Rare-earth acetates as alternative precursors for rare-earth cluster-based metal-organic frameworks.

RE-UiO-66 analogues are synthesized using RE acetates as precursors for the first time. These MOFs are fully characterized and the influence of the precursor on the materials obtained is studied. Additionally, the influence of water on the yield of the syntheses and the quality of the materials is explored.

Remodelling a shp: Transmetalation in a Rare-Earth Cluster-Based Metal-Organic Framework.

Postsynthetic modification of metal-organic frameworks (MOFs) is an important strategy for accessing MOF analogues that cannot be easily synthesized de novo. In this work, the rare-earth (RE) cluster-based MOF Y-CU-10 with shp topology was modified through transmetalation using a series of RE ions, including La(III), Nd(III), Eu(III), Tb(III), Er(III), Tm(III), and Yb(III). In all cases, metal exchange higher than 70% was observed, with reproducible results. All transmetalated materials were fully characterized and compared to the parent MOF Y-CU-10 with regard to crystallinity, surface area, and morphology. Additionally, single-crystal X-ray diffraction measurements were performed to provide further evidence of transmetalation occurring in the nonanuclear cluster nodes of the MOF.

Synthetic approaches for accessing rare-earth analogues of UiO-66.

Rare-earth (RE) analogues of UiO-66 with non-functionalised 1,4-benzenedicarboxylate linkers are synthesised for the first time, and a series of synthetic approaches is provided to troubleshoot the synthesis. RE-UiO-66 analogues are fully characterised, and demonstrate a high degree of crystallinity, high surface area and thermal stability, consistent with the UiO-66 archetype.

Molecular Copper(I)-Copper(II) Photosensitizer-Catalyst Photoelectrode for Water Oxidation.

Copper(II)-based electrocatalysts for water oxidation in aqueous solution have been studied previously, but photodriving these systems still remains a challenge. In this work, a bis(diimine)copper(I)-based donor-chromophore-acceptor system is synthesized and applied as the light-harvesting component of a photoanode. This molecular assembly was integrated onto a zinc oxide nanowire surface, and upon photoexcitation, chronoamperometric studies reveal that the integrated triad can inject electrons directly into the conduction band of zinc oxide, generating oxidizing equivalents that are then transferred to a copper(II) water oxidation catalyst in aqueous solution, yielding O2 from water with a Faradaic efficiency of 76%.

Rare-earth metal-organic frameworks: from structure to applications.

In the past 30 years, metal-organic frameworks (MOFs) have garnered widespread attention owing to their diverse chemical structures, and tunable properties. As a result, MOFs are of interest for a wide variety of potential applications spanning multiple scientific and engineering disciplines. MOFs have been synthesized using several elements from the periodic table, including those with metal nodes containing s-, p-, d-, and f-block elements. MOFs synthesized with rare-earth (RE) elements, which include scandium, yttrium and the series of fifteen lanthanides are an intriguing family of MOFs from the standpoint of both structure and function. While RE-MOFs can possess many of the same properties common to all MOF families (i.e., permanent porosity, tunable pore size/shape, accessible Lewis acidic sites), they can also display unique structures and properties owing to the high coordination numbers and distinct optical properties of RE-elements. In this review, we present the progress, and highlight several discoveries from research conducted on the topic of RE-MOFs. First, diverse structures of RE-MOFs are presented, divided into classes based on the composition of the RE-metal node being RE(iii)-ions, RE(iii)-chains, or RE(iii)-clusters. Then, several potential applications of RE-MOFs are presented, highlighting examples in the areas of chemical sensing, white light emission, biological imaging, drug delivery, near infrared emission, catalysis, gas adsorption, and chemical separations.

The impact of pelvic balance, physical activity, and fear-avoidance on the outcome after decompression and instrumented fusion for degenerative lumbar stenosis.

PURPOSE: To evaluate the impact of pelvic balance, physical activity, and fear-avoidance in a cohort of patients undergoing decompression and instrumented fusion for degenerative lumbar stenosis. MATERIALS AND METHODS: This study includes consecutive patients undergoing decompression and instrumented fusion for degenerative lumbar stenosis by one main surgeon from January 2014 to January 2015. Patients were interviewed by a psychologist and underwent standing whole spine X-ray. Lumbar and pelvic parameters (PI, SS, PT, iPT, LL) were measured by an independent spinal surgeon. Physical activity was measured with the International Physical Activity Questionnaire (IPAQ). The "fear-avoidance" was measured with the Tampa Scale for Kinesiophobia (TSK). Back pain was assessed by the Graphic Rating Scale (GRS). The disability was assessed by the Roland-Morris Low Back Pain and Disability Questionnaire. Statistical interpretation of the data was performed using SPSS v19 software (SPSS Inc, Chicago, Illinois). RESULTS: The sample included 51 patients underwent standard posterior laminectomy and instrumented fusion. Surgery has a positive global impact on the perceived low back pain. No significant (Spearman) correlations emerged among pelvic parameters and the pre- and post-surgical GSR. Patients were divided into three groups according to the IPAQ scores after the operation: "inactive" (I), "minimally inactive" (m-I), and "HEPA". Significant differences emerged between IPAQ and Roland-Morris scores (F(2, 48) = 5.48, p = 0.007): the "inactive" (M(R-M) = 11.3) or "minimally active" (M(R-M) = 9.8) groups scored significantly higher than the "HEPA" group (M(R-M) = 4.7). Tampa scores correlated with gender (rho = -0.408, p = 0.003) and with BMI (rho = -0.369, p = 0.008). Females and obese patients reported higher levels of Tampa scores. Significant relationship was found between Tampa scores and pre-GSR (rho(pre) = 0.250, p = 0.08) and significant with post-surgical GSR (rho(post) = 0.275, p = 0.05) and with post-Roland-Morris score (rho(post) = 0.599, p < 0.01). CONCLUSION: The fear-avoidance and the physical inactivity are related to the highest levels of low back pain, more than pelvic imbalance. "Inactive" and "fear-avoidant" patients have also the worst outcome after surgery and the worst level of disability.

Pott's disease: medical and surgical treatment.

OBJECTIVES: To evaluate the best treatment of Pott's disease. MATERIALS AND METHODS: 7 cases of Pott's disease were treated in the department of Neurosurgery of Sapienza University of Rome (Italy) between 2004 to 2011. RESULTS: All patients underwent surgical drainage of abscess and vertebral stabilization. In all cases culture exam showed positivity after 40 days of incubation. After surgery for a period of one year chemotherapy was administered. In all cases MRI scan with gd of the spinal column were performed 12 months after surgery and no recurrence of disease has been shown. DISCUSSION: Pott's disease is defined as vertebral involvement of extrapulmonary Tubercolosis (TB), involving mainly toraco-lumbar tract of the spine. MRI with gd represents the gold standard for the diagnosis. Treatment can be medical, surgical or usually both. The slippery course of the disease often causes a delay in getting to a diagnosis that is not made prior to rising signs, such as large abscess, neurological impairment or vertebral fractures. In these cases medical treatment alone did not show effective results, because no specific antibiotic drug can permeate the abscess's capsule, and an effective concentration is not achieved in the infection's site. Therefore, surgical treatment is necessary to abscess draining and setting the correct medical treatment to mycobacterial eradication.