New Computerized Planning Algorithm and Clinical Testing of Optimized Nuss Bar Design for Patients with Pectus Excavatum.

BACKGROUND Computer-aided design (CAD) has been used in the Nuss procedure to determine the bar length and shape. Despite computer aid, the shape and design remain quite intuitive. We tested a new algorithm to determine the optimal bar shape. MATERIAL AND METHODS The normal sterno-vertebral distance was defined on computed tomography (CT) scans of patients without pectus excavatum (PEx) at the same level where the deepest depression was found on CT scans of 97 patients with PEx. Four points were marked on the CT scan of 60 patients with PEx at the deepest deformity: P1: edge of the vertebra; P2: edge of the deformity; P3: the expected contact point of the bar and the rib; and P4: the expected end of the bar. The algorithm generated 3 circles upon these points, and the fusion of the arcs drew the line of the ideal bar. Corrected and normal sterno-vertebral distance values were compared with the Mann-Whitney U test. Ten bars were bent manually guided by a 1: 1 printout of the designed bar and were implanted in 10 adolescents. RESULTS The shortest sterno-vertebral distance was 3 cm below the intermammillary line in PEx patients. The normal mean sterno-vertebral distance at this level was 10.16±1.35 cm in non-PEx patients. The mean virtually corrected sterno-vertebral distance was 10.28±1.27 cm. No significant difference was found (P=0.44). The bars were seamless and were successfully implanted. No bar needed adjustment, the operation time was shorter, and the patient satisfaction score was 9.4/10. CONCLUSIONS With our new algorithm, an optimal Nuss bar can be designed.

Investigation of the Effect on the Albumin Binding Moiety for the Pharmacokinetic Properties of 68Ga-, 205/206Bi-, and 177Lu-Labeled NAPamide-Based Radiopharmaceuticals.

Although radiolabeled alpha-melanocyte stimulating hormone-analogue NAPamide derivatives are valuable melanoma-specific diagnostic probes, their rapid elimination kinetics and high renal uptake may preclude them from being used in clinical settings. We aimed at improving the pharmacokinetics of radiolabeled DOTA-NAPamide compounds by incorporating a 4-(p-iodo-phenyl)-butanoic acid (IPB) into the molecules. Followed by 68Ga-, 205/206Bi-, and 177Lu-labelling, the radiopharmaceuticals ([68Ga]Ga-DOTA-IPB-NAPamide, [205/206Bi]Bi-DOTA-IPB-NAPamide, [177Lu]Lu-DOTA-IPB-NAPamide) were characterized in vitro. To test the imaging behavior of the IPB-containing probes, B16F10 tumor-bearing C57BL/6 mice were subjected to in vivo microPET/microSPECT/CT imaging and ex vivo biodistribution studies. All tracers were stable in vitro, with radiochemical purity exceeding 98%. The use of albumin-binding moiety lengthened the in vivo biological half-life of the IPB-carrying radiopharmaceuticals, resulting in elevated tumor accumulation. Both [68Ga]Ga-DOTA-IPB-NAPamide (5.06 ± 1.08 %ID/g) and [205/206Bi]Bi-DOTA-IPB-NAPamide (4.50 ± 0.98 %ID/g) exhibited higher B16F10 tumor concentrations than their matches without the albumin-binding residue ([68Ga]Ga-DOTA-NAPamide and [205/206Bi]Bi-DOTA-NAPamide: 1.18 ± 0.27 %ID/g and 3.14 ± 0.32; respectively), however; the large amounts of off-target radioactivity do not confirm the benefits of half-life extension for short-lived isotopes. Enhanced [177Lu]Lu-DOTA-IPB-NAPamide tumor uptake even 24 h post-injection proved the advantage of IPB-based prolonged circulation time regarding long-lived radionuclides, although the significant background noise must be addressed in this case as well.

[Pulmonary histiocytic sarcoma]. / A tüdo histiocytás sarcomája.

Histiocytic sarcoma is an uncommon hematological malignancy. Its occurrence in the lung is very rare. Due to the small number of cases and the clinical and pathological features of the disease, the diagnosis can be challenging. Its optimal treatment is not yet known, in locally confined cases - depending on the location and size - surgical removal is part of complex oncotherapy. We report the case of a 52-year-old man with a tumor of central localization in the left lung. Pulmonectomy was performed. Histology verified histiocytic sarcoma of the lung. An overview of clinical features of the entity is presented in connection with our case report. Orv Heti. 2023; 164(34): 1350-1357.

Gallium(III)- and Thallium(III)-Encapsulated Polyoxopalladates: Synthesis, Structure, Multinuclear NMR, and Biological Activity Studies.

Three gallium(III)- and thallium(III)-containing polyoxopalladates (POPs) have been synthesized and structurally characterized in the solid state and in solution, namely, the phosphate-capped 12-palladate nanocubes [XPd12O8(PO4)8]13- (X = GaIII, GaPd12P8; X = TlIII, TlPd12P8) and the 23-palladate double-cube [Tl2IIIPd23P14O70(OH)2]20- (Tl2Pd23P14). The cuboid POPs, GaPd12P8 and TlPd12P8, are solution stable as verified by the respective 31P, 71Ga, and 205Tl nuclear magnetic resonance (NMR) spectra. Of prime interest, the spin-spin coupling schemes allowed for an intimate study of the solution behavior of the TlIII-containing POPs via a combination of 31P and 205Tl NMR, including the stoichiometry of the major fragments of Tl2Pd23P14. Moreover, biological studies demonstrated the antitumor and antiviral activity of GaPd12P8 and TlPd12P8, which were validated to be as efficient as cis-platinum against human melanoma and acute promyelocytic leukemia cells. Furthermore, GaPd12P8 and TlPd12P8 exerted inhibitory activity against two herpetic viruses, HSV-2 and HCMV, in a dose-response manner.

[Rare case of primary pulmonary myxoid sarcoma]. / Primer myxoid tüdosarcoma ritka esete.

Mesenchymal tumors of the lungs are rare, mostly aggressive, with a high metastatic rate, representing only 0.013-1.1% of all pulmonary malignancies. Primary pulmonary myxoid sarcoma is an extremely rare type of lung sarcoma and stands as a separate entity in the 2015 WHO classification, characterized by EWSR1-CREB fusion gene. So far, 37 myxoid sarcoma cases have been reported. We offer an overview of the most important characteristics of pulmonary myxoid sarcoma and differential diagnosis, while reviewing the reported cases. We present the case of a 47-year-old patient with pulmonary myxoid sarcoma, who was diagnosed with a right central pulmonary mass, showing rapid endobronchial progression, complicated by empyema. EWSR1 gene translocation could not be detected. During chemotherapy, tumor progression occurred. Molecular genetic examinations revealed MET gene exon 14 skipping mutation, based on which tyrosine-kinase inhibitor treatment was administered. Pulmonary myxoid sarcoma can be classified as a nonvascular, spindle cell entity of mesenchymal tumors, with the characteristic EWSR1-CREB1 gene translocation. The male-female ratio is similar, with a slightly higher incidence in middle-aged women (1.5 : 1). Patients' average age is 44 years; with predilection in the right upper lobe (62%), or endobronchially (85%). Without specific symptoms, diagnosis is often cumbersome. Immunohistochemical methods, typical hystological image and molecular genetic tests confirm the diagnosis. Pulmonary myxoid sarcoma is a rare entity, without specific symptoms. In our case, myxoid sarcoma was complicated by empyema, which was drained. Because of advanced stage, surgical resection was not an option. Radical surgery offers the best results, in inoperable cases therapeutic recommendations for sarcomas are the guiding principles. Our case belongs to the rare group of myxoid sarcomas, where MET activating mutation was detected, making it eligible for targeted treatment. Orv Hetil. 2023; 164(27): 1077-1083.

Relationship between gadolinium-based MRI contrast agent consumption and anthropogenic gadolinium in the influent of a wastewater treatment plant.

Gadolinium-based contrast agents (GBCAs) used in magnetic resonance imaging (MRI) are highly resistant in the environment. They pass through wastewater treatment plants (WWTPs) unhindered escaping degradation. Although GBCAs are subjects of intensive research, we recognized that a quantitative approach to the mass balance of gadolinium, based on known input and output data, is missing. The administered amount of Gd as GBCAs, the number of out- and inpatients and the concentration of rare earth elements (REEs) in wastewater were monitored for 45 days in a medium sized city (ca. 203,000 inhabitants) with two MRI centres. An advection-dispersion type model was established to describe the transport of Gd in the wastewater system. The model calculates with patient locality, excretion kinetics of Gd and the yield of wastewater. The estimated and measured daily amount of anthropogenic gadolinium released to the WWTP were compared. GBCAs (Omniscan and Dotarem) were administered to 1008 patients representing a total of 700 ± 1 g Gd. The amount of total Gd entering the WWTP was 531 ± 2 g, of which the anthropogenic contribution (i.e. GBCAs) was 261 ± 6 g (49 ± 1 % of the total Gd) during the sampling campaign. Local residents and inpatients should fully release Gd in the city, but outpatients only partially. Overall, 37 ± 1 % of the total administered Gd was recovered in the wastewater, so the remaining 63 ± 1 % of administered Gd is expected to be dispensed outside of the sewer system. Our approach enables to better understand the dispersion of GBCAs originated Gd in an urban environment.

Canine Saliva as a Possible Source of Antimicrobial Resistance Genes.

While the One Health issues of intensive animal farming are commonly discussed, keeping companion animals is less associated with the interspecies headway of antimicrobial resistance. With the constant advance in veterinary standards, antibiotics are regularly applied in companion animal medicine. Due to the close coexistence of dogs and humans, dog bites and other casual encounters with dog saliva (e.g., licking the owner) are common. According to our metagenome study, based on 26 new generation sequencing canine saliva datasets from 2020 and 2021 reposited in NCBI SRA by The 10,000 Dog Genome Consortium and the Broad Institute within Darwin's Ark project, canine saliva is rich in bacteria with predictably transferable antimicrobial resistance genes (ARGs). In the genome of potentially pathogenic Bacteroides, Capnocytophaga, Corynebacterium, Fusobacterium, Pasteurella, Porphyromonas, Staphylococcus and Streptococcus species, which are some of the most relevant bacteria in dog bite infections, ARGs against aminoglycosides, carbapenems, cephalosporins, glycylcyclines, lincosamides, macrolides, oxazolidinone, penams, phenicols, pleuromutilins, streptogramins, sulfonamides and tetracyclines could be identified. Several ARGs, including ones against amoxicillin-clavulanate, the most commonly applied antimicrobial agent for dog bites, were predicted to be potentially transferable based on their association with mobile genetic elements (e.g., plasmids, prophages and integrated mobile genetic elements). According to our findings, canine saliva may be a source of transfer for ARG-rich bacteria that can either colonize the human body or transport ARGs to the host bacteriota, and thus can be considered as a risk in the spread of antimicrobial resistance.

Modern treatment of massive hemothorax / A masszív haemothorax modern kezelése

Introduction and objective: Hemothorax is an umbrella term for pathologies with an extremely wide range of etiology and severity. Most commonly it is of tramuatic origin, frequently iatrogenic (intervention, blood coagulation altering therapy) and rarely unknown. Depending on the cause, volume, and dynamics, it requires a patient-adapted treatment determined by access to certain therapeutical methods. We aim to provide a practical overview of these. Methods: Retrospective analysis of patients treated for haemothorax at the Thoracic Surgery Department of Borsod-Abaúj-Zemplén County Teaching Hospital in the period 1 January 2017­31 December 2021 has been performed. We used the hospital's database to collect data. In this paper, we analyze the cause of hemothorax, method of treatment, the efficacy of chosen therapeutic modality, duration of hospital stay, complication rate, 30-day survival. Results: 77 patients were treated with hemothorax, 57 male, 20 female patients. Average age was 53,4 (23­90, SD:14,9) years. Surgery was performed in 31 cases, with 10 cases needing reintervention. In 7 cases, multimodal approach was chosen, with chest wall stabilization. Average hospital stay: 14 (2­79) days. 30-day survival: 95%. Discussion: Thoracic drainage is our first therapeutic choice. The methods used in the treatment of hemothorax in our practice have been extended with the use of digital subtraction angiography (DSA), which yields immediate and effective bleeding control. We performed video-assisted thoracoscopic surgery (VATS) in increasing numbers. Conclusions: As long as the intensity of bleeding and patient's general status allows it, after drainage, the first therapeutic option ­ when accessible ­ should be DSA bleeding control. In cases which do not resolve after drainage, VATS evacuation of hematoma is a safe method used in the treatment of hemothorax. In the past 5 years, we used thoracoscopy in increasing numbers while treating this entity. Based on our results and the literature, we can safely state that the use of thoracoscopy in the treatment of hemothorax is a safe and reliable option in eligible patients, and the results are comparable with those treated by thoracotomy.

Synthesis, Physicochemical, Labeling and In Vivo Characterization of 44Sc-Labeled DO3AM-NI as a Hypoxia-Sensitive PET Probe.

Hypoxia promotes angiogenesis, which is crucial for tumor growth, and induces malignant progression and increases the therapeutic resistance. Positron emission tomography (PET) enables the detection of the hypoxic regions in tumors using 2-nitroimidazole-based radiopharmaceuticals. We describe here a physicochemical study of the Sc(DO3AM-NI) complex, which indicates: (a) relatively slow formation of the Sc(DO3AM-NI) chelate in acidic solution; (b) lower thermodynamic stability than the reference Sc(DOTA); (c) however, it is substantially more inert and consequently can be regarded as an excellent Sc-binder system. In addition, we report a comparison of 44Sc-labeled DO3AM-NI with its known 68Ga-labeled analog as a hypoxia PET probe. The in vivo and ex vivo biodistributions of 44Sc- and 68Ga-labeled DO3AM-NI in healthy and KB tumor-bearing SCID mice were examined 90 and 240 min after intravenous injection. No significant difference was found between the accumulation of 44Sc- and 68Ga-labeled DO3AM-NI in KB tumors. However, a significantly higher accumulation of [68Ga]Ga(DO3AM-NI) was found in liver, spleen, kidney, intestine, lung, heart and brain than for [44Sc]Sc(DO3AM-NI), leading to a lower tumor/background ratio. The tumor-to-muscle (T/M) ratio of [44Sc]Sc(DO3AM-NI) was approximately 10-15-fold higher than that of [68Ga]Ga(DO3AM-NI) at all time points. Thus, [44Sc]Sc(DO3AM-NI) allows the visualization of KB tumors with higher resolution, making it a promising hypoxia-specific PET radiotracer.

A New Oxygen Containing Pyclen-Type Ligand as a Manganese(II) Binder for MRI and 52Mn PET Applications: Equilibrium, Kinetic, Relaxometric, Structural and Radiochemical Studies.

A new pyclen-3,9-diacetate derivative ligand (H23,9-OPC2A) was synthesized possessing an etheric O-atom opposite to the pyridine ring, to improve the dissociation kinetics of its Mn(II) complex (pyclen = 3,6,9,15-tetraazabicyclo(9.3.1)pentadeca-1(15),11,13-triene). The new ligand is less basic than the N-containing analogue (H23,9-PC2A) due to the non-protonable O-atom. In spite of its lower basicity, the conditional stability of the [Mn(3,9-OPC2A)] (pMn = -log(Mn(II)), cL = cMn(II) = 0.01 mM. pH = 7.4) remains unaffected (pMn = 8.69), compared to the [Mn(3,9-PC2A)] (pMn = 8.64). The [Mn(3,9-OPC2A)] possesses one water molecule, having a lower exchange rate with bulk solvents (kex298 = 5.3 ± 0.4 × 107 s-1) than [Mn(3,9-PC2A)] (kex298 = 1.26 × 108 s-1). These mild differences are rationalized by density-functional theory (DFT) calculations. The acid assisted dissociation of [Mn(3,9-OPC2A)] is considerably slower (k1 = 2.81 ± 0.07 M-1 s-1) than that of the complexes of diacetates or bisamides of various 12-membered macrocycles and the parent H23,9-PC2A. The [Mn(3,9-OPC2A)] is inert in rat/human serum as confirmed by 52Mn labeling (nM range), as well as by relaxometry (mM range). However, a 600-fold excess of EDTA (pH = 7.4) or a mixture of essential metal ions, propagated some transchelation/transmetalation in 7 days. The H23,9-OPC2A is labeled efficiently with 52Mn at elevated temperatures, yet at 37 °C the parent H23,9-PC2A performs slightly better. Ultimately, the H23,9-OPC2A shows advantageous features for further ligand designs for bifunctional chelators.

Invasion inhibition effects and immunogenicity after vaccination of SPF chicks with a Salmonella Enteritidis live vaccine.

OBJECTIVE: Meat and eggs from chickens infected with Salmonella Enteritidis, Salmonella Typhimurium and Salmonella Infantis are considered to be an important source of Salmonella infections for humans. In order to control Salmonella infections in chickens, basic biosecurity measures are taken in combination with inactivated or attenuated live vaccines. Apart from an adaptive immune response, some live vaccines also induce innate immune mechanisms that prevent or inhibit systemic invasion with homologous Salmonella serovars. It is unknown whether these invasion inhibition effects are also directed against heterologous Salmonella serovars. Furthermore, it is unclear whether the adaptive immune response after vaccination with a Salmonella Enteritidis phage type 4 live vaccine is also directed against other phage types of Salmonella Enteritidis and Typhimurium. MATERIAL AND METHODS: Specific pathogen-free day-old chicks were vaccinated orally with a commercially available Salmonella Enteritidis live vaccine. To test the invasion inhibition effect, the animals were challenged orally with a labelled Salmonella Typhimurium or Salmonella Infantis strain 1 day after vaccination. To demonstrate the adaptive immune response against non-phage type 4 Salmonella Enteritidis strains and a monophasic Salmonella Typhimurium strain, the chickens were challenged with Salmonella Enteritidis strains of phage types 1, 8 and 21 and a monophasic Salmonella Typhimurium strain (Definitive Type 193). After challenge, the abundance of the challenge strain in liver and cecal tissue was enumerated and compared with a corresponding control group. RESULTS: Findings showed that the live Salmonella Enteritidis vaccine inhibits systemic invasion after early infection with Salmonella Typhimurium and Salmonella Infantis. Furthermore, adaptive immunity against the tested non-phage type 4 Salmonella Enteritidis strains and the monophasic Salmonella Typhimurium strain was demonstrated. CONCLUSION AND CLINICAL RELEVANCE: The results of this study demonstrate that vaccination with the Salmonella Enteritidis phage type 4 live vaccine significantly inhibits the invasion of Salmonella Typhimurium and Infantis. Furthermore, an adaptive immune response was also detected against non-phage type 4 Salmonella Enteritidis strains and a monophasic Salmonella Typhimurium strain.

Exploring Cyclic Aminopolycarboxylate Ligands for Sb(III) Complexation: PCTA and Its Derivatives as a Promising Solution.

In recent years Auger electron emitters have been suggested as promising candidates for radiotherapy with no side effects in cancer treatment. In this work we report a detailed coordination chemistry study of [Sb(PCTA)] (PCTA: 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene-3,6,9-triacetic acid), a macrocyclic aminopolycarboxylate-type complex of antimony(III), whose 119Sb isotope could be a suitable low-energy electron emitter for radiotherapy. The thermodynamic stability of the chelate obtained by pH-potentiometry and UV-vis spectrophotometry is high enough (log K[Sb(PCTA)] = 23.2(1)) to prevent the hydrolysis of the metal ion near physiological pH. The formation of [Sb(PCTA)] is confirmed by NMR and electrospray ionization mass spectrometry measurements in solution; furthermore, the structure of [Sb(PCTA)]·NaCl·3H2O and [Sb(PCTA)]·HCl·3H2O is described by X-ray and density functional theory calculations. Consequently, the [Sb(PCTA)] is the first thermodynamically stable antimony(III) complex bearing polyamino-polycarboxylate macrocyclic platform. Our results demonstrate the potential of rigid (pyclen derivative) ligands as chelators for future applications of Sb(III) in a targeted radiotherapy based on the 119Sb isotope.

Complexes of Bifunctional DO3A-N-(α-amino)propinate Ligands with Mg(II), Ca(II), Cu(II), Zn(II), and Lanthanide(III) Ions: Thermodynamic Stability, Formation and Dissociation Kinetics, and Solution Dynamic NMR Studies.

The thermodynamic, kinetic, and structural properties of Ln3+ complexes with the bifunctional DO3A-ACE4- ligand and its amide derivative DO3A-BACE4- (modelling the case where DO3A-ACE4- ligand binds to vector molecules) have been studied in order to confirm the usefulness of the corresponding Gd3+ complexes as relaxation labels of targeted MRI contrast agents. The stability constants of the Mg2+ and Ca2+ complexes of DO3A-ACE4- and DO3A-BACE4- complexes are lower than for DOTA4- and DO3A3-, while the Zn2+ and Cu2+ complexes have similar and higher stability than for DOTA4- and DO3A3- complexes. The stability constants of the Ln(DO3A-BACE)- complexes increase from Ce3+ to Gd3+ but remain practically constant for the late Ln3+ ions (represented by Yb3+). The stability constants of the Ln(DO3A-ACE)4- and Ln(DO3A-BACE)4- complexes are several orders of magnitude lower than those of the corresponding DOTA4- and DO3A3- complexes. The formation rate of Eu(DO3A-ACE)- is one order of magnitude slower than for Eu(DOTA)-, due to the presence of the protonated amine group, which destabilizes the protonated intermediate complex. This protonated group causes the Ln(DO3A-ACE)- complexes to dissociate several orders of magnitude faster than Ln(DOTA)- and its absence in the Ln(DO3A-BACE)- complexes results in inertness similar to Ln(DOTA)- (as judged by the rate constants of acid assisted dissociation). The 1H NMR spectra of the diamagnetic Y(DO3A-ACE)- and Y(DO3A-BACE)- reflect the slow dynamics at low temperatures of the intramolecular isomerization process between the SA pair of enantiomers, R-Λ(λλλλ) and S-Δ(δδδδ). The conformation of the Cα-substituted pendant arm is different in the two complexes, where the bulky substituent is further away from the macrocyclic ring in Y(DO3A-BACE)- than the amino group in Y(DO3A-ACE)- to minimize steric hindrance. The temperature dependence of the spectra reflects slower ring motions than pendant arms rearrangements in both complexes. Although losing some thermodynamic stability relative to Gd(DOTA)-, Gd(DO3A-BACE)- is still quite inert, indicating the usefulness of the bifunctional DO3A-ACE4- in the design of GBCAs and Ln3+-based tags for protein structural NMR analysis.

Complexation of Mn(II) by Rigid Pyclen Diacetates: Equilibrium, Kinetic, Relaxometric, Density Functional Theory, and Superoxide Dismutase Activity Studies.

We report the Mn(II) complexes with two pyclen-based ligands (pyclen = 3,6,9,15-tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene) functionalized with acetate pendant arms at either positions 3,6 (3,6-PC2A) or 3,9 (3,9-PC2A) of the macrocyclic fragment. The 3,6-PC2A ligand was synthesized in five steps from pyclen oxalate by protecting one of the secondary amine groups of pyclen using Alloc protecting chemistry. The complex with 3,9-PC2A is characterized by a higher thermodynamic stability [log KMnL = 17.09(2)] than the 3,6-PC2A analogue [log KMnL = 15.53(1); 0.15 M NaCl]. Both complexes contain a water molecule coordinated to the metal ion, which results in relatively high 1H relaxivities (r1p = 2.72 and 2.91 mM-1 s-1 for the complexes with 3,6-PC2A and 3,9-PC2A, respectively, at 25 °C and 0.49 T). The coordinated water molecule displays fast exchange kinetics with the bulk in both cases; the rates (kex298) are 140 × 106 and 126 × 106 s-1 for [Mn(3,6-PC2A)(H2O)] and [Mn(3,9-PC2A)(H2O)], respectively. The two complexes were found to be remarkably inert with respect to their dissociation, with half-lives of 63 and 21 h, respectively, at pH = 7.4 in the presence of excess Cu(II). The r1p values recorded in blood serum remain constant at least over a period of 120 h. Cyclic voltammetry experiments show irreversible oxidation features shifted to higher potentials with respect to [Mn(EDTA)(H2O)]2- (H4EDTA = ethylenediaminetetraacetic acid) and [Mn(PhDTA)(H2O)]2- (H4PhDTA = phenylenediamine-N,N,N',N'-tetraacetic acid), indicating that the PC2A complexes reported here have a lower tendency to stabilize Mn(III). The superoxide dismutase activity of the Mn(II) complexes was tested using the xanthine/xanthine oxidase/p-nitro blue tetrazolium chloride assay at pH = 7.8. The Mn(II) complexes of 3,6-PC2A and 3,9-PC2A are capable of assisting decomposition of the superoxide anion radical. The kinetic rate constant of the complex of 3,9-PC2A is smaller by 1 order of magnitude than that of 3,6-PC2A.

Shape and Size Tuning of BiIII-Centered Polyoxopalladates: High Resolution 209Bi NMR and 205/206Bi Radiolabeling for Potential Pharmaceutical Applications.

We have discovered five bismuth(III)-containing polyoxopalladates (POPs) which were fully characterized by solution and solid-state physicochemical techniques: the cube-shaped [BiPd12O32(AsPh)8]5- (BiPd12AsL), [BiPd12O32(AsC6H4N3)8]5- (BiPd12AsLN), and [BiPd12O32(AsC6H4COO)8]13- (BiPd12AsLC) as well as the star-shaped [BiPd15O40(PO)10H6]11- (BiPd15P) and [BiPd15O40(PPh)10]7- (BiPd15PL), respectively. The organically modified capping groups phenylarsonate, p-azidophenylarsonate, and p-carboxyphenylarsonate were chosen as the azido (-N3) and carboxyl (-COOH) groups open up opportunities to covalently conjugate (via click reaction, amide coupling, etc.) with targeting vectors. The synthesis of p-azidophenylarsonate is reported here for the first time. The effects of the BiIII template and the organoarsonate vs -posphonate capping groups on the resulting POP shape (cube vs star) are discussed. The 209Bi NMR (I = 9/2) spectra of BiPd12AsL, BiPd12AsLN, and BiPd12AsLC revealed narrow peaks (ν1/2 ∼ 200 Hz) at 5470 ppm with a longitudinal relaxation time in the millisecond range (at 8.46 T). The absence of a quadrupolar relaxation contribution could be attributed to the allocation of BiIII in the highly symmetrical cuboid POP host cage. Similar peaks were absent in the 209Bi-NMR spectra of the star-shaped POPs BiPd15P and BiPd15PL due to the less symmetric coordination environment around the central BiIII ion. Further, 205/206Bi-radiolabeled POPs have been synthesized by incorporating a 205/206BiIII ion in the center of the POP structures. Carrier-free 205/206Bi radioisotopes (as surrogates of α-emitting 213Bi) were incorporated into the POP host-cage for the preparation of 205/206BiPd12AsL, 205/206BiPd12AsLN, 205/206BiPd12AsLC, and 205/206BiPd15PL, respectively. The radiometal incorporation was complete (>99% radiochemical yield) in 10 min according to radio-thin-layer chromatography. The 205/206BiPd12AsL polyanion was purified by solid-phase extraction. The incubation in rat serum showed the formation of a 205/206BiPd12AsL-protein aggregate.

Global-scale brittle plastic rheology at the cometesimals merging of comet 67P/Churyumov-Gerasimenko.

Observations of comet nuclei indicate that the main constituent is a mix of ice and refractory materials characterized by high porosity (70-75%) and low bulk strength (10-4-10-6 MPa); however, the nature and physical properties of these materials remain largely unknown. By combining surface inspection of comet 67P/Churyumov-Gerasimenko and three-dimensional (3D) modeling of the independent concentric sets of layers that make up the structure of its two lobes, we provide clues about the large-scale rheological behavior of the nucleus and the kinematics of the impact that originated it. Large folds in the layered structure indicate that the merging of the two cometesimals involved reciprocal motion with dextral strike-slip kinematics that bent the layers in the contact area without obliterating them. Widespread long cracks and the evidence of relevant mass loss in absence of large density variations within the comet's body testify that large-scale deformation occurred in a brittle-plastic regime and was accommodated through folding and fracturing. Comparison of refined 3D geologic models of the lobes with triaxial ellipsoids that suitably represent the overall layers arrangement reveals characteristics that are consistent with an impact between two roughly ellipsoidal cometesimals that produced large-scale axial compression and transversal elongation. The observed features imply global transfer of impact-related shortening into transversal strain. These elements delineate a model for the global rheology of cometesimals that could be possible evoking a prominent bonding action of ice and, to a minor extent, organics.

Indium in Polyoxopalladate(II) Chemistry: Synthesis of All-Acetate-Capped [InPd12O8(OAc)16]5- and Controlled Transformation to Phosphate-Capped Double-Cube and Monocube.

We have prepared the indium(III)-centered, all-acetate-capped polyoxopalladate(II) nanocube [InPd12O8(OAc)16]5- (InPd12Ac16), which can be further used as precursor to form the phosphate-capped (i) double-cube [In2Pd23O17(OH)(PO4)12(PO3OH)]21- (In2Pd23P13) and (ii) monocube [InPd12O8(PO4)8]13- (InPd12P8). All three novel polyoxopalladates (POPs) were synthesized using conventional one-pot techniques in aqueous solution and characterized in the solid state (single-crystal XRD, IR, elemental analysis), in solution (115In, 31P, and 13C NMR), and in the gas phase (ESI-MS).

PIDAZTA: Structurally Constrained Chelators for the Efficient Formation of Stable Gallium-68 Complexes at Physiological pH.

Two structurally constrained chelators based on a fused bicyclic scaffold, 4-amino-4-methylperhydro-pyrido[1,2-a][1,4]diazepin-N,N',N'-triacetic acids [(4R*,10aS*)-PIDAZTA (L1) and (4R*,10aR*)-PIDAZTA (L2)], were designed for the preparation of GaIII -based radiopharmaceuticals. The stereochemistry of the ligand scaffold has a deep impact on the properties of the complexes, with unexpected [Ga(L2)OH] species being superior in terms of both thermodynamic stability and inertness. This peculiar behavior was rationalized on the basis of molecular modeling and appears to be related to a better fit in size of GaIII into the cavity of L2. Fast and efficient formation of the GaIII chelates at room temperature was observed at pH values between 7 and 8, which enables 68 Ga radiolabeling under truly physiological conditions (pH 7.4).

[Spontaneous haemothorax - thoracic surgeon and intervention radiologist successful cooperation]. / Spontán haemothorax ­ mellkassebész és intervenciós radiológus sikeres együttmuködése.

The definition of spontaneous haemothorax is accumulation of blood within the pleural space without trauma or iatrogenic causes. A case of a 17-year-old male patient with a history of multiple abnormal arterial fistulas between systemic circulation and pulmonary circulation as a cause of bleeding is presented. An overview of the causes, the clinical features of haemothorax and the interventional radiological methods that can solve some causes of haemothorax are presented in connection of our case report.

Effect of the Nature of Donor Atoms on the Thermodynamic, Kinetic and Relaxation Properties of Mn(II) Complexes Formed With Some Trisubstituted 12-Membered Macrocyclic Ligands.

During the past few years increasing attention has been devoted to Mn(II) complexes as possible substitutes for Gd(III) complexes as contrast agents in MRI. Equilibrium (log KMnL or pMn value), kinetic parameters (rates and half-lives of dissociation) and relaxivity of the Mn(II) complexes formed with 12-membered macrocyclic ligands were studied. The ligands were selected in a way to gain information on how the ligand rigidity, the nature of the donor atoms in the macrocycle (pyridine N, amine N, and etheric O atom), the nature of the pendant arms (carboxylates, phosphonates, primary, secondary and tertiary amides) affect the physicochemical parameters of the Mn(II) complexes. As expected, decreasing the denticity of DOTA (to afford DO3A) resulted in a drop in the stability and inertness of [Mn(DO3A)]- compared to [Mn(DOTA)]2-. This decrease can be compensated partially by incorporating the fourth nitrogen atom into a pyridine ring (e.g., PCTA) or by replacement with an etheric oxygen atom (ODO3A). Moreover, the substitution of primary amides for acetates resulted in a noticeable drop in the stability constant (PC3AMH), but it increased as the primary amides (PC3AMH) were replaced by secondary (PC3AMGly) or tertiary amide (PC3AMPip) pendants. The inertness of the Mn(II) complexes behaved alike as the rates of acid catalyzed dissociation increased going from DOTA (k1 = 0.040 M-1s-1) to DO3A (k1 = 0.45 M-1s-1). However, the rates of acid catalyzed dissociation decreased from 0.112 M-1s-1 observed for the anionic Mn(II) complex of PCTA to 0.0107 M-1s-1 and 0.00458 M-1s-1 for the cationic Mn(II) complexes of PC3AMH and PC3AMPip ligands, respectively. In spite of its lower denticity (as compared to DOTA) the sterically more hindered amide complex ([Mn(PC3AMPip)]2+) displays surprisingly high conditional stability (pMn = 8.86 vs. pMn = 9.74 for [Mn(PCTA)]-) and excellent kinetic inertness. The substitution of phosphonates for the acetate pendant arms (DOTP and DO3P), however, resulted in a noticeable drop in the conditional stability as well as dissociation kinetic parameters of the corresponding Mn(II) complexes ([Mn(DOTP)]6- and [Mn(DO3P)]4-) underlining that the phosphonate pedant should not be considered as a suitable building block for further ligand design while the tertiary amide moiety will likely have some implications in this respect in the future.