Constructing a P2W18O626--Containing Hybrid Photocatalyst via Noncovalent Interactions for Enhanced H2 Production.

Polyoxometalates (POMs) have gained significant research attention because of their excellent properties in photocatalytic (PC) hydrogen production. Exploring POM-based compounds for heterogeneous photocatalysis is an ongoing task. Here, we obtain a water-insoluble inorganic-organic hybrid compound, (P2W18O62)3(C12N3H10)6(C12N3H11)6·9.5H2O (P-PW), formed by Dawson-type POM P2W18O626- (P2W18) anions and protonated 2-(pyridin-4-yl)-1H-benzo[d]imidazole (PHB) cations via noncovalent interactions. In the presence of the sacrificial agent triethanolamine, P-PW exhibits a PC H2 generation rate of 0.418 mmol/g/h, surpassing that of P2W18 and PHB by 15 and 17 times, respectively. This enhancement in PC performance of P-PW can be attributed to its band structure change from the precursor compounds, leading to increased light absorption and therefore more efficient PC hydrogen production.

Palladium-Catalyzed Synthesis of Indanone via C-H Annulation Reaction of Aldehydes with Norbornenes.

A novel methodology for the synthesis of indanone derivates has been developed. The palladium-catalyzed annulation reaction of o-bromobenzaldehydes with norbornene derivatives is achieved through extremely concise reaction processes. The indanone skeleton was established directly via C-H activation of the aldehyde group under a mild reaction condition. This method is simple and practical, which simplified the traditional synthesis method for the rapid construction of indanone.

Simultaneously tuning the luminescent color and realizing an optical temperature sensor by negative thermal expansion in Sc2(WO4)3:Tb/Eu phosphors.

At present, many researchers are focusing on trivalent lanthanide (Ln3+)-doped thermally enhanced upconversion luminescent (UCL) materials with negative thermal expansion (NTE) properties. However, selective anti-thermal quenching downshifting emissions of the activator and thermal quenching of the sensitizer in a phosphor with NTE properties are not implemented. Herein, Tb3+/Eu3+ co-doped Sc2(WO4)3 phosphors synthesized by the solid-state method are explored in selectively enhanced red emission (Eu3+:5D0 → 7F2) due to the energy-transfer efficiency from Tb3+ to Eu3+ and the promoted radiative transition probability. The selective thermally quenched green emission (Tb3+:5D4 → 7F5) is owing to the change of energy transfer from Tb3+ to Eu3+ as the temperature increased. Moreover, under ultraviolet 365 nm excitation, the thermally stimulated color emission tuned from yellow to red with the increase in temperature. Based on the radically different thermal response downshifting the luminescence of the activator and sensitizer, the luminescence intensity ratio (LIR) of non-thermally coupled levels (NTCLs) for 5D0 (Eu3+) and 5D4 (Tb3+) is adopted for optical temperature sensing. The optimal relative sensitivity of temperature sensing in the Sc2(WO4)3:25%Tb3+/3%Eu3+ sample could reach 2.94% K-1 at 347 K. All these indicate that this Sc2(WO4)3:Tb3+/Eu3+ material is a promising candidate for high-sensitivity optical temperature sensing.

Multistimuli-responsive multicolor solid-state luminescence tuned by NH-dependent switchable hydrogen bonds.

Revealing the stimuli-responsive mechanism is the key to the accurate design of stimuli-responsive luminescent materials. We report herein the multistimuli-responsive multicolor solid-state luminescence of a new dicopper(I) complex [{Cu(bpmtzH)}2(µ-dppa)2](ClO4)2 (1), and the multistimuli-responsive mechanism is clarified by investigating its four different solvated compounds 1·2CH3COCH3·2H2O, 1·2DMSO·2H2O, 1·4CH3OH, and 1·4CH2Cl2. It is shown that luminescence mechanochromism is associated with the breakage of the hydrogen bonds of bmptzH-NH with counter-ions such as ClO4- induced by grinding, while luminescence vapochromism is attributable to the breaking and forming of hydrogen bonds of dppa-NH with solvents, such as acetone, dimethylsulfoxide, and methanol, caused by heating and vapor fuming. In addition, those results might provide new insights into the design and synthesis of multistimuli-responsive multicolor luminescent materials by using various structure-sensitive functional groups, such as distinct N-H ones, to construct switchable hydrogen bonds.

Site regulation and luminescence properties of Eu3+, Eu2+ in (La, Mg):SrAl12O19 matrix.

The partially and equivalent substitution of La + Mg â†’ Sr + Al in SrAl12O19 lattice is an effective strategy to provide trivalent sites, reduce the site occupation splitting of Al and stabilize the entire lattice. When excited by 397 nm, the Eu3+ activated La, Mg:SrAl12O19 (ASL) phosphor shows intense linear emission through the 5D0→7F4 transition at 707 nm when compared with SrAl12O19:Eu3+. Especially, the Eu, Mg co-doped Sr1-xLaxMgxAl12-xO19 with certain amount of x = 1/3 exhibits the significant intense photoluminescence, which was demonstrated through a lattice evolutional model. Eu2+ in the host with 1/3 ratio of (La, Mg) substitution shows broad blue emission and as short fluorescence lifetime as 248 ns. The temperature-depended fluorescence quenching behavior confirms the essence of strong electric-phonon coupling originated from distorted and polarized crystal field around Eu2+/Sr2+ site. Basing on site regulation of SrAl12O19 matrix, our study provides a reference for exploration on efficient rare earth ions activated luminescent laser or scintillation materials.

Simultaneous Thermal Enhancement of Upconversion and Downshifting Luminescence by Negative Thermal Expansion in Nonhygroscopic ZrSc(WO4)2PO4:Yb/Er Phosphors.

Thermal quenching (TQ) is still a critical challenge for lanthanide (Ln3+)-doped luminescent materials. Herein, we report the novel negative thermal expansion nonhygroscopic phosphor ZrSc(WO4)2PO4:Yb3+/Er3+. Upon excitation with a 980 nm laser, a simultaneous thermal enhancement is realized on upconversion (UC) and downshifting (DS) emissions from room temperature to 573 K. In situ temperature-dependent X-ray diffraction and photoluminescence dynamics are used to reveal the luminescence mechanism in detail. The coexistence of the high energy transfer efficiency and the promoted radiative transition probability can be responsible for the thermally enhanced luminescence. On the basis of the luminescence intensity ratio of thermally coupled energy levels 2H11/2 and 4S3/2 at different temperatures, the relative and absolute sensitivities of the targeted samples reach 1.10% K-1 and 1.21% K-1, respectively, and the low-temperature uncertainty is approximately 0.1-0.4 K on the whole temperature with a high repeatability (98%). Our findings highlight a general approach for designing a hygro-stable, thermostable, and highly efficient Ln3+-doped phosphor with UC and DS luminescence.

Site-splitting inhibition and near-infrared luminescence properties of Cr3+ activated magnetoplumbite SrAl12O19 modified by La and Mg.

Near-infrared phosphor-converted light-emitting diodes (pc-LEDs) are attractive in application like in vivo imaging and nondestructive examination in food industry. Plenty of aluminium oxides with high melting point and rigidity have been researched towards high photoluminescence quantum yield and thermal stability. In this work, a series of Cr3+ activated La, Mg modified SrAl12O19 phosphors, i.e. Sr0.7La0.3Mg0.3Al11.7O19, are prepared via a solid-state reaction route. The site splitting and structural evolution towards relative thermodynamic stability in the modified host are discussed, Cr3+ ions with multisite occupation in the host show intense zero-phonon-line (ZPL) emission and tunable broadband emission. The optimized phosphor exhibits excellent luminescence thermal stability, with 98% residual integrity intensity of that at room temperature at 473 K. The results provide a reference for developing novel NIR-emitting magnetoplumbite phosphor with high efficiency and excellent thermal quenching resistance.

Thermally boosted upconversion and downshifting luminescence in Sc2(MoO4)3:Yb/Er with two-dimensional negative thermal expansion.

Rare earth (RE3+)-doped phosphors generally suffer from thermal quenching, in which their photoluminescence (PL) intensities decrease at high temperatures. Herein, we report a class of unique two-dimensional negative-thermal-expansion phosphor of Sc2(MoO4)3:Yb/Er. By virtue of the reduced distances between sensitizers and emitters as well as confined energy migration with increasing the temperature, a 45-fold enhancement of green upconversion (UC) luminescence and a 450-fold enhancement of near-infrared downshifting (DS) luminescence of Er3+ are achieved upon raising the temperature from 298 to 773 K. The thermally boosted UC and DS luminescence mechanism is systematically investigated through in situ temperature-dependent Raman spectroscopy, synchrotron X-ray diffraction and PL dynamics. Moreover, the luminescence lifetime of 4I13/2 of Er3+ in Sc2(MoO4)3:Yb/Er displays a strong temperature dependence, enabling luminescence thermometry with the highest relative sensitivity of 12.3%/K at 298 K and low temperature uncertainty of 0.11 K at 623 K. These findings may gain a vital insight into the design of negative-thermal-expansion RE3+-doped phosphors for versatile applications.

A multidentate polymer microreactor route for green mass fabrication of mesoporous NaYF4 clusters.

We report a "multidentate polymer microreactor" method for the creation of secondary structures of colloidal nanocrystals. Using NaYF4:Yb,Er as an example, we demonstrate that the use of sodium polyacrylate (PAAS) as a "multidentate polymer microreactor" allows the controllable growth of primary nanocrystals and induces aggregation of the nanocrystals into well-defined mesoporous clusters.

NaLaMgWO6:Mn4+/Pr3+/Bi3+ bifunctional phosphors for optical thermometer and plant growth illumination matching phytochrome PR and PFR.

Phytochromes PR and PFR distributed in different organs of plant can effectively absorb red and far-red light, respectively. Therefore, plant growth can be controlled by changing the ratio of red light to far-red light. The emission of Pr3+ (transition from 3P0→3F2,3) and Mn4+(transition from 2Eg→4A2g) is located at the red and far-red range which matches with the absorption band of PR and PFR, respectively. Herein, NaLaMgWO6:Mn4+/Pr3+/Bi3+ phosphors with improving luminescence properties via Bi3+ doping have been successfully prepared by the sol-gel method. With the variation of temperature, the photoluminescence (PL) of Pr3+/Mn4+ (corresponding to PFR/PR) of titled phosphors can be tuned, which is very useful for controlling the plant growth. Moreover, based on the fluorescence intensity ratios (FIR) of the two activator Mn4+ and Pr3+, the maximum relative sensitivity was approximately 3.39%/K at 298 K. All the results indicated that the titled phosphor is a bifunctional material for plant growth illumination with high matching phytochrome (PR and PFR) and temperature sensing with high sensitivity.

Family of Chiral ZnII-LnIII (Ln = Dy and Tb) Heterometallic Complexes Derived from the Amine-Phenol Ligand Showing Multifunctional Properties.

A family of chiral 3d-4f heterometallic complexes, namely, [Zn2Ln(R,R-L)2(H2O)4](ClO4)3) [Ln = Dy (1), Tb (3)], [Zn2Ln(S,S-L)2(H2O)4](ClO4)3 [Ln = Dy (2), Tb (4)], [Zn2Ln2(R,R-L)2(CO3)2(NO3)2]·2CH3OH [Ln = Dy (5), Tb (7)], and [Zn2Ln2(S,S-L)2(CO3)2(NO3)2]·2CH3OH [Ln = Dy (6), Tb (8)] {H2L = cyclohexane-1,2-diylbis(azanediyl)bis(methylene)bis(2-methoxyphenol)}, has been synthesized and characterized. Crystal structure analysis reveals that complexes 1-4 are isostructural trinuclear clusters crystallized in chiral space group C2221, and 5-8 are isostructural tetranuclear clusters crystallized in chiral space group P1. Interestingly, the adjacent [ZnLn] units within the tetranuclear cluster in 5-8 are bridged by two carbonate anions via in situ incorporation of CO2 from air. Magnetic measurements indicate that complexes 1 and 3 exhibit field-induced single-molecule magnet behavior with energy barriers (Ueff) of 22.46 and 38.70 K (or 41.87 K), respectively. Complex 5 displays typical SMM behavior with Ueff = 19.61 K under zero dc field, while for complex 7, no obvious out-of-phase signals are observed even under 2 kOe dc field, the absence of SMM behavior. The solid-state luminescence studies reveal that all complexes display the characteristic fluorescence emission of lanthanide ions. Furthermore, the Kurtz-Perry measurements reveal these complexes are potential nonlinear optical materials.

Electrochemical sensor based on a nanocomposite prepared from TmPO4 and graphene oxide for simultaneous voltammetric detection of ascorbic acid, dopamine and uric acid.

A nanocomposite is described that consists of TmPO4 and graphene oxide (GO) and is used to modify a glassy carbon electrode (GCE) to obtain a sensor for simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA). GO and TmPO4 were synthesized via the Hummers method and by a hydrothermal method, respectively. The nanocomposite was characterized by transmission electron microscopy, energy dispersive X-ray spectroscopy, powder X-ray diffraction and Fourier transform infrared spectroscopy. The electrochemical properties of the modified GCE were studied by electrochemical impedance spectroscopy and cyclic voltammetry. The good performance of the modified GCE results from the synergistic effects between GO with its good electrical conductivity and of TmPO4 as the electron mediator that accelerates the electron transfer rate. Compared to a bare GCE, a GO/GCE and a TmPO4/GCE, the GO/TmPO4/GCE exhibits three well-defined and separated oxidation peaks (at -0.05, +0.13 and + 0.26 V vs. SCE). Responses to AA, DA and UA are linear in the 0.1-1.0 mM, 2-20 µM and 10-100 µM concentration ranges, respectively. Graphical abstract Schematic presentation of a nanocomposite that consists TmPO4 and graphene oxide (GO) and is used to modify a glassy carbon electrode (GCE) to obtain a sensor for simultaneous determination of ascorbic acid (AA), dopamine (DA) and uric acid (UA).

3d-4f heterometallic trinuclear complexes derived from amine-phenol tripodal ligands exhibiting magnetic and luminescent properties.

A new family of 3d-4f heterometallic trinuclear complexes, namely [M2LnL2]·2ClO4·H2O (H3L = tris(((2-hydroxy-3-methoxybenzy1)amino)ethyl)amine, where M = Ni, Ln = Gd (1), Dy (2), and M = Zn, Ln = Gd (3), Dy (4)) were synthesized via the reaction of H3L and Ln(NO3)3·6H2O and Ni(ClO4)2·6H2O or Zn(ClO4)2·6H2O in a 2 : 1 : 2 ratio in the solution. Complexes 1-4 consisted of three metal ions arranged in an isosceles triangle manner. Magnetic properties investigations showed that complexes 1 and 2 exhibited weak ferromagnetic coupling between the Ni(ii) and Ln(iii) ions, whereas complex 4 displayed lanthanide single-ion magnetic properties. The alternating current (ac) magnetic susceptibilities of 4 revealed that both the in-phase (χ') and out-of-phase (χ'') signals are frequency- and temperature-dependent, which are typical features of the field-induced slow relaxation of the magnetization with Ueff = 124.5 K. Complex 4 also exhibited an obvious butterfly-shaped hysteresis loop at 2 K, indicating that it is a single-ion magnet. Moreover, complex 4 showed stronger fluorescent emissions, which were typical narrow emission bands of lanthanide ions. Therefore, complex 4 can be considered as a molecular magnetic and luminescent material. Comparably, complex 2 showed very weak DyIII-based emissions because the paramagnetic NiII ions quench the fluorescence and thereby lower the population of the triplet state.

Solitary fibrous tumor of the ilium: A case report.

RATIONALE: Solitary fibrous tumors (SFTs) are rare spindle cell tumors that are most commonly found in the mediastinal pleura. Although there are increasingly more reports of extra-pleural SFTs, reports of SFTs in bone are very rare. To our knowledge, a SFT of the ilium has not yet been reported. With low specificity on computer tomograpy and magnetic resonance imaging, SFTs are easily misdiagnosed. PATIENT CONCERNS: A 33-year-old man visited our hospital due to repeated right ilium pain for 3 months. The pain was dull and bearable, with no hip joint dyskinesia. The relevant physical examinations are negative. The patient was healthy before and had a negative family history. Radiologically, a large mass with inhomogeneous attenuation and intensity and obvious heterogeneous enhancement was misdiagnosed as a giant cell tumor of ilium. DIAGNOSES: The man was diagnosed as the solitary fibrous tumor of right ilium. INTERVENTIONS: The patient was performed an "incision biopsy of the right ilium" and "extended resection of tumor". OUTCOMES: The pathology and immunohistochemistry was confirmed as the solitary fibrous tumors. The patient was followed-up by computed tomography of pelvis in local hospital every 6 mouths, and there is no recurrence and any symptoms. LESSONS: We learned that the solitary fibrous tumor could locate in the ilium, and when we see imaging manifestations like this case, we should think it may be SFT.

Temperature- and vapor-induced reversible single-crystal-to-single-crystal transformations of three 2D/3D GdIII-organic frameworks exhibiting significant magnetocaloric effects.

By using Gd2O3, propanedioic acid (H2pda) and oxalic acid (H2ox), a new Gd-based metal-organic framework (MOF) [Gd(pda)(ox)0.5(H2O)2]n (1) has been successfully constructed and structurally characterized. Interestingly, temperature- and vapor-induced reversible single-crystal-to-single-crystal transformations occurred and two new MOFs, namely [Gd(pda)(ox)0.5(H2O)]n (1a) and [Gd(pda)(ox)0.5]n (1b), have been obtained. Complex 1 displays a two-dimensional (2D) layer structure composed of zigzag [Gd(pda)]n chains and it could also be made up of numerous Gd6 macrocycles. Thermal dehydration leads to more complicated three-dimensional (3D) 'pillar-layer' structures (1a and 1b) with the same coordination mode of pda2- anions. Magnetic studies suggest the presence of ferromagnetic couplings between the intrachain or intralayer GdIII ions and large magnetocaloric effects (MCEs) with -ΔS = 45.0 J kg-1 K-1 (1), 46.1 J kg-1 K-1 (1a) and 46.8 J kg-1 K-1 (1b) under a 7 T applied field. Therefore, the interest of 'robust magnetocaloric MOFs' is now extended to compounds showing weak ferromagnetic couplings and hence having better magnetocaloric performances for small field changes.

Tricarboxylate-based Gd(III) coordination polymers exhibiting large magnetocaloric effects.

Two Gd(III) coordination polymers with the formula [Gd(cit)(H2O)]∞ () and [Gd(nta)(H2O)2]∞ () (H4cit = citric acid, H3nta = nitrilotriacetic acid) have been successfully prepared under hydrothermal conditions. Complex exhibits a three-dimensional (3D) structure based on carboxylate-bridged layers, while complex is a double-layer structure containing eight-coordinated Gd(III). Magnetic investigations reveal that weak antiferromagnetic couplings between adjacent Gd(III) ions in both and with different Weiss values result in large cryogenic magnetocaloric effects. It is notable that the maximum entropy changes (-ΔS) of and reach 31.3 J kg(-1) K(-1) and 32.2 J kg(-1) K(-1) at 2 K for a moderate field change (ΔH = 3 T), and a remarkable -ΔS (41.5 J kg(-1) K(-1) for and 42.0 J kg(-1) K(-1) for ) could be obtained for ΔH = 7 T.

Co-precipitation synthesis and luminescence properties of K2TiF6:Mn4⁺ red phosphors for warm white light-emitting diodes.

K2TiF6:Mn(4+) red phosphors with different Mn(4+) doping concentrations were obtained using the co-precipitation method. X-Ray diffraction, scanning electron microscopy, Raman spectra, Fourier transform infrared spectroscopy, photoluminescence excitation and emission spectra and decay curves were used to characterize the properties of K2TiF6:Mn(4+) phosphors. Under excitation at 470 nm, an intense red emission peak around 631 nm corresponding to the (2)E(g)-(4)A2 transition of Mn(4+) was observed for 2.48 mol% K2TiF6:Mn(4+) phosphors and was used as the optimum doping concentration. The excellent luminescent properties of K2TiF6:Mn(4+) suggest that this material might be a promising red phosphor for generating warm white light in phosphor-converted white light-emitting diodes.

[Expression of S100A8 and A100A9 in giant cell tumor of bone and its relation with CT and MR imaging findings].

OBJECTIVE: To investigate the mRNA and protein expression levels of S100A8 and S100A9 in giant cell tumor (GCT) of bone, and its relation with radiological findings and biological behavior. METHODS: Forty three patient with GCT of bone admitted in Ruijin Hospital Shanghai Jiaotong University School of Medicine from January 2009 to June 2012 were enrolled in the study. The expression levels of S100A8 and S100A9 mRNA and protein were detected by using semiquantitative RT-PCR and Western blotting in 43 specimens of GCT and 6 specimens of normal bone marrow. The CT and MRI findings of patients were retrospectively reviewed, its relation with tissue expression of S100A8 and S100A9 was analyzed. RESULTS: Among 43 GCT cases 40 showed positive expression of S100A8 and S100A9 mRNA and protein, and the expression levels were significantly higher than those in normal bone marrow P<0.05). The expression level of S100A8 protein was significantly different in bone GCT with different composition ratio on MRI (P<0.05).The expression level of S100A9 protein was significantly different in GCT with different degree of bone destruction on CT scan (P<0.05). CONCLUSION: The expression of S100A8 and S100A9 mRNA and protein is up-regulated in GCT of bone. The expression of S100A8 and S100A9 is associated with the real composition ratio and the degree of bone destruction, respectively, indicating that S100A8 and S100A9 may be involved in the biological behavior of bone GCT.

Giant cell-rich osteosarcoma in long bones: clinical, radiological and pathological features.

PURPOSE: The purpose of this study was to review the clinical presentation, imaging, pathology and outcome of patients with giant cell-rich osteosarcoma (GCRO) of long bones. MATERIALS AND METHODS: Radiography (n=9), magnetic resonance imaging (MRI) (n=6), computed tomography (CT) (n=3) and clinical course of nine patients (five males and four females; mean age, 26 years) with pathologically confirmed GCRO were retrospectively reviewed. Specific imaging findings, including size, eccentricity, ossification, lysis, cystic change, expansile growth, periosteal reaction, cortical destruction, soft tissue extension and joint involvement were documented. RESULTS: Presenting symptoms were pain in six patients and pain and palpable mass in three. An ill-defined margin surrounding a predominantly osteolytic lesion was detected at the proximal tibia (n=7) or femur (n=2) on imaging studies. Seven cases showed limited ossification. Three cases had tumours in the metaphysis and six in the metaepiphysis. The average maximum tumour dimension was 4.7 cm×5.2 cm×7.8 cm. Microscopically, tumours were composed of atypical cells with scanty osteoid formation and multinucleated giant cells. All patients received chemotherapy, and surgery was performed in eight patients. Three patients were dead and six were alive at the last follow-up. CONCLUSIONS: GCRO is a rarer variant that has very close resemblance to giant cell tumour. Patients usually present nonspecific symptoms of pain and palpable mass. It usually shows an osteolytic lesion with locally spared new bone formation in the metaphysis and/or metaepiphysis on imaging. Histologically, the atypical tumour cells with osteoid formation and multinucleated giant cells are the key factor in the diagnosis and differential diagnosis.

Recurrence in giant cell tumour of bone: imaging features and risk factors.

PURPOSE: This study was done to investigate X-ray, computed tomography (CT) and magnetic resonance (MR) imaging features of recurrence in giant cell tumour of bone (GCTB) and to evaluate risk factors. MATERIALS AND METHODS: Medical records and imaging data were reviewed for 55 cases of recurrent GCTB. All images were reviewed retrospectively and independently by two radiologists experienced in skeletal musculature. The common radiological findings; factors related to tumour recurrence such as gender, age, location; pathological fracture, Campanacci grading and surgical procedure were analysed by nonparametric test (Mann-Whitney U test for two independent samples test and Kruskal-Wallis H test for multiple independent samples test). p values <0.05 were considered to indicate a statistically significant difference. RESULTS: The imaging features of recurrent GCTB were as follows: osteolytic destruction or bone resorption of graft bone or around the polymethylmethacrylate (PMMA), soft tissue mass formation and expansile change. Tumour parenchyma showed markedly heterogeneous enhancement, except for necrotic cystic cavities, on contrast-enhanced MR images. Wide resection had a smaller (p=0.031) risk of local recurrence than did intralesional curettage. There was no statistical significance in gender, age, location, pathological fracture and Campanacci staging (p>0.05). CONCLUSIONS: The risk of recurrence in GCTB was influenced by the type of surgery and adjuvants. Bone transformaresorption, soft tissue mass formation and aggravated expansile change are reliable signs of recurrence on imaging.