Influencing ionic conductivity and mechanical properties of ionic liquid polymer electrolytes by designing the chemical monomer structure.

Polymeric single chloride-ion conductor networks based on acrylic imidazolium chloride ionic liquid monomers AACXImCYCl as reported previously are prepared. The chemical structure of the polymers is varied with respect to the acrylic substituents (alkyl spacer and alkyl substituent in the imidazolium ring). The networks are examined in detail with respect to the influence of the chemical structure on the resulting properties including thermal behavior, rheological behavior, swelling behavior, and ionic conductivity. The ionic conductivities increase (by two orders of magnitude from 10-6 to 10-4 S·cm-1 with increasing temperature), while the complex viscosities of the polymer networks decrease simultaneously. After swelling in water for 1 week the ionic conductivity reaches values of 10-2 S·cm-1. A clear influence of the spacer and the crosslinker content on the glass transition temperature was shown for the first time in these investigations. With increasing crosslinker content, the Tg values and the viscosities of the networks increase. With increasing spacer length, the Tg values decrease, but the viscosities increase with increasing temperature. The results reveal that the materials represent promising electrolytes for batteries, as proven by successful charging/discharging of a p(TEMPO-MA)/zinc battery over 350 cycles.

High-Resolution Tracking of Multiple Distributions in Metallic Nanostructures: Advanced Analysis Was Carried Out with Novel 3D Correlation Thermal Field-Flow Fractionation.

Multifunctional metallic nanostructures are essential in the architecture of modern technology. However, their characterization remains challenging due to their hybrid nature. In this study, we present a novel photoreduction-based protocol for augmenting the inherent properties of imidazolium-containing ionic polymers (IIP)s through orthogonal functionalization with gold nanoparticles (Au NPs) to produce IIP_Au NPs, as well as novel and advanced characterization via three-dimensional correlation thermal field-flow fractionation (3DCoThFFF). Coordination chemistry is applied to anchor Au3+ onto the nitrogen atom of the imidazolium rings, for subsequent photoreduction to Au NPs using UV irradiation. Thermal field-flow fractionation (ThFFF) and the localized surface plasmon resonance (LSPR) of Au NPs are both dependent on size, shape, and composition, thus synergistically co-opted herein to develop mutual correlation for the advanced analysis of 3D spectral data. With 3DCoThFFF, multiple sizes, shapes, compositions, and their respective distributions are synchronously correlated using time-resolved LSPR, as derived from multiple two-dimensional UV-vis spectra per unit ThFFF retention time. As such, higher resolutions and sensitivities are observed relative to those of regular ThFFF and batch UV-vis. In addition, 3DCoThFFF is shown to be highly suitable for monitoring and evaluating the thermostability and dynamics of the metallic nanostructures through the sequential correlation of UV-vis spectra measured under incremental ThFFF temperature gradients. Comparable sizes are measured for IIP and IIP_Au NPs. However, distinct elution profiles and UV-vis absorbances are recorded, thereby reaffirming the versatility of ThFFF as a robust tool for validating the successful functionalization of IIP with Au to produce IIP_Au NPs.

P-Ru-Complexes with a Chelate-Bridge-Switch: A Comparison of 2-Picolyl and 2-Pyridyloxy Moieties as Bridging Ligands.

Starting from [Ru(pyO)2(nbd)] 1 and a N,P,N-tridentate ligand (2a: PhP(pic)2, 2b: PhP(pyO)2) (nbd = 2,5-norbornadiene, pic = 2-picolyl = 2-pyridylmethyl, pyO = 2-pyridyloxy = pyridine-2-olate), the compounds [PhP(µ-pic)2(µ-pyO)Ru(κ2-pyO)] (3a) and [PhP(µ-pyO)3Ru(κ2-pyO)] (3b), respectively, were prepared. Reaction of compounds 3 with CO and CNtBu afforded the opening of the Ru(κ2-pyO) chelate motif with the formation of compounds [PhP(µ-pic)2(µ-pyO)Ru(κ-O-pyO)(CO)] (4a), [PhP(µ-pic)2(µ-pyO)2Ru(CNtBu)] (5a), [PhP(µ-pyO)4Ru(CO)] (4b) and [PhP(µ-pyO)4Ru(CNtBu)] (5b). In dichloromethane solution, 4a underwent a reaction with the solvent, i.e., substitution of the dangling pyO ligand by chloride with the formation of [PhP(µ-pic)2(µ-pyO)Ru(Cl)(CO)] (6a). The new complexes 3a, 4a, 5a, 5b and 6a were characterized by single-crystal X-ray diffraction analyses and multi-nuclear (1H, 13C, 31P) NMR spectroscopy. The different coordination behaviors of related pairs of molecules (i.e., pairs of 3, 4 and 5), which depend on the nature of the P-Ru-bridging ligand moieties (µ-pic vs. µ-pyO), were also studied via computational analyses using QTAIM (quantum theory of atoms in molecules) and NBO (natural bond orbital) approaches, as well as the NCI (non-covalent interactions descriptor) for weak intramolecular interactions.

Radiomics analysis at PET/CT contributes to prognosis of recurrence and survival in lung cancer treated with stereotactic body radiotherapy.

We sought to quantify contribution of radiomics and SUVmax at PET/CT to predict clinical outcome in lung cancer patients treated with stereotactic body radiotherapy (SBRT). 150 patients with 172 lung cancers, who underwent SBRT were retrospectively included. Radiomics were applied on PET/CT. Principal components (PC) for 42 CT and PET-derived features were examined to determine which ones accounted for most of variability. Survival analysis quantified ability of radiomics and SUVmax to predict outcome. PCs including homogeneity, size, maximum intensity, mean and median gray level, standard deviation, entropy, kurtosis, skewness, morphology and asymmetry were included in prediction models for regional control (RC) [PC4-HR:0.38, p = 0.02], distant control (DC) [PC4-HR:0.51, p = 0.02 and PC1-HR:1.12, p = 0.01], recurrence free probability (RFP) [PC1-HR:1.08, p = 0.04], disease specific survival (DSS) [PC2-HR:1.34, p = 0.03 and PC3-HR:0.64, p = 0.02] and overall survival (OS) [PC4-HR:0.45, p = 0.004 and PC3-HR:0.74, p = 0.02]. In combined analysis with SUVmax, PC1 lost predictive ability over SUVmax for RFP [HR:1.1, p = 0.04] and DC [HR:1.13, p = 0.002], while PC4 remained predictive of DC independent of SUVmax [HR:0.5, p = 0.02]. Radiomics remained the only predictors of OS, DSS and RC. Neither SUVmax nor radiomics predicted recurrence free survival. Radiomics on PET/CT provided complementary information for prediction of control and survival in SBRT-treated lung cancer patients.

Old wine in new bottles: validating the clinical utility of SPECT in predicting cognitive performance in mild traumatic brain injury.

The neural underpinnings of cognitive dysfunction in mild traumatic brain injury (TBI) are not fully understood. Consequently, patient prognosis using existing clinical imaging is somewhat imprecise. Single photon emission computed tomography (SPECT) is a frequently employed investigation in this population, notwithstanding uncertainty over the clinical utility of the data obtained. In this study, subjects with mild TBI underwent (99m)Tc-ECD SPECT scanning, and were administered a brief battery of cognitive tests and self-report symptom scales of concussion and emotional distress. Testing took place 2 weeks (n=84) and 1 year (n=49) post-injury. Multivariate analysis (i.e., partial least squares analysis) revealed that frontal perfusion in right superior frontal and middle frontal gyri predicted poorer performance on the Stroop test, an index of executive function, both at initial and follow-up testing. Conversely, SPECT scans categorized as normal or abnormal by radiologists did not differentiate cognitively impaired from intact subjects. These results demonstrate the clinical utility of SPECT in mild TBI, but only when data are subjected to blood flow quantification analysis.

Differentiating between visual hallucination-free dementia with Lewy bodies and corticobasal syndrome on the basis of neuropsychology and perfusion single-photon emission computed tomography.

INTRODUCTION: Dementia with Lewy bodies (DLB) and Corticobasal Syndrome (CBS) are atypical parkinsonian disorders with fronto-subcortical and posterior cognitive dysfunction as common features. While visual hallucinations are a good predictor of Lewy body pathology and are rare in CBS, they are not exhibited in all cases of DLB. Given the clinical overlap between these disorders, neuropsychological and imaging markers may aid in distinguishing these entities. METHODS: Prospectively recruited case-control cohorts of CBS (n =31) and visual hallucination-free DLB (n =30), completed neuropsychological and neuropsychiatric measures as well as brain perfusion single-photon emission computed tomography and structural magnetic resonance imaging (MRI). Perfusion data were available for forty-two controls. Behavioural, perfusion, and cortical volume and thickness measures were compared between the groups to identify features that serve to differentiate them. RESULTS: The Lewy body with no hallucinations group performed more poorly on measures of episodic memory compared to the corticobasal group, including the delayed and cued recall portions of the California Verbal Learning Test (F (1, 42) =23.1, P <0.001 and F (1, 42) =14.0, P =0.001 respectively) and the delayed visual reproduction of the Wechsler Memory Scale-Revised (F (1, 36) =9.7, P =0.004). The Lewy body group also demonstrated reduced perfusion in the left occipital pole compared to the corticobasal group (F (1,57) =7.4, P =0.009). At autopsy, the Lewy body cases all demonstrated mixed dementia with Lewy bodies, Alzheimer's disease and small vessel arteriosclerosis, while the corticobasal cases demonstrated classical corticobasal degeneration in five, dementia with agyrophilic grains + corticobasal degeneration + cerebral amyloid angiopathy in one, Progressive Supranuclear Palsy in two, and Frontotemporal Lobar Degeneration-Ubiquitin/TAR DNA-binding protein 43 proteinopathy in one. MRI measures were not significantly different between the patient groups. CONCLUSIONS: Reduced perfusion in the left occipital region and worse episodic memory performance may help to distinguish between DLB cases who have never manifested with visual hallucinations and CBS at earlier stages of the disease. Development of reliable neuropsychological and imaging markers that improve diagnostic accuracy will become increasingly important as disease modifying therapies become available.

Phase I trial of intraoperative detection of tumor margins in patients with HER2-positive carcinoma of the breast following administration of 111In-DTPA-trastuzumab Fab fragments.

INTRODUCTION: Our aim was to conduct a Phase I clinical trial to determine the feasibility of intraoperative detection of tumor margins in HER2 positive breast carcinoma using a hand-held γ-probe following administration of (111)In-DTPA-trastuzumab Fab fragments. Accurate delineation of tumor margins is important for preventing local recurrence. METHODS: Six patients with HER2-positive in situ or invasive ductal carcinoma were administered 74MBq (0.5mg) of (111)In-DTPA-trastuzumab Fab fragments and counts in the tumor, surgical cavity wall and en face margins were measured intraoperatively at 72h post-injection using the Navigator or C-Trak γ-probes. Margins were evaluated histologically. Quantitative whole body planar imaging was performed to estimate radiation absorbed doses using OLINDA/EXM software. SPECT imaging of the thorax was performed to evaluate tumor uptake. The pharmacokinetics of elimination from the blood and plasma were determined over 72h. RESULTS: There were no acute adverse reactions from (111)In-DTPA-trastuzumab Fab fragments and no changes in hematological or biochemical indices were found over a 3month period. (111)In-DTPA-trastuzumab Fab fragments exhibited a biphasic elimination from the blood and plasma with t1/2α=11.9h and 7.5h, respectively, and t1/2ß=26.6 and 20.7h, respectively. The radiopharmaceutical accumulated in the liver, spleen and kidneys. SPECT imaging did not reveal tumor in any patient. The mean effective dose was 0.146mSv/MBq (10.8mSv for 74MBq). Counts in excised tumors were low but were higher than in margins. Margins in two patients harboured tumor but this was not correlated with counts obtained using the γ-probes. Surgical cavity counts were high and likely due to detection of γ-photons outside the surgical field. CONCLUSION: We conclude that it was not feasible, at least at the administered amount of radioactivity used in this study, to reliably detect the margins of disease in patients with in situ or invasive ductal carcinoma intraoperatively using a hand-held γ-probe and (111)In-DTPA-trastuzumab Fab fragments due to low uptake in the tumor and involved margins.

Randomized, double-blinded, placebo-controlled, trial of risedronate for the prevention of bone mineral density loss in nonmetastatic prostate cancer patients receiving radiation therapy plus androgen deprivation therapy.

PURPOSE: Androgen deprivation therapy (ADT) has been used as an adjuvant treatment to radiation therapy (RT) for the management of locally advanced prostate carcinoma. Long-term ADT decreases bone mineral density (BMD) and increases the risk of osteoporosis. The objective of this clinical trial was to evaluate the efficacy of risedronate for the prevention of BMD loss in nonmetastatic prostate cancer patients undergoing RT plus 2 to 3 years of ADT. METHODS AND MATERIALS: A double-blinded, placebo-controlled, randomized trial was conducted for nonmetastatic prostate cancer patients receiving RT plus 2 to 3 years of ADT. All had T scores > -2.5 on dual energy x-ray absorptiometry at baseline. Patients were randomized 1:1 between risedronate and placebo for 2 years. The primary endpoints were the percent changes in the BMD of the lumbar spine at 1 and 2 years from baseline, measured by dual energy x-ray absorptiometry. Analyses of the changes in BMD and bone turnover biomarkers were carried out by comparing mean values of the intrapatient changes between the 2 arms, using standard t tests. RESULTS: One hundred four patients were accrued between 2004 and 2007, with 52 in each arm. Mean age was 66.8 and 67.5 years for the placebo and risedronate, respectively. At 1 and 2 years, mean (±SE) BMD of the lumbar spine decreased by 5.77% ± 4.66% and 13.55% ± 6.33%, respectively, in the placebo, compared with 0.12% ± 1.29% at 1 year (P=.2485) and 0.85% ± 1.56% (P=.0583) at 2 years in the risedronate. The placebo had a significant increase in serum bone turnover biomarkers compared with the risedronate. CONCLUSIONS: Weekly oral risedronate prevented BMD loss at 2 years and resulted in significant suppression of bone turnover biomarkers for 24 months for patients receiving RT plus 2 to 3 years of ADT.

Rapid improvement in pain and functional level in a patient with metastatic renal cell carcinoma: a case report and review of the literature.

Renal cell carcinoma (RCC) represents approximately 3% of all adult cancers and is more common in males. Systemic treatment for RCC has improved following the introduction of sunitinib. Bone metastases are present in up to 50% of RCC patients. We report a case of rapid improvement in metastatic bone lesions, recorded by nuclear bone scan, in a male patient receiving localized palliative radiotherapy in addition to systemic sunitinib and zoledronic acid. Concurrently, quality of life and performance status improved dramatically. Although we are unsure of the exact mechanism for such rapid improvement in metastatic bone lesions, the swiftness this improvement deserves reporting.

Breast metastasis by medullary thyroid carcinoma detected by FDG positron emission tomography.

Medullary thyroid carcinoma (MTC) is an uncommon thyroid cancer comprising 5% to 8% of thyroid neoplasms. In contrast to common thyroid tumors, this tumor originates from the calcitonin-producing C cells. Regional metastases to cervical lymph nodes occur early in the disease, whereas distant metastasis occurs late. Common metastatic sites include the liver, bone, brain, and adrenal medulla. We present a case of MTC metastatic to the breast. We report on this case for the following reasons: (1) metastasis to the breast is an extremely rare occurrence and could be easily confused clinically and pathologically with a primary breast neoplasm and (2) this is the first reported case of detection of breast metastasis by an MTC using FDG ((18)F-fluoro-2-deoxy-D-glucose) positron emission tomography with an accompanying histologic description.

18F-fluorodeoxyglucose positron emission tomography-computed tomography for suspected recurrent papillary thyroid cancer: early experience at Sunnybrook Health Sciences Centre.

OBJECTIVES: To report the initial experience with combined 18F-fluorodeoxyglucose positron emission tomography (FDG PET)/computed tomography (CT) imaging for suspected recurrent papillary differentiated thyroid cancer (DTC) at Sunnybrook Health Sciences Centre (SHSC), Toronto. DESIGN: Single institution retrospective study. METHODS: Consecutive patients from SHSC who underwent FDG PET/CT imaging for suspected recurrent DTC over a period of 2.5 years were identified and their charts reviewed. MAIN OUTCOME MEASURE: Qualitative appraisal of FDG PET/CT imaging in suspected recurrent DTC. RESULTS: Sixteen patients (14F, 2M) were identified accounting for 17 FDG PET/CT scans. Three scans (18%) in 3 different patients were reported as suspicious for recurrent disease in the neck (1-3 lesions) and were considered "positive". All were subsequently confirmed pathologically (4-13 positive lymph nodes post operatively). Prior conventional imaging was abnormal in two patients. Two patients had an elevated non-stimulated thyroglobulin (TG) < 10 ng/mL (4.9 and 9.4). The remaining patient had a TG < 0.3 ng/mL but was anti-TG antibody positive (84 IUx10-3/L). With a median follow up of 15 months (range 7-36) there were no false positive or negative scans. Incidental pathology (breast cancer, large bowel polyps) was identified on a further 2/17 scans (12%). CONCLUSIONS: FDG PET/CT imaging is able to detect recurrent DTC in patients with low TG levels. It can complement conventional imaging findings and exclude distant FDG-avid metastases prior to surgery. It may underestimate the number of positive lymph nodes in the neck. Occult pathology may be identified with whole body FDG PET/CT.

Sentinel lymph node in vulvar cancer.

BACKGROUND: The aim of the study was to assess the feasibility, efficacy, and accuracy of the sentinel lymph node (SLN) procedure in vulvar cancer. METHODS: From April 2004 to September 2006, all patients with vulvar cancer, clinical stages I and II, underwent SLN detection, followed by a complete inguinofemoral lymphadenectomy. Demographic, surgical, and pathologic data on all patients were prospectively entered in a database. RESULTS: Forty-two patients underwent the SLN procedure. One patient was excluded from further analysis due to metastases to the vulva. The detection rate for at least 1 SLN per patient was 95%, with bilateral SLNs detected in 46% of patients. There was a trend toward improved ability to detect bilateral SLNs and proximity of the cancer to the midline (r = 0.996; P = .057). No contralateral SLNs were identified in patients with lateral vulvar lesions (>1 cm from the midline). For 'close-to-midline' (< or =1 cm from the midline) lesions, SLNs were detected in 93% of ipsilateral groins and bilateral SLNs were found in 46% of patients, whereas lesions abutting the midline had unilateral and bilateral SLN detected in 100% and 93%, respectively. Sixteen of 41 patients (39%) and 18 of 68 groins (26%) revealed metastatic disease in the lymph nodes; all were correctly identified by the SLN procedure. There were no false-negative SLN results. CONCLUSIONS: SLN dissection is feasible and safe to perform in vulvar cancer. The ability to identify bilateral sentinel inguinal lymph nodes appears to be related to the proximity of the vulvar cancer to the midline.

The impact of (18)FDG-PET on target and critical organs in CT-based treatment planning of patients with poorly defined non-small-cell lung carcinoma: a prospective study.

PURPOSE: To prospectively study the impact of coregistering (18)F-fluoro-deoxy-2-glucose hybrid positron emission tomographic (FDG-PET) images with CT images on the planning target volume (PTV), target coverage, and critical organ dose in radiation therapy planning of non-small-cell lung carcinoma. METHODS AND MATERIALS: Thirty patients with poorly defined tumors on CT, referred for radical radiation therapy, underwent both FDG-PET and CT simulation procedures on the same day, in radiation treatment position. Image sets were coregistered using external fiducial markers. Three radiation oncologists independently defined the gross tumor volumes, using first CT data alone and then coregistered CT and FDG-PET data. Standard margins were applied to each gross tumor volume to generate a PTV, and standardized treatment plans were designed and calculated for each PTV. Dose-volume histograms were used to evaluate the relative effect of FDG information on target coverage and on normal tissue dose. RESULTS: In 7 of 30 (23%) cases, FDG-PET information changed management strategy from radical to palliative. In 5 of the remaining 23 (22%) cases, new FDG-avid nodes were found within 5 cm of the primary tumor and were included in the PTV. The PTV defined using coregistered CT and FDG-PET would have been poorly covered by the CT-based treatment plan in 17--29% of cases, depending on the physician, implying a geographic miss had only CT information been available. The effect of FDG-PET on target definition varied with the physician, leading to a reduction in PTV in 24-70% of cases and an increase in 30-76% of cases. The relative change in PTV ranged from 0.40 to 1.86. On average, FDG-PET information led to a reduction in spinal cord dose but not in total lung dose, although large differences in dose to the lung were seen for a few individuals. CONCLUSION: The coregistration of planning CT and FDG-PET images made significant alterations to patient management and to the PTV. Ultimately, changes to the PTV resulted in changes to the radiation treatment plans for the majority of cases. Where possible, we would recommend that FDG-PET data be integrated into treatment planning of non-small-cell lung carcinoma, particularly for three-dimensional conformal techniques.