Salicylaldehyde-Cobalt(II)-Catalyzed C-H Alkoxylation of Indoles with Secondary Alcohols.

A straight and efficient protocol for the synthesis of hindered indole-ethers via C-H alkoxylation of indoles was developed by a cobalt-catalyzed cross-dehydrogenative coupling reaction with secondary alcohols. The selection of the salicylaldehyde-Co(II) catalyst enables the reaction to proceed under conditions without acid or base addition in the presence of limited alcohols. The protocol has broad substrate scope for both indole and secondary alcohols and exhibits good functional tolerance. The synthetic applications are proven by gram-scale reaction and further diversification of the product. Preliminary mechanistic investigations indicate that the activation of C-H bonds is not the rate-determining step of the reaction.

Stepwise Increase of NdIII -Based Phosphorescence by AIE-Active Sensitizer: Broadening the AIPE Family from Transition Metals to Discrete Near-Infrared Lanthanide Complexes*.

We designed two near-infrared (NIR) lanthanide complexes [(L)2 -Nd(NO3 )3 ] (L=TPE2 -BPY for 1, TPE-BPY for 2) by employing aggregation-induced emission (AIE)-active tetraphenylethylene (TPE) derivatives as sensitizers, which possessed matched energy to NdIII , prevented competitive deactivation under aggregation, even shifted the excitation window toward 600 nm by twisted intramolecular charge transfer. Furthermore, benefiting from the 4 f electron shielding effect and antenna effect, the enhanced excitation energies of the AIE-active sensitizers by structural rigidification transferred into the inert NdIII excited state through 3 LMCT, affording the first aggregation-induced phosphorescence enhancement (AIPE)-active discrete NIR-emitting lanthanide complexes. As 1 equipped with more AIE-active TPE than 2, L→Nd energy transfer efficiency in the former was higher than that in the latter under the same conditions. Consequently, the crystal of 1 exhibited one of the longest lifetimes (9.69 µs) among NdIII -based complexes containing C-H bonds.

Discrete Heteropolynuclear Yb/Er Assemblies: Switching on Molecular Upconversion Under Mild Conditions.

The salts {[Ln2 Ln*(Hhmq)3 (OAc)3 (hfac)2 ]+ [Ln*(hfac)3 (OAc)(MeOH)]- } (Hhmq=2-methanolquinolin-8-oxide, hfac=hexafluoroacetylacetonate; Ln, Ln*=Er, Gd, Yb) feature a discrete heteronuclear cation consisting of two types of lanthanide atoms. The quinolinoxy O-atom serves as a µ2 -bridge to two Ln atoms and as a µ3 -bridge to all three atoms, with metal⋅⋅⋅metal distances being around 3.7 Å. For 1 ([Yb2 Er]+ ), near-infrared downshifted luminescence is switched to competitive upconversion luminescence upon irradiation by a 980 nm laser under an extremely low excitation power (0.288 W cm-2 ) through introduction of fluoride ions. The stability of 1 after addition of fluoride was confirmed by powder X-ray diffraction and multistage mass spectrometry, associated with the 1 H NMR of 6 ([La2 Eu]+ ). More importantly, the at least 20-fold enhancement of the quantum yield in non-deuterated solvents at room temperature under low power densities (2 W cm-2 ) is the highest among the few molecular examples reported.

Thermally Induced trans-to-cis Isomerization and Its Photoinduced Reversal Monitored using Absorption and Luminescence: Cooperative Effect of Metal Coordination and Steric Substituent.

For ethene derivatives with large groups the cis-isomer is often quite unstable and unavailable. Herein, we report an exception of two stable coordination complexes, (cis-L)ZnCl2 , starting from trans-1,2-bis(1-R-benzo[d]imidazol-2-yl)ethene (R=H, L1; R=CH3 , L2) ligands under solvothermal condition (T ≥140 °C). Using the intensity of the absorption and luminescence spectra as probes we proposed its progressive cis-to-trans reversal upon irradiation with UV light, which was confirmed by powder X-ray diffraction (PXRD). Similar results observed in the series of (cis-L2)MII Cl2 [M=Fe (4), Co (5), Ni (6)] demonstrate the universal strategy. The results of PXRD, NMR spectroscopy, ESI-MS and DFT calculations support the above conclusion. NMR spectroscopy indicates that irradiation of 1 converts an optimized 71 % of the cis-isomer to trans, whereas the free trans-L1 ligand transforms to only 15 % cis-isomer under similar conditions.

Hierarchical Assembly and Aggregation-Induced Enhanced Emission of a Pair of Isostructural Zn14 Clusters.

Information of solid-state and solution structures is crucial in the characterization of molecular clusters and in advancing the understanding of their diverse properties. [Et3NH]2[Zn14(hmq)8(OH)4X10] [X = Cl and Br; H2hmq = 2-(hydroxymethyl)quinolin-8-ol] consist of a peanut-shaped Zn10O12 core, in which the Zn atoms occupy the faces and corners of an octahedron and are protected by bonded halogen atoms and bulky organic ligands. Observation of the [Zn14(hmq)8(OH)4X10]2- fragment in electrospray ionization mass spectrometry (ESI-MS) suggests that the cluster is stable in solution. ESI-MS analyses from dissolved crystals and mother liquors reveal that Zn(hmq) self-assembles to Zn5(hmq)4Cl, then dimerizes through four [OH]- bridges to Zn10(hmq)8(OH)4Cl2, and progressively captures four ZnCl2 one-by-one to [Zn14(hmq)8(OH)4Cl10]2-. Because the supramolecular interactions between the anion and cation in the solid suppress the rotation/vibration of the halogen atoms and confine the movable organic ligands on the rigid Zn-O core, both crystal phases exhibit intense photoluminescence, much stronger than that in solution. This is the first coordination cluster to exhibit "aggregation-induced enhanced emission". In addition, preliminary tests indicate that these coordination clusters are promising for organic-light-emitting-diode applications.

Assembly of a Highly Stable Luminescent Zn5 Cluster and Application to Bio-Imaging.

The assembly sequence of the coordination cluster [Zn5 (H2 L(n) )6 ](NO3 )4 ]⋅8 H2 O⋅2 CH3 OH (Zn5 , H3 L(n) =(1,2-bis(benzo[d]imidazol-2-yl)-ethenol) involves in situ dehydration of 1,2-bis(benzo[d]imidazol-2-yl)-1,2-ethanediol (H4 L) through the formation of the [Zn(H3 L)2 ](+) monomer, dimerization to [Zn2 (H3 L)2 ](+) , dehydration of the ligand to [Zn2 (H2 L(n) )2 ](+) , and the final formation of the pentanuclear cluster. The cluster has the following special characteristics: 1) high stability in both refluxing 37 % HCl and 27 % NH3 , 2) low cytotoxicity, and 3) pH-sensitive fluorescence in the visible-to-near-infrared (Vis/NIR) region in the solid state and in solution. We have applied it as a fluorescent probe both in vivo and in vitro. Its H-bonding ability is the key to its affinity and selectivity for imaging lysosomes in HeLa cells and tumors in male BALB/C mice. It provides a new type of sensitive and biocompatible fluorescent probe for detecting small tumors (13.5 mm(3) ).

A survey of urolithiasis in young children fed infant formula contaminated with melamine in two townships of Gansu, China.

OBJECTIVE: To determine the prevalence of urolithiasis in young children fed infant formula (IF) contaminated with melamine, and the association between IF consumption and urolithiasis. DESIGN: A total of 2 733 children < or = 3 years of age on September 1, 2008 in two townships of Gansu Province, China were studied. Cases of urolithiasis were diagnosed by ultrasonography. Milk product consumption was determined by their caregivers. Remaining IF samples were tested for melamine and cyanuric acid. RESULTS: Of 2 733 eligible children in the two townships, 2 186 (80%) were enrolled in our study. Overall, 16.6% (362) of 2 186 children had urolithiasis. The prevalence was 24.6% in children exclusively fed Sanlu brand IF, 9.7% in those fed other IF, and 8.5% in those fed exclusively on other milk products. For children exclusively breast-fed, no urolithiasis was found (P < 0.05). The prevalence of urolithiasis was 11.4% in children fed 400 g of Sanlu IF, rising to 37.5% in children fed over 25 600 g. Of 48 Sanlu IF samples, 91.7% contained melamine (median = 1 800 ppm; range = 45-4 700) and 66.7% contained cyanuric acid (median = 1.2 ppm; range = 0.4-6.3). Melamine was also detected in 22.2% of 36 other brand IF (median = 27.5 ppm, range = 4-50). CONCLUSIONS: Urolithiasis was associated with melamine-contaminated IF. Although one product caused most morbidity, other milk products may have also contributed to the outbreak.

Evaluating photoneutron dose equivalents for lung cancer using PMMA phantoms undergoing 15 MV IMRT.

BACKGROUND: According to statistics of the Ministry of Health and Welfare in 2017, the second leading cause of death in Taiwan was lung cancer. OBJECTIVE: Routine treatment planning does not consider photoneutron dose equivalent (PNDE) of patient induced secondary radiation resulting from primary exposure of lung cancer. However, such treatment is potentially important for improving estimates of health risks. METHODS: This study used 10, 30, 50, 70, and 90 kg of polymethylmethacrylate (PMMA) phantoms as patient to measure PNDE varying anatomical area during lung cancer of intensity modulated radiotherapy (IMRT) treatment. Paired thermoluminescent dosimeters (TLD-600 and 700) were calibrated using university reactor neutrons. TLDs were inserted into phantom which was closely corresponded of the represented tissues or organs. RESULTS: Neutron doses (ND) of organ or tissue (N⁢DT) were determined in these phantoms using paired TLDs approach. The risks of incurring fatal secondary malignancies, maximum statistical and total errors were estimated. Evaluated PNDE ranged from 0.80 ± 0.12 to 0.56 ± 0.08 mSv/Gy for these phantoms. CONCLUSION: The estimated N⁢DT decreased with increasing distance that is from the central axis. Evaluated PNDE and N⁢D𝑠𝑘𝑖𝑛 for these phantoms were discussed. This investigation also identified secondary risks associated with PNDE relating to radiation protection.

Coordination-directed self-assembly of molecular motors: towards a two-wheel drive nanocar.

Designing and constructing hierarchical and stimuli-responsive motorized nanocar systems to perform useful tasks on-demand is highly imperative towards molecular nanotechnology. In this work, a most simplified two-wheel nanocar was successfully prepared through a facile strategy of coordination-directed self-assembly. The nanocar meso-AgL2 features a central pseudo square-planar Ag(I) which was bridged by two enantiomeric motors as the wheels that ensure the car moves in the same direction when observed externally. Thanks to the electronic push-pull characteristic of L and 3ILCT triplet sensitization, this nanocar can be driven by visible light up to 500 nm. Furthermore, it could be disassembled into individual motor elements through the addition of pyridine, thus allowing dynamic regulation over the function of the nanocar. Importantly, our STM imaging results showed very organized tilted layered structures for meso-AgL2 on highly oriented pyrolytic graphite (HOPG) that are quite similar to its crystalline ones, paving the way for future single molecule manipulations. The nanocar reported here represents the first example of integrating individual motors into a hierarchical motorized nanocar system via the facile coordination-directed self-assembly method and may offer a good starting point to realize its robotic functions, e.g., metal transportation and release.

Conformation changes and luminescent properties of Au-Ln (Ln = Nd, Eu, Er, Yb) arrays with 5-ethynyl-2,2'-bipyridine.

Reaction of polymeric gold(I) acetylide species (bpyC[triple bond]CAu)n (bpyC[triple bond]CH = 5-ethynyl-2,2'-bipyridine) with diphosphine ligands Ph2P(CH2)nPPh2 (n = 2-6) or 1,1'-bis(diphenylphosphino)-ferrocene (dppf) in dichloromethane induces isolation of binuclear gold(I) complexes (bpyC[triple bond]CAu)2{mu-Ph2P(CH2)nPPh2} or (bpyC[triple bond]CAu)2(mu-dppf). Complexation of Ln(hfac)3 (hfac = hexafluoroacetylacetonate, Ln = Nd, Eu, Er, Yb) subunits to the binuclear gold(I) complexes through 2,2'-bipyridyl chelation gives the corresponding Au4Ln4 or Au2Ln2 heteropolynuclear complexes. Noticeably, upon formation of the Au4Ln4 arrays by complexation of (bpyC[triple bond]CAu)2(mu-Ph2P(CH2)4PPh2) (3) with Ln(hfac)3 units, trans-conformation in 3 transforms dramatically to the cis-arranged form due to the strong driving force from ligand-unsupported Au-Au contacts between two Au2Ln2 subunits. In contrast, cis-conformation in (bpyC[triple bond]CAu)2(mu-dppf) (6) stabilized by Au-Au interactions is reversed to the trans-oriented form upon formation of Au2Ln2 arrays by introducing Ln(hfac)3 units through 2,2-bipyridyl chelation. The binuclear gold(I) complexes show bright blue luminescence featured by ligand-centered pi --> pi* (C[triple bond]Cbpy) states together with low-energy emission at 500-540 nm, associated with 3(pi-->pi*) excited states, mixed probably with some characteristic from (Au-Au) --> (C[triple bond]Cbpy) 3MMLCT transition. For Au4Ln4 or Au2Ln2 complexes, sensitized lanthanide luminescence is achieved by energy transfer from Au-acetylide chromophores with lifetimes in the sub-millisecond range for EuIII complexes, whereas in the microsecond range for near-infrared emitting NdIII, ErIII, and YbIII species.

Controlled synthesis of up-conversion luminescent Gd/Tm-MOFs for pH-responsive drug delivery and UCL/MRI dual-modal imaging.

Using a facile one-step hydrothermal method, a series of metal-organic frameworks containing Gd/Tm (Gd/Tm-MOFs) were prepared successfully. Through the mutual activation of Gd3+ and Tm3+, Gd/Tm-MOFs showed unexpected excellent up-conversion luminescence (UCL) and a superior positive magnetic resonance image (MRI). Using doxorubicin hydrochloride (DOX) as a drug model, the feasibility of Gd/Tm-MOFs as a multifunctional drug carrier was demonstrated. Through modifying Gd/Tm-MOFs with uniform mesoporous silica (mSiO2) shells and folic acid (FA), the drug loading was improved up to 41.5 mg g-1, and pH responsive drug release increased to 64% from 12% by regulating the pH from 5.8 to 7.4. Also, the particles were tracked by MRI, and the second highest longitudinal relaxivity (r1) among the reported gadolinium complexes of 225.86 mM-1 s-1 was achieved. The cell imaging shows obvious blue and red luminescence under 980 nm laser excitation, and the up-conversion luminescence is unique because there is no autofluorescence from cells under 980 nm excitation. This indicates their promising application in the biological field. All the experiments indicate the promising application of Gd/Tm-MOFs in diagnosis and treatment.

Sensitized near infrared emission through supramolecular d → f energy transfer within an ionic Ru(ii)-Er(iii) pair.

The newly synthesized ionic triple salt Ru-Er, {[RuII(bpy)2(dbim)][ErIII(hfac)4][CF3COO]·H2O} (bpy = 2,2'-bipyridine; hfac- = hexafluoroacetylacetonate; dbim = 2,2'-dibenzimidazole) exhibits near-infrared (NIR) emission at 1535 nm by intermolecular Ru → Er (d → f) energy transfer across supramolecular interactions when pumped within the Ru(ii) 3MLCT band. It is the first such observation for a transition metal-lanthanide ionic pair.

Regulating structural dimensionality and emission colors by organic conjugation between SmIII at a fixed distance.

The conjugation of bridging bis(diphenylphosphine oxide) alkane or arene ligands was found to control the structural dimensionality and the emission color of complexes from reactions with SmIII(hfac)3(H2O)2 (hfac- = hexafluoroacetylacetonato) while retaining the SmSm distances. Bis(diphenylphosphine oxide)-1,4-butane (L1) affords a one-dimensional (1D) ribbon {Sm(hfac)3(L1)}∞ (1) that emits red color, while bis(diphenyl-phosphinoyl)-1,4-benzene (L2) results in a two-dimensional (2D) network {Sm(hfac)2(CF3COO)(L2)3}∞ (2) and near-white emission, but bis(diphenyl-phosphinoyl)-9,10-anthracene (L3) forms a zero-dimensional (0D) cyclic structure {Sm(hfac)3(L3)}2 (3) with strong ππ interactions that emit green color. Noticeably, the conjugation change is accompanied by a configurational change of coordination from trans for 1 and 2 to cis for 3. The color change is associated with the superposition of ligand and Sm based electronic band energies and their intensities. Such white light emission by a single compound having contributions from different building components is quite rare.

Heterododecanuclear Pt(6)Ln(6) (Ln = Nd, Yb) arrays of 4-ethynyl-2,2'-bipyridine with sensitized near-IR lanthanide luminescence by Pt --> Ln energy transfer.

Heterododecanuclear Pt(6)Ln(6) (Ln = Nd, Yb) complexes of 4-ethynyl-2,2'-bipyridine (HC[triple bond, length as m-dash]Cbpy), prepared using emissive Pt(Me(3)SiC[triple bond, length as m-dash]Cbpy)(C[triple bond, length as m-dash]Cbpy)(2) as an alkynyl bridging "ligand", afford sensitized near-infrared (NIR) lanthanide luminescence by Pt --> Ln energy transfer from both Pt(bpy)(acetylide)(2) and Pt(2)(dppm)(2)(acetylide)(2) chromophores.

Diplatinum alkynyl chromophores as sensitisers for lanthanide luminescence in Pt2Ln2 and Pt2Ln4 (Ln = Eu, Nd, Yb) arrays with acetylide-functionalized bipyridine/phenanthroline.

Incorporation of diplatinum complex Pt2(micro-dppm)2(bpyC[triple bond]C)4 or Pt2(mu-dppm)2(phenC[triple bond]C)4 with Ln(hfac)3(H2O)2 (Ln = Nd, Eu, Yb) gave a series of Pt2Ln2 and Pt2Ln4 bimetallic arrays, in which the excitation of d(Pt) -->pi*(R-C[triple bond]C) MLCT absorption induces sensitisation of lanthanide luminescence through efficient d --> f energy transfer from Pt(II) alkynyl chromophores.

[Grafting reaction of tetrabutyltin on the MCM-41 surface and characterization of the grafted product].

MCM-41 modified with tetrabutyltin and Sn-O-MCM-41 obtained from calcination of the modified MCM-41 in pure oxygen were characterized by XRD, FTIR, UV-Vis DRS, and TG analysis. It was found that the hydrothermal stability, surface acidity, and coordinative states of tin atoms on both samples were evidently different. After calcination, the surface tin atoms of sample remained in the tetrahedronal structure, and the hydrothermal stability and surface acidity were improved. According to the results, the reason for the enhancement of catalytic activity of Sn-O-MCM-41 was discussed.

Switchable sensitizers stepwise lighting up lanthanide emissions.

Analagous to a long-ranged rocket equipped with multi-stage engines, a luminescent compound with consistent emission signals across a large range of concentrations from two stages of sensitizers can be designed. In this approach, ACQ, aggregation-caused quenching effect of sensitizers, would stimulate lanthanide emission below 10(-4) M, and then at concentrations higher than 10(-3) M, the "aggregation-induced emission" (AIE) effect of luminophores would be activated with the next set of sensitizers for lanthanide emission. Simultaneously, the concentration of the molecules could be monitored digitally by the maximal excitation wavelengths, due to the good linear relationship between the maximal excitation wavelengths and the concentrations {lg(M)}. This model, wherein molecules are assembled with two stages (both AIE and ACQ effect) of sensitizers, may provide a practicable strategy for design and construction of smart lanthanide bioprobes, which are suitable in complicated bioassay systems in which concentration is variable.

Walkable dual emissions.

Walkable dual emissions, in which the emission bands of the walker reversibly cross or leave those of the stationary ones depending on temperature and concentration, have been demonstrated in cyclic dimeric lanthanide complexes [Ln(hfac)3(PAnPO2)]2 (Ln = Eu(III), Tb(III); hfac(-) = hexafluoroacetylacetonate; PAnPO2 = 9,10-bis(diphenylphosphino) anthracene dioxide), providing a concept model for signals exchanging and dispatching. Additionally, good linear relationships are observed between the maximum emission bands of the walker vs the concentrations {lg(M)} and the measurement temperatures (K), implying such materials could be served as potential concentration and temperature sensors.

Sensitized luminescence in dinuclear lanthanide(III) complexes of bridging 8-hydroxyquinoline derivatives with different electronic properties.

Three new dinuclear lanthanide(III) complexes {Eu(hfac)(3)(H(2)O)}(2)(µ-HPhMq)(2) (2) and {Ln(hfac)(3)(H(2)O)}(2)(µ-HMe(2)NC(6)H(4)Mq)(2) (Ln = Eu, 3; Nd, 4) with 8-hydroxylquinoline derivatives in µ-phenol mode were synthesized and characterized, where hfac(-) = hexafluoroacetylacetonate, HPhMq = 2-methyl-5-phenylquinolin-8-ol, and HMe(2)C(6)H(4)Mq = 5-(4-(dimethylamino)phenyl)-2-methylquinolin-8-ol. Compared with that (400 nm) for {Eu(hfac)(3)}(2)(µ-HMq)(2) (1, HMq = 2-methy-8-hydroxylquinoline), the excitation wavelength for sensitized lanthanide luminescence is extended to ca. 420 nm for 2, and 500 nm for 4 by introducing a phenyl or 4-(dimethylamino)phenyl to 8-hydroxylquinoline. These dinuclear lanthanide(III) complexes exhibit distinctly fluoride-induced lanthanide(III) emission enhancement in both intensity and lifetime due to replacing coordination water molecules or formation of strong O-H···F hydrogen bonds with coordinated H(2)O and µ-phenol, thus suppressing significantly the non-radiative O-H oscillators.

Syntheses, structures and photophysical properties of heterotrinuclear Zn2Ln clusters (Ln = Nd, Eu, Tb, Er, Yb).

Heterotrinuclear Zn(2)Ln (Ln = Nd 2, Eu 3, Tb 4, Er 5, Yb 6) clusters [(Znq(2))(2)](mu-CH(3)COO){Ln(hfac)(2)} (q = 8-hydroxylquinolinate, hfac = hexafluoroacetylacetonate) have been synthesized. The Zn(2)Ln framework is ligated by two q ligands featuring mu-phenoxo and two q ligands featuring mu(3)-phenoxo coordination modes, and one mu-CH(3)COO(-) anions. Since the short intramolecular separations of Zn...Ln (ca. 3.354-3.373 A) allow energy transfer from Znq(2)-based sensitizers to the Ln(III) centres through two energy transfer pathways, the lanthanide luminescence is indeed "lighted up" by excitation of the Znq(2)-based chromopores. Photophysical measurements revealed that these Zn(2)Ln complexes exhibit the so-called "dual emission" originating from both Znq(2)-based luminophores and lanthanide emitters. By virtue of the dual luminescence with complementary colours, the Znq(2)-based cyan emission and Eu(III)-centred red luminescence are combined to generate a white-light emission in the Zn(2)Eu (3) complex.