemistry

Light-Induced Proton-Coupled Electron Transfer Inside a Nanocage

Triggering proton-coupled electron-transfer (PCET) reactions with light in a nanoconfined host environment would bring about temporal control on the reactive pathways via kinetic stabilization of intermediates. Using a water-soluble octahedral Pd₆L₄ molecular cage as a host, we show that optical pumping of host–guest charge transfer (CT) states lead to generation of kinetically stable phenoxyl radical of the incarcerated 4-hydroxy-diphenylamine (1-OH). Femtosecond broadband transient absorption studies reveal that CT excitation initiates the proton movement from the 1-OH radical cation to a solvent water molecule in ∼890 fs, faster than the time scale for bulk solvation. Our work illustrates that optical host–guest CT excitations can drive solvent-coupled ultrafast PCET reactions inside nanocages and if optimally tuned should provide a novel paradigm for visible-light photocatalysis

Laparoscopic surgery of inguinal hernia in children - experience with 110 repairs

Background: Laparoscopic inguinal herniorraphy has been in practice in adults since its initial description by Ger in 1921. However there is no standardized technique for children until now. We present a series 110 repairs of hernias in infants and children treated laparoscopically. The aim of this study is to document authors' experience with laparoscopy in inguinal hernia in girls and boys. Material and Methods: The procedure was performed with three ports, one telescopic and the other two for needle holders. The internal inguinal ring was closed with or without dissection of sac with stitches of 3-0® Vicryl. A total of 80 children underwent surgery. Results: Once the technique of intracorporeal suturing technique is mastered, the procedure is straightforward requiring 25 minutes for unilateral and 35 minutes for bilateral hernias. Age of the patient and size of the internal inguinal ring do not influence the outcome because of magnifying effect of laparoscopy. In more than half of our patients, the preoperative diagnosis could not be matched unequivocally with the intraoperative findings. There were three recurrences in the earlier phase of study before mastering the intracorporeal suturing technique. Apart from one case which developed transient hydrocele postoperatively, no other serious complications were noted. Conclusion: Laparoscopic repair of inguinal hernia in children has proved to be feasible, safe and reliable technique. A contralateral patent processus vaginalis (PPV) is present in a surprising number of young children and laparoscopy offers safe alternative to treat both sides at the same sitting. Cosmesis is superb

On the Emergence of Electric Fields at the Water-C12E6 Surfactant Interface

We study the properties of the interface of water and the surfactant Hexaethylene Glycol Monododecyl Ether (C12E6)with a combination of Heterodyne-Detected Vibrational Sum Frequency Generation (HD-VSFG), Kelvin-Probe measurements, and Molecular Dynamics (MD) simulations. We observe that the addition of C12E6 close to the critical micelle concentration (CMC), induces a drastic hydrogen bond strength enhancement of the water molecules close to the interface, as well as a flip in their net orientation. The mutual orientation of the water and C12E6 molecules, leads to the emergence of a broad (~ 3 nm) interface with a large electric field of ~ 1V/nm, as evidenced by the Kelvin-Probe measurements and MD simulations. Our findings may open the door for the design of novel electric-field tuned catalytic and light harvesting systems anchored at water-surfactant air interface. <br /

Emergence of Electric Fields at the Water-C12E6 Surfactant Interface

We study the properties of the interface of water and the surfactant hexaethylene glycol monododecyl ether (C12E6) with a combination of heterodyne-detected vibrational sum frequency generation (HD-VSFG), Kelvin-probe measurements, and molecular dynamics (MD) simulations. We observe that the addition of the hydrogen-bonding surfactant C12E6, close to the critical micelle concentration (CMC), induces a drastic enhancement in the hydrogen bond strength of the water molecules close to the interface, as well as a flip in their net orientation. The mutual orientation of the water and C12E6 molecules leads to the emergence of a broad (∼3 nm) interface with a large electric field of ∼1 V/nm, as evidenced by the Kelvin-probe measurements and MD simulations. Our findings may open the door for the design of novel electric-field-tuned catalytic and light-harvesting systems anchored at the water-surfactant-air interface.Fil: Gera, Rahul. Fom Institute For Atomic And Molecular Physics; Países Bajos. Dutch Research Council; Países BajosFil: Bakker, Huib J.. Fom Institute For Atomic And Molecular Physics; Países Bajos. Dutch Research Council; Países BajosFil: Franklin Mergarejo, Ricardo. The Abdus Salam. International Centre for Theoretical Physics; Italia. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Morzan, Uriel. The Abdus Salam. International Centre for Theoretical Physics; Italia. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Falciani, Gabriele. Politecnico di Torino; ItaliaFil: Bergamasco, Luca. Politecnico di Torino; ItaliaFil: Versluis, Jan. Fom Institute For Atomic And Molecular Physics; Países BajosFil: Sen, Indraneel. Uppsala Universitet; SueciaFil: Dante, Silvia. Istituto Italiano Di Tecnologia; ItaliaFil: Chiavazzo, Eliodoro. Politecnico di Torino; ItaliaFil: Hassanali, Ali A.. The Abdus Salam. International Centre for Theoretical Physics; Itali

Role of miR-944/MMP10/AXL- axis in lymph node metastasis in tongue cancer

MMP10, which is upregulated in 86% of primary tongue tumors with lymph node metastases, is negatively regulated by miR-944 and promotes nodal metastasis in an orthotopic tongue cancer mouse model through the AXL signaling pathway