X-ray-Sensitive Doped CaF2-Based MRI Contrast Agents for Local Radiation Dose Measurement.

Ionizing radiation has become widely used in medicine, with application in diagnostic techniques, such as computed tomography (CT) and radiation therapy (RT), where X-rays are used to diagnose and treat tumors. The X-rays used in CT and, in particular, in RT can have harmful side effects; hence, an accurate determination of the delivered radiation dose is of utmost importance to minimize any damage to healthy tissues. For this, medical specialists mostly rely on theoretical predictions of the delivered dose or external measurements of the dose. To extend the practical use of ionizing radiation-based medical techniques, such as magnetic resonance imaging (MRI)-guided RT, a more precise measurement of the internal radiation dose internally is required. In this work, a novel approach is presented to measure dose in liquids for potential future in vivo applications. The strategy relies on MRI contrast agents (CAs) that provide a dose-sensitive signal. The demonstrated materials are (citrate-capped) CaF2 nanoparticles (NPs) doped with Eu3+ or Fe2+/Fe3+ ions. Free electrons generated by ionizing radiation allow the reduction of Eu3+, which produces a very small contrast in MRI, to Eu2+, which induces a strong contrast. Oxidative species generated by high-energy X-rays can be measured indirectly using Fe2+ because it oxidizes to Fe3+, increasing the contrast in MRI. Notably, in the results, a strong increase in the proton relaxation rates is observed for the Eu3+-doped NPs at 40 kV. At 6 MV, a significant increase in proton relaxation rates is observed using CaF2 NPs doped with Fe2+/Fe3+ after irradiation. The presented concept shows great promise for use in the clinic to measure in vivo local ionizing radiation dose, as these CAs can be intravenously injected in a saline solution.

Magnetic properties of γ-Fe2O3nanoparticles in a porous SiO2shell for drug delivery.

A method is presented for synthesizing core-shell nanoparticles with a magnetic core and a porous shell suitable for drug delivery and other medical applications. The core contains multiple $\gamma$-Fe$_2$O$_3$ nanoparticles ($\sim$15~nm) enclosed in a SiO$_2$ ($\sim$100-200~nm) matrix using either methyl (denoted TMOS-$\gamma$-Fe$_2$O$_3$) or ethyl (TEOS-$\gamma$-Fe$_2$O$_3$) template groups. Low-temperature M{\"o}ssbauer spectroscopy showed that the magnetic nanoparticles have the maghemite structure, $\gamma$-Fe$_2$O$_3$, with all the vacancies in the octahedral sites. Saturation magnetization measurements revealed that the density of $\gamma$-Fe$_2$O$_3$ was greater in the TMOS-$\gamma$-Fe$_2$O$_3$ nanoparticles than TEOS-$\gamma$-Fe$_2$O$_3$ nanoparticles, presumably because of the smaller methyl group. Magnetization measurements showed that the blocking temperature is around room temperature for the TMOS-$\gamma$-Fe$_2$O$_3$ and around 250~K for the TEOS-$\gamma$-Fe$_2$O$_3$. Three dimensional topography analysis shows clearly that the magnetic nanoparticles are not only at the surface but have penetrated deep in the silica to form the core-shell structure.

Characterization of Luminescent Materials with 151Eu Mössbauer Spectroscopy.

The application of Mössbauer spectroscopy to luminescent materials is described. Many solids doped with europium are luminescent, i.e., when irradiated with light they emit light of a longer wavelength. These materials therefore have practical applications in tuning the light output of devices like light emitting diodes. The optical properties are very different for the two possible valence states Eu 2 + and Eu 3 + , the former producing ultraviolet/visible light that shifts from violet to red depending on the host and the latter red light, so it is important to have a knowledge of their behavior in a sample environment. Photoluminescence spectra cannot give a quantitative analysis of Eu 2 + and Eu 3 + ions. Mössbauer spectroscopy, however, is more powerful and gives a separate spectrum for each oxidation state enabling the relative amount present to be estimated. The oxidation state can be identified from its isomer shift which is between - 12 and - 15 mm/s for Eu 2 + compared to around 0 mm/s for Eu 3 + . Furthermore, within each oxidation state, there are changes depending on the ligands attached to the europium: the shift is more positive for increased covalency of the bonding ligand X, or Eu concentration, and decreases for increasing Eu⁻X bond length.

Topotactic Fluorine Insertion into the Channels of FeSb2O4-Related Materials.

This paper discusses the fluorination characteristics of phases related to FeSb2O4, by reporting the results of a detailed study of Mg0.50Fe0.50Sb2O4 and Co0.50Fe0.50Sb2O4. Reaction with fluorine gas at low temperatures (typically 230 °C) results in topotactic insertion of fluorine into the channels, which are an inherent feature of the structure. Neutron powder diffraction and solid state NMR studies show that the interstitial fluoride ions are bonded to antimony within the channel walls to form Sb-F-Sb bridges. To date, these reactions have been observed only when Fe2+ ions are present within the chains of edge-linked octahedra (FeO6 in FeSb2O4) that form the structural channels. Oxidation of Fe2+ to Fe3+ is primarily responsible for balancing the increased negative charge associated with the presence of the fluoride ions within the channels. For the two phases studied, the creation of Fe3+ ions within the chains of octahedra modify the magnetic exchange interactions to change the ground-state magnetic symmetry to C-type magnetic order in contrast to the A-type order observed for the unfluorinated oxide parents.

Oxygen Insertion Reactions within the One-Dimensional Channels of Phases Related to FeSb2O4.

The structure of the mineral schafarzikite, FeSb2O4, has one-dimensional channels with walls comprising Sb3+ cations; the channels are separated by edge-linked FeO6 octahedra that form infinite chains parallel to the channels. Although this structure provides interest with respect to the magnetic and electrical properties associated with the chains and the possibility of chemistry that could occur within the channels, materials in this structural class have received very little attention. Here we show, for the first time, that heating selected phases in oxygen-rich atmospheres can result in relatively large oxygen uptakes (up to ∼2% by mass) at low temperatures (ca. 350 °C) while retaining the parent structure. Using a variety of structural and spectroscopic techniques, it is shown that oxygen is inserted into the channels to provide a structure with the potential to show high one-dimensional oxide ion conductivity. This is the first report of oxygen-excess phases derived from this structure. The oxygen insertion is accompanied not only by oxidation of Fe2+ to Fe3+ within the octahedral chains but also Sb3+ to Sb5+ in the channel walls. The formation of a defect cluster comprising one 5-coordinate Sb5+ ion (which is very rare in an oxide environment), two interstitial O2- ions, and two 4-coordinate Sb3+ ions is suggested and is consistent with all experimental observations. To the best of our knowledge, this is the first example of an oxidation process where the local energetics of the product dictate that simultaneous oxidation of two different cations must occur. This reaction, together with a wide range of cation substitutions that are possible on the transition metal sites, presents opportunities to explore the schafarzikite structure more extensively for a range of catalytic and electrocatalytic applications.

Streamlining Throughput with the Implementation of a CT Coordinator.

Imaging departments today are challenged with streamlining processes to keep up with advancements in healthcare, the increasing complexity of imaging studies and procedures, and bundling of charges for services rendered. Ordering providers are often required to get insurance pre-authorizations for imaging orders, and what is pre-authorized must be the study/procedure performed or reimbursement is not guaranteed. Insurance companies have inhibited radiologists from providing optimal service by placing restrictions on changing orders per radiologist protocol to best meet the individual needs of each patient. Many healthcare systems that are using a central scheduling model are losing money due to scans and procedures being inappropriately ordered and pre-authorized. Implementing a computed tomography (CT) coordinator can streamline throughput of imaging services in radiology departments. The CT improvement project described here used a Lean methodology Plan-Do-Check-Act (PDCA) approach to increase the effectiveness of an organization's ability to maximize process efficiency and revenue.

The magnetic and crystal structures of Sr1-δFeO2-xFx, a new oxyfluoride.

A new quasi-two-dimensional oxyfluoride, Sr1-δFeO2-xFx, has been successfully synthesized by combining topotactic fluoridation and CaH2 reduction. The introduction of F through this synthesis provides a new route to introducing charge carriers into the square layered lattice through the formation of Fe(1+) ions. While the average crystal symmetry and magnetic structure remain the same as in the parent compound, the addition of F results in an enhanced buckling of the Fe(O/F)2 square plaquettes that is most likely topologically driven.

The reaction mechanism of FeSb(2) as anode for sodium-ion batteries.

The electrochemical reaction of FeSb2 with Na is reported for the first time. The first discharge (sodiation) potential profile of FeSb2 is characterized by a gentle slope centered at 0.25 V. During charge (Na removal) and the subsequent discharge, the main reaction takes place near 0.7 V and 0.4 V, respectively. The reversible storage capacity amounts to 360 mA h g(-1), which is smaller than the theoretical value of 537 mA h g(-1). The reaction, studied by ex situ and in situ X-ray diffraction, is found to proceed by the consumption of crystalline FeSb2 to form an amorphous phase. Upon further sodiation, the formation of nanocrystalline Na3Sb domains is evidenced. During desodiation, Na3Sb domains convert into an amorphous phase. The chemical environment of Fe, probed by (57)Fe Mössbauer spectroscopy, undergoes significant changes during the reaction. During sodiation, the well-resolved doublet of FeSb2 with an isomer shift around 0.45 mm s(-1) and a quadrupole splitting of 1.26 mm s(-1) is gradually converted into a doublet line centered at about 0.15 mm s(-1) along with a singlet line around 0 mm s(-1). The former signal results from the formation of a Fe-rich FexSb alloy with an estimated composition of 'Fe4Sb' while the latter signal corresponds to superparamagnetic Fe due to the formation of nanosized pure Fe domains. Interestingly the signal of 'Fe4Sb' remains unaltered during desodiation. This mechanism is substantially different than that observed during the reaction with Li. The irreversible formation of a Fe-rich 'Fe4Sb' alloy and the absence of full desodiation of Sb domains explain the lower than theoretical practical storage capacity.

Orthotopic heart transplantation in a child with hereditary spherocytosis.

Hereditary spherocytosis (HS) is a genetic, frequently familial hemolytic blood disease that presents with varying degrees of hemolytic anemia, splenomegaly, and jaundice.The disease arises as a result of defects in any of a number of proteins responsible for maintaining the shape and flexibility of the red blood cell, resulting in an osmotically fragile and characteristically spherical red blood cell. Theoretically, cardiopulmonary bypass can exacerbate hemolysis and subsequent renal dysfunction.There are few reports of open heart surgery for patients with HS and none for orthotopic heart transplantation.We report a 6-year-old boy with HS who underwent orthotopic heart transplantation.

Cardiopulmonary bypass flow rate: a risk factor for hyperlactatemia after surgical repair of secundum atrial septal defect in children.

OBJECTIVE: Early postoperative hyperlactatemia is seen in some children after surgical repair of secundum atrial septal defect despite apparently normal cardiac output. The objective of the study was to investigate the intraoperative risk factors for hyperlactatemia in patients undergoing atrial septal defect repair. METHODS AND RESULTS: A retrospective review of 68 consecutive patients who underwent isolated atrial septal defect repair at Arkansas Children's Hospital between January 2001 and March 2006 was performed. Perioperative factors in the high lactate group (lactate >3 mmol/L, n = 26) were compared with those in the low lactate group (n = 42). Early hyperlactatemia was seen in 38% of the cohort. The high lactate group showed significantly lower weight-indexed cardiopulmonary bypass flow rate (101 + or - 6.5 mL/kg(-1)/min(-1) vs 131 + or - 6.0 mL/kg(-1)/min(-1), P = .0013), oxygen delivery during cardiopulmonary bypass (mean 12.7 + or - 0. 7 mL/kg(-1)/min(-1) vs 17.0 + or - 1 mL/kg(-1)/min(-1), P = .0009), and higher postoperative glucose (191 + or - 8.6 mg/dL vs 151 + or - 5.4 mg/dL, P = .003) compared with the LL group. Multivariate logistic regression analysis showed that weight-indexed cardiopulmonary bypass flow rate (P = .007) and average mean arterial blood pressure during cardiopulmonary bypass (P = .009) were independent risk factors for postoperative hyperlactatemia. Cardiopulmonary bypass flow rate less than 100 mL/kg(-1)/min(-1) was associated with an odds ratio of 7.67 (95% confidence interval, 1.28-45.86; P = .026) for postoperative hyperlactatemia. CONCLUSION: Lower weight-indexed cardiopulmonary bypass flow rate is an independent risk factor for early postoperative hyperlactatemia in children after atrial septal defect repair.

Anesthetic vaporizer mount malfunction resulting in oxygenation failure after initiating cardiopulmonary bypass: specific recommendations for the pre-bypass checklist.

Modern technologic advances in medicine have allowed commonly used machines to perform safely with very low risk and a high degree of success. To detect or prevent potential malfunctions, professionals routinely perform pre-use checks for equipment such as anesthesia machines and cardiopulmonary bypass (CPB) machines. These machine checklists are not only critical for a safe operation but also have large impacts on outcomes. For example, when malfunctions are encountered that could have potential negative ramifications or adverse outcomes, multi-approach strategies should be used to identify rectifiable causes and find solutions that are practical. This information can be used to promulgate safe practice guidelines. This case report identifies a machine-based contributing factor to precipitous hypoxia on initiation of bypass in one of our patients. After a detailed approach to identify preventable root causes, we made simple additions to our pre-bypass checklist and recommend these changes to other institutions.

Preliminary single center North American experience with the Berlin Heart pediatric EXCOR device.

For children requiring mechanical circulatory support as a bridge to cardiac transplantation in North America, options previously were limited to extracorporeal membrane oxygenation (ECMO) or centrifugal pump ventricular assist, both of which were suitable for only very short term application and were associated with significant complications and limitations. The Berlin Heart EXCOR ventricular assist device (VAD) was recently introduced into practice in North America to address this deficiency. We report a preliminary single center experience with the EXCOR in 17 children, 13 who received only a left-sided pump and four who required biventricular support. Before EXCOR placement, six patients were on ECMO, and one was on a centrifugal VAD. Eleven children were bridged to transplantation, one was bridged to recovery, and one remains on support. Three children died during support and one died after explantation. There was one late death nearly 2 years after transplant. Complications included stroke in seven patients, two of which were ultimately fatal. Five patients required re-operations for bleeding or evacuation of hematoma. Despite a disappointing rate of neurologic morbidity, our preliminary experience with the EXCOR has been very encouraging.

Management of a pediatric patient on the Berlin Heart Excor ventricular assist device with argatroban after heparin-induced thrombocytopenia.

We report a 15-year-old male patient who developed type II heparin-induced thrombocytopenia (HIT) after 6 weeks of heparin administration and placement of a Berlin Heart Excor left ventricular assist device (LVAD).

Superior vena cava perforation in a child from a lawnmower projectile.

Lawnmowers are one of the most frequent causes of mutilating injuries to children. The majority of accidents are caused by negligence of the operator. Most injuries of this type are caused by direct contact with the spinning blade and, less frequently, by projectiles propelled by the blade. Such projectiles usually produce bruises, but can penetrate skin and soft tissues. This report presents a 6-year-old child who suffered a small, outwardly insignificant puncture wound of the chest from a lawnmower-propelled projectile who presented with fever and chest pain the following day. The diagnostic work up and treatment of this deceptively life-threatening wound are discussed.

Cardiopulmonary bypass for adults with congenital heart disease: pitfalls for perfusionists.

The fixed incidence of congenital heart defects and improved survival have resulted in increasing numbers of adults with congenital heart disease (CHD) who have undergone complex repairs and/or palliations. Eventually, there will be more adults with CHD than children. They will require cardiac surgical interventions associated with progression of their CHD or for age-related disease, such as coronary revascularization. During bypass, anatomical shunts may exist within or without the heart. Left-to-right shunts can result in dramatically lower systemic blood flow than pump flow due to 'steal', while pulmonary edema ensues due to excessive pulmonary flow. Right-to-left shunts carry risks of massive air embolism and double or triple venous cannulation may be necessary. Cannulation of composite reconstructed aortas may be difficult, risking dissection or aortic obstruction, and double arterial cannulation may be indicated. Aberrant coronary arterial and venous anatomy may .preclude adequate myocardial preservation with common techniques and can be complicated by aortic insufficiency. Valves and conduits may exhibit failure. Conventional monitoring, such as central venous oximetry, may be misleading. Monitoring, such as serial lactate measurement, near-infrared spectroscopy and transcranial Doppler blood velocity, offer advantages for such patients. The perfusionist needs to be aware of such conditions as much congenital aberrancy may present unexpectedly during cardiac surgery.

The first successful DeBakey VAD child implantation as a bridge to transplant.

A 14-year-old boy with repaired transposition of the great arteries and ventricular septal defect presented with atrial flutter and severe congestive heart failure. Despite successful cardioversion and optimal medical therapy, the patient deteriorated and was supported with extracorporeal membrane oxygenation (ECMO). Two days after initiating ECMO support, we implanted the DeBakey VAD Child ventricular assist device (MicroMed Technology, Inc., Houston, TX) under the Humanitarian Device Exemption program. Later, he was able to pursue normal daily activities including physical rehabilitation and ambulation in the hospital. After 56 days, he underwent a successful cardiac transplantation. After 3 months, he had good cardiac function and no evidence of rejection. The DeBakey VAD Child device is a valuable option for cardiac support as a bridge to transplantation.

Management of continuous venous gas emboli during extracorporeal life support utilizing the Kolobow gas trap.

Extracorporeal life support (ECLS) with a roller pump system uses a closed cardiopulmonary bypass (CPB) circuit not equipped with a venous reservoir. Hence, gas emboli cannot escape the ECLS circuit, predisposing to clot formation, membrane failure and potential gas embolism. Rarely, some patients may develop a continuous release of gas into the venous circulation from multiple sources. Two pediatric ECLS cases are presented with continuous venous gas embolism. A 'gas trap' was devised by creating a column of fluid erected vertically on the venous line. This allowed gas to rise within the column, separating it from the ECLS circuit, thus, preventing gas from lodging in the membrane.