Sensitised lanthanide luminescence using a RuII polypyridyl functionalised dipicolinic acid chelate.

A visible light absorbing [RuII(tpy)2]2+-type chromophore appended with a dipicolinic acid LnIII chelator has been prepared and complexed with several differing lanthanide cations to form the corresponding heterobimetallic d-f assemblies. The subseqent solution speciation analysed by 1H NMR spectroscopy revealed an unexpected decrease in the LnIII chelate complex stability, in particular for the 1 : 3 complex, when compared to the parent dipicolinic acid. As a result, the desired Ln(ML)3 complexes could not be isolated, and the 1 : 1 LnIII-ML complexes were instead characterised and investigated using steady state absorption and emission spectroscopy. Sensitised NIR emission from the YbIII, NdIII and ErIII complexes was observed upon 1MLCT excitation of the RuII based metalloligand in the visible region at ca. 485 nm. Investigations using transient absorption spectroscopy revealed essentially quantitative intersystem crossing to form the 3MLCT excited state, as expected, which then acts as the energy donor for the metalloligand based antennae effect, facilitating sensitisation efficiencies of 4.8, 17.0 and 37.4% respectively for the YbIII, ErIII and NdIII cations.

Enhanced Near-Infrared Emission from Eight-Coordinate vs Nine-Coordinate YbIII Complexes Using 2-(5-Methylpyridin-2-yl)-8-hydroxyquinoline.

Enhanced near-infrared (NIR) luminescence from two structurally related heterobinuclear NaIYbIII eight-cooridnate and heterobinuclear YbIIINaI eight-coordinate (CN = 8) complexes is reported and compared to a nine-coordinate (CN = 9) homoleptic complex. For the heteroleptic complex, [Yb(MPQ2)(acac)], the YbIII cation is coordinated to two tridentate 2-(5-methylpyridin-2-yl)-8-quinolinate (MPQ) anions, with a bidentate acetylacetonate (acac) anion completing the coordination sphere. Instead, the heterobinuclear [NaYb(MPQ)4] complex comprises a total of four anionic MPQ ligands, two of which exhibit κ3-coordination to the YbIII cation. The remaining two MPQ anions are unidentate toward the lanthanide and form µ2-bridges via the deprotonated quinolinate oxygens to a bound NaI cation which is also coordinated to the remaining nitrogen donor atoms. The structural properties of these complexes were evaluated by single-crystal X-ray diffraction (SXRD), continuous shape measure (CShM) analysis, and 1H NMR spectroscopy using a diamagnetic LuIII analogue. The corresponding photophysical properties were examined in CH2Cl2 solution by using absorption and emission spectroscopy. For both the complexes, characteristic YbIII emission is observed at ca. 980 nm, with recorded photoluminescence quantum yields (Φobs) and NIR luminescence lifetimes (τobs) of 2.0% and 14.0 µs vs 1.5% and 11.6 µs for the [NaYb(MPQ)4] and [Yb(MPQ)2(acac)] complexes, respectively. Interestingly, the eight-coordinate YbIII complexes both have higher photoluminescence quantum yields when compared to the homoleptic [Yb(MPQ)3] complex, which has a reported quantum yield of 1.0% and a NIR lifetime determined herein of 13.3 µs under identical conditions. These results have been rationalized by considering the overall efficiency of the ligand-centered sensitization process (ηsens = Φisc × Φeet), together with subsequent radiative (kr) and nonradiative (knr) deactivation of the YbIII cation. Moreover, the efficiency of the intersystem crossing (Φisc) and electronic energy transfer (Φeet) processes involved in the antennae effect have been quantified for the new complexes using a combination of nanosecond and femtosecond transient absorption techniques and have been compared to our previous results using [Ln(MPQ)3] complexes with Ln = Yb and Lu.

Quantitative Sensitization Efficiencies in NIR-Emissive Homoleptic Ln(III) Complexes Using 2-(5-Methylpyridin-2-yl)-8-hydroxyquinoline.

A series of isostructural lanthanide complexes [Ln(MPQ)3] (Ln = Nd, Gd, Er, Yb, Lu) using a monoanionic tridentate methylpyridyl-substituted 8-hydroxyquinoline ligand (MPHQ = 2-(5-methylpyridin-2-yl)-8-hydroxyquinoline) have been prepared and characterized using elemental analysis (CHN), single-crystal X-ray diffraction (XRD), and 1H NMR spectroscopy. This ligand forms homoleptic charge-neutral lanthanide complexes with three coordinated ligands arranged in an "up-up-down" fashion around the metal center. The photophysical properties of the Nd, Er, and Yb complexes were investigated using absorption and emission spectroscopy, with the latter species displaying efficient sensitization in the Near Infra-Red (NIR) region and a photoluminescence quantum yield (PLQY) as high as 1.0% in CH2Cl2 solution. The intersystem crossing and energy-transfer processes involved in the antenna effect were further investigated using transient absorption techniques, which revealed essentially quantitative sensitization efficiencies for the NIR-emitting cations.

Relationship between bone turnover and density with teriparatide, denosumab or both in women in the DATA study.

BACKGROUND: While changes in biochemical markers of bone turnover (BTM) have been reported to predict changes in bone mineral density (BMD), the relationship between changes in BMD and BTMs with combined antiresorptive/anabolic therapy is unknown. METHODS: In the DATA study, 94 postmenopausal osteoporotic women (ages 51-91) received either teriparatide 20-mcg SC daily, denosumab 60-mg SC every 6months, or both for 2years. Pearson's correlation coefficients (R) were calculated to determine the relationship between baseline and early changes in BTMs (as well as serum sclerostin) and 2-year changes in BMD. RESULTS: In women receiving teriparatide, baseline BTMs did not correlate with 2-year BMD changes though 12-month increases in osteocalcin and P1NP were associated with 2-year increases in spine BMD. In women receiving denosumab, spine and hip BMD gains correlated with both baseline and changes in P1NP and C-telopeptide. In women receiving combined teriparatide/denosumab, while both baseline and decreases in P1NP were associated with spine BMD gains, distal radius increases were associated with less CTX suppression. Neither baseline nor changes in serum sclerostin correlated with BMD in any treatment group. SUMMARY AND CONCLUSIONS: In women treated with teriparatide or denosumab, early BTM changes (increases and decreases, respectively) predict 2-year BMD gains, especially at the spine. In women treated with combined teriparatide/denosumab therapy, BMD increases at the distal radius were associated with less suppression of bone turnover. These results suggest that efficacy of combination therapy at cortical sites such as the radius may depend on residual bone remodeling despite RANKL inhibition.

Structure and efficient luminescence upconversion of Ln(iii) aromatic N-oxide coordination polymers.

A series of lanthanide-based coordination polymers {[Yb1-xErx(4,4'-bpdo)3(H2O)2](CF3SO3)3}∞ were synthesised by solvent diffusion techniques, where 4,4'-bpdo = 4,4'-bipyridine-N,N'-dioxide, and using differing mole fractions of Yb(iii) and Er(iii) which were systematically varied (x = 0, 0.05, 0.20, 0.50 and 1). All of the materials obtained were characterised using elemental analyses, single-crystal X-ray diffraction (SXRD) and solid-state photoluminescence studies. Structurally, the coordination polymers crystallise as an isomorphous series of infinite 2D sheets, which contain two inner sphere water molecules, and are isostructural with a previously characterised homometallic Yb(iii) compound. In addition to the normal Near Infra-Red (NIR) luminescence, these compounds also demonstrate upconversion emission upon 980 nm excitation. Upconversion luminescence measurements reveal visible emission in the red, green, and blue regions corresponding to the (2)H11/2→(4)I15/2, (4)F9/2→(4)I15/2 and (2)H9/2→(4)I15/2 transitions of the Er(iii) cation upon two and three-photon excitation. We also observed weak emission from the Er(iii) cation in the UV region for the first time in a Ln-MOF based material.

Effects of Two Years of Teriparatide, Denosumab, or Both on Bone Microarchitecture and Strength (DATA-HRpQCT study).

CONTEXT: In postmenopausal osteoporosis, combining denosumab and teriparatide increases hip and spine bone mineral density more than either monotherapy. OBJECTIVE: The objective of the study was to determine the effects of 2 years of combination therapy on bone microarchitecture and estimated strength. DESIGN: This was an open-label, randomized controlled trial. PARTICIPANTS AND METHODS: We performed high-resolution peripheral quantitative computed tomography at the distal tibia and radius in 94 postmenopausal osteoporotic women randomized to 2 years of teriparatide 20 µg sc daily, denosumab 60 mg sc every 6 months, or both. RESULTS: Total volumetric bone mineral density (vBMD) at the radius and tibia, trabecular vBMD at the radius, and cortical vBMD at the tibia all increased more in the combination group than both monotherapy groups (P < .002 for all comparisons with combination). Cortical thickness at the tibia also increased more in the combination group (8.1% ± 4.3%) than both other groups (P < .001). Cortical porosity at both the radius and tibia increased progressively over the 24-month treatment period in the teriparatide group but was stable in both other groups (P < .001 teriparatide vs both other groups). Trabecular vBMD at the tibia increased similarly in all groups, whereas radius trabecular vBMD increased more in the combination group than the other groups (P < .01 for both comparisons). Finite element analysis-estimated strength improved or was maintained by all treatments at both the radius and tibia. CONCLUSIONS: Two years of combined teriparatide and denosumab improves bone microarchitecture and estimated strength more than the individual treatments, particularly in cortical bone. These findings suggest that this regimen may be beneficial in postmenopausal osteoporosis.

Δ122p53, a mouse model of Δ133p53α, enhances the tumor-suppressor activities of an attenuated p53 mutant.

Growing evidence suggests the Δ133p53α isoform may function as an oncogene. It is overexpressed in many tumors, stimulates pathways involved in tumor progression, and inhibits some activities of wild-type p53, including transactivation and apoptosis. We hypothesized that Δ133p53α would have an even more profound effect on p53 variants with weaker tumor-suppressor capability. We tested this using a mouse model heterozygous for a Δ133p53α-like isoform (Δ122p53) and a p53 mutant with weak tumor-suppressor function (mΔpro). The Δ122p53/mΔpro mice showed a unique survival curve with a wide range of survival times (92-495 days) which was much greater than mΔpro/- mice (range 120-250 days) and mice heterozygous for the Δ122p53 and p53 null alleles (Δ122p53/-, range 78-150 days), suggesting Δ122p53 increased the tumor-suppressor activity of mΔpro. Moreover, some of the mice that survived longest only developed benign tumors. In vitro analyses to investigate why some Δ122p53/mΔpro mice were protected from aggressive tumors revealed that Δ122p53 stabilized mΔpro and prolonged the response to DNA damage. Similar effects of Δ122p53 and Δ133p53α were observed on wild-type of full-length p53, but these did not result in improved biological responses. The data suggest that Δ122p53 (and Δ133p53α) could offer some protection against tumors by enhancing the p53 response to stress.

Oral Kaposi's sarcoma in a non-AIDS patient.

Kaposi's sarcoma involving the oral cavity is seen frequently in AIDS patients but rarely in transplant patients. When the oral cavity is involved in transplant patients, it usually is located on the palate or the oropharynx. This article reports a renal transplant patient who developed Kaposi's sarcoma which mimicked a gingival hyperplasia in the oral cavity.

Radon and health.

Radon and its daughter decay products are thought to be the cause of 5% of lung cancer in the UK. This assessment has been made by the National Radiological Protection Board (NRPB) after a national survey of radon levels in homes, when more houses than anticipated were found to have high levels, and after a reappraisal upwards of the effectiveness of radon and its daughter products in causing lung cancer. A review of the scientific evidence reveals no direct evidence to incriminate radon or its decay products at the levels found in our homes in lung cell carcinogenesis. The issue involves different scientific disciplines and is highly complex. Debate between scientists is required and more epidemiological studies of lung cancer and low radon exposure are necessary. Meanwhile the indirect evidence linking low levels of radon exposure to lung cancer is insufficient to warrant the remedial action proposed by the NRPB and accepted by the UK government.

Blitz rape and confidence rape: implications for clinical intervention.

Corroborating a typology of rape proposed 10 years earlier, a recent demographic study of 1,000 incidents of rape concluded that the two predominant types of assault were blitz and confidence rape. Blitz rape is characterized by sudden surprise attack by an unknown assailant using force or the threat of violence to gain control over the victim. In confidence rape, the assailant is known to some degree, however slight, and gains control over his victim by winning her trust. The characteristic details that differentiate one type of rape from the other suggest that the psychological impact on the victim will differ according to the type of rape. Specific clinical approaches for the mental health care of each victim group need to be provided. The immediate concerns of blitz rape victims center around their sense of safety, their fear that the rapist may return, and their dismay at having failed to ward off their attacker. They may respond like typical trauma victims with nightmares, flashbacks, sleep and appetite disturbances, heightened startle responses, anxiety, and depression. Treatment--usually sought soon after the rape--may include psychotherapy, medication, and behavioral desensitization. The confidence rape victims' chief concerns are guilt and self-blame. The rape may be revealed only years later. There is often significant delay between the rape and the victims' request for help. The victims need to be assured that they are deserving of help and need the meaning and definition of rape clarified. Providing services may require active and sustained involvement on the part of clinicians. Confidence rape victims will have strong doubts about their ability to discern who is truly trustworthy.(ABSTRACT TRUNCATED AT 250 WORDS)

Blitz rape and confidence rape: a typology applied to 1,000 consecutive cases.

The case records of 1,000 consecutive rape victims seen at a crisis center were analyzed to identify important categories of rape victimization. The most noteworthy finding was a replication and extension of the blitz rape and confidence rape typology. The distinction between these two types of rape corresponded to a series of significant differences in the victims' characteristics, the rape settings, the victims' activities before they were raped, the assailants' characteristics, and the victims' immediate responses to the assaults. The authors discuss the implications of these differences with respect to specific strategies of outreach and treatment for victims of different types of rape.

Use of a sex rap group in an adolescent medical clinic.

This paper reports on a five-year experience with an open-ended weekly group in an Adolescent Medical Clinical. An interdisciplinary staff leading this group includes a counselor trained in sex education, a nurse, a pediatrician and a psychiatrist. The object of the group is to offer an opportunity to adolescent boys and girls to focus on diverse problems of concern to them in an atmosphere of support and sharing. The initial focus is on sexual issues and leads to family planning, but more importantly, there is a general focus on the constructive organization of their life and on investigation of the growth of personal relationships. This teen group gives staff a medium for understanding clinical problems which concern adolescents, while the adolescents are supported in gaining understanding of themselves. In this process there is a development of trust in the clinic as a whole, with better utilization of the entire Adolescent Program.

Quantitative optical and electron-probe studies of the opaque phases.

Ilmenite, chrome-titanium spinel, ulvöspinel, troilite, native iron, iron-nickel alloy, and native copper are present. In addition mackinawite is provisionally identified. Three additional opaque phases are present but not identified. Modal analysis indicates that the breccia is enriched in iron relative to ilmenite and troilite, and the high nickel content of this iron suggests that it is largely of meteoritic origin. The bulk composition of liquids corresponding to iron/troilite droplets in the rocks indicates an oxygen fugacity no greater than 10(-15.5) and a sulfur fugacity of 10(-6) bar. Complete melting of rocks produced a glass containing complex iron/troilite globules and skeletal ilmenites.