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[Co2(HL1)2(H2O)2](NO3) (1), [Cu2(H2L1)(HL1) (CH3COO)]·H2O (2), [Cu4(HL1)4(C2H5OH)]·C2H5OH·H2O (3), and [Mn3(HL2)2(CH3OH)2(CH3COO)4]·2(CH3OH)·H2O (4) {H3L1 = 2-ethyl-2-(2-hydroxybenzylideneamino)propane-1,3-diol, H3L2 = 2-ethyl-2-[(2-hydroxynaphthalene-1-yl)methyleneamino]propane-1,3-diol} have been synthesized and characterized by IR spectra, elemental analyses, single-crystal X-ray diffraction, TGA, XRD, and magnetic measurements. Compound 1 possesses mixed-valence dinuclear {Co2(μ2-O)2} with Co(II) and Co(III) ions linked through μ2-hydroxyl of Schiff base ligands. Compound 2 displays a binuclear structure with {Cu2(μ2-O)(η2-COO)} containing one μ2-hydroxyl and a single syn–syn acetate bridge. Compound 3 is tetranuclear with a cube-shaped {Cu4(μ3-O)4} core constructed by four Cu(II) centers and four μ3-hydroxyls of Schiff base ligands. Compound 4 displays a linear trinuclear {Mn3(μ2-O)2(η2-COO)2} structure in which the terminal Mn(III) and the central Mn(II) ions are linked by a μ2-hydroxyl of Schiff ba...

Eight mixed-ligand coordination compounds, [Zn(PA)(bpp)]n (1), {[Cd(PA)2(Hbpp)2(H2O)2]·2H2O}n (2), [Zn(PA)(bbi)]n (3), [Cd(PA)(bbi)(H2O)]n (4), {[Cd3(PA)2(bbi)3(Cl)2]}n (5), {[Zn6(PA)5(datrz)2(Hdatrz)2(H2O)2]·16DMF}n (6), [Cd2(PA)(datrz)2(DMF)2]n (7), and {[Cd2(PA)2(bix)2(DMF)2]·4DMF}n (8) (bpp = 1,3-bi(4-pyridyl)propane, bbi = 1,4-bis(imidazol-1-yl)butane, H2datrz = 3,5-diamino-1,2,4-triazole, bix = 1,4-bis(imidazol-1-ylmethyl)benzene), have been synthesized through the reaction of zinc and cadmium salts with pamoic acid (H2PA) and different N-donor ligands. The assembly of the ligands in different coordination modes and conformations leads to fascinating structures. 1 and 3 afford an interpenetrating polythreaded 2D → 3D motif composed of 44 sql undulated sheets, while right- and left-helices are alternatively arranged in 3. 2 possesses an interesting 3-D supramolecular network with 1-D hydrogen-bonded chains spanning different directions. 4 and 5 display both polyrotaxane and polycatenane characteristics. In 4, two 2,4-connected (4·85) nets interlocked with each other, forming a 2D → 2D polycatenating network. 5 exhibits a twofold interpenetrated (3,5,6)-connected (3·5·6)(3·52·67)(32·54·66·72·9) topology. 6 and 7 represent rare pentanodal (3,4)-connected and binodal (3,4)-connected frameworks with topologies of (4·5·6)(4·8·10)(52·6·8·9·11)(4·5·6·8·92)(4·5·7) and (4·6·8)(4·62·83), respectively. 8 displays 3-fold interpenetrated 4-connected SrAl2 topology with flexible bix ligands bridging Cd centers to form right- and left-helices. The mixed-ligand effect of the conformations of the PA ligand and N-heterocyclic coligands as well as the metal centers on the assembly of frameworks is unravelled in detail. Solid-state luminescence properties of all compounds were reported as well. Moreover, fluorescence properties of compounds 6 and 8 in various solvent suspensions at room temperature have also been investigated.

An isomorphous family of mixed 3d-4f dodenuclear aggregates, {[Mn(III)8Ln4(Clshi)8(OAc)6(μ3-OCH3)2(μ3-O)2(CH3OH)12(H2O)2]·4CH3OH·xH2O)} (where Ln = Eu(III) (1), Gd(III) (2), Tb(III) (3), and Dy(III) (4); ClshiH3 = 5-chlorosalicylhydroxamic acid; x = 5 for 1 and 3; x = 6 for 2; x = 2 for 4), were synthesized and characterized. They were obtained from the reaction of ClshiH3 with Mn(OAc)2·4H2O and Ln(NO3)3·6H2O. These isomorphous mixed 3d-4f compounds represent a family of novel structures with lanthanide ions in the metallacrown (MC) ring. Each dodecanuclear aggregate contains two offset stacked 14-MC-5 units with M-N-O-M-N-O-Ln-O-N-M-O-N-M connectivity to capture one Ln(III) ion in the core of each MC. Two 14-MC-5 units are connected through O ions with four Mn ions and six O atoms arranged in a double Mn4O6 cubane. Magnetic measurement indicates that antiferromagnetic interactions are present between the metal ions. The Dy(III) analogue with high anisotropy and large spin shows slow magnetization relaxation at a direct-current field of 2 kOe.

Two new compounds, [Ni2(L1)(Py)6]Py·CH3OH(1) and [Ni3(L2)2(Py)4]·2DMF(2)(H4L1=N,N′-bisalicyl-bisthiocarbamide; H3L2=3-hydroxyl-2-naphthalene thiosemicarbazide; Py=pyridine; DMF=dimethyl fumarate), based upon two thiosemicarbazone ligands have been obtained and characterized by elemental analysis, Fourier transform infrared(FTIR) and X-ray diffraction(XRD). Compound 1 possesses a binuclear cluster, in which the bisalicylbisthiocarbamide acts as a hexadentate bridge. Compound 2 exhibits a linear trinuclear cluster with the triply-deprotonated ligand acting as pentadentate bridge. C—H…O, C—H…π and C—H…S weak interactions further link these molecules to form interesting supramolecular networks.

A variety of linear and side-chained p-nitrostilbene derivatives with various numbers of bromine atoms were prepared to survey the crystal structural properties, the photoluminescence, and heavy atom effect on the singlet oxygen generation by two-photo absorption (TPA). Single crystals of 4-nitro-4′-(4″-bromo-phenyl-methyl-oxy)-diphenylethylene (C2), 4-nitro-4′-(3″,5″-dibromo-phenyl-methyl-oxy)-diphenylethylene (C3), 4-nitro-4′-(2′,3″,4′,5″,6″-pentabromo-phenyl-methyl-oxy)-diphenylethylene (C4) were obtained, and the structural characteristics were analyzed by X-ray diffraction. One- and two-photon optical properties of the photosensitizers are shown dependence on the numbers of substituted bromine atoms. While TPA cross-sections of the photosensitizers are diminished more considerably, singlet oxygen quantum yields of the photosensitizers are enhanced at some extents by the substituted bromine atoms. Side-chained photosensitizers display correspondingly higher singlet oxygen quantum yields and larger TPA cross-sections than the molecules with single bromine-substituted aromatic segment. Molecular modeling was also performed to reveal the fundamental reasons of the experimental observation. Photooxidation reaction of singlet oxygen with some substrates was employed to confirm singlet oxygen generation under one- and two-photon irradiation.

Two 1-D cobalt coordination polymers, [Co(mbtx)(hpht)(H2O)] n (1) and [Co(mbix)(hpht)] n (2) (mbtx = 1,3-bis(1,2,4-triazol-1-ylmethyl)benzene, mbix = 1,3-bis(imidazol-1-ylmethyl)benzene, H2hpht = homophthalic acid), were synthesized by hydrothermal reactions and characterized by elemental analyzes, IR spectroscopy, thermogravimetry, and single-crystal X-ray diffraction. Complex 1 is a 1-D heterostranded double-helical chain as a result of bridging hpht and mbtx, and the 1-D chains are further self-assembled into a 2-D layer structure through hydrogen bonds. Complex 2 shows a 1-D molecular ladder structure, linked through C–H···π interactions to give a 2-D layer structure, which is further linked through C–H⋯O hydrogen bonds to form a 3-D framework. The mbtx adopts cis-conformation in 1, while for 2, mbix has trans-conformation. Factors causing the differences between 1 and 2 are discussed.

Two enantiomorphic MgII/carboxylate coordination polymers [Mg(bpda)(H2O)4]n (1M and 1P) have been obtained by spontaneous resolution from achiral precursors, 2,2′-bipyridyl-3,3′-dicarboxylic acid (H2bpda) and Mg(NO3)2·6H2O, upon crystallization without any chiral auxiliary. X-ray structural analysis shows that chiral transmission from molecular axially chiral conformations to crystal chirality is established through concerted coordination and H-bonding interactions. In addition, the CD data, and the thermal and photoluminescence properties in the solid state have also been discussed.

Reactions of 2,4-dihydroxyacetophenone oxime with manganese salts yielded two manganese crowns, [Mn3(μ 3-O)(4-OH-Me-sao)3(HCOO)(MeOH)5]·MeOH (1) and [Mn3(μ 3-O)(4-OH-Me-sao)3(CH3COO)(MeOH)5]·MeOH (2) (4-OH-Me-saoH2=2,4-dihydroxyacetophenone oxime). Both compounds possess [MnIII 3(μ 3-O)]7+ cores which contain 9-MC-3 metallacrown (MC) rings with the repeating pattern [–Mn–N–O–]. However, the difference in the structures of both compounds is coordinated carboxylates. In 1 and 2, the MC molecules are connected with each other through intermolecular hydrogen bonds, generating similar 3-D supramolecular networks. Magnetic properties reveal that in 1 and 2 the metal ions exhibit ferromagnetic exchange coupling.

A novel one-dimensional helical mixed-valence cobalt coordination polymer (1) {[CoIICoIII(HL)2(OAc)]·CH3OH·H2O}n, (H3L = 2-ethyl-2-((2-hydroxynaphthalen-1-yl)methyleneamino)propane-1,3-diol) has been synthesized and characterized. Single-crystal X-ray diffraction analyses reveal that complex 1 crystallizes in the tetragonal I4(1)/a space group. It consists of a bimetallic CoIICoIII(μ2-O)2 core, and the adjacent CoII(2) centers are sequentially bridged by carboxylate groups in the syn–anti fashion, affording to a one-dimensional infinite helical chain along the c-axis. Adjacent chains are stacked via C H···π interactions to form the overall three-dimensional supramolecular networks. Magnetic and in vitro anticancer activities of the complex have been investigated in detail.

A novel coordination polymer [Co(bpbc)(H 2 O) 2 ] n ( 1 ) was synthesized by hydrothermal reaction of Co(OAc) 2 ·2H 2 O and 2,2′-bipyridine-4,4′-dicarboxylate acid (H 2 bpbc). X-ray single diffraction studies reveal that compound 1 exhibits chiral two-fold interpenetrating 3-D network, which contains different numbers of left- and right-handed helical chains. The magnetic property is also investigated.

Background The lack of a general clinic-relevant model for human cancer is a major impediment to the acceleration of novel therapeutic approaches for clinical use. We propose to establish and characterize primary human hepatocellular carcinoma (HCC) xenografts that can be used to evaluate the cytotoxicity of adoptive chimeric antigen receptor (CAR) T cells and accelerate the clinical translation of CAR T cells used in HCC. Methods Primary HCCs were used to establish the xenografts. The morphology, immunological markers, and gene expression characteristics of xenografts were detected and compared to those of the corresponding primary tumors. CAR T cells were adoptively transplanted into patient-derived xenograft (PDX) models of HCC. The cytotoxicity of CAR T cells in vivo was evaluated. Results PDX1, PDX2, and PDX3 were established using primary tumors from three individual HCC patients. All three PDXs maintained original tumor characteristics in their morphology, immunological markers, and gene expression. Tumors in PDX1 grew relatively slower than that in PDX2 and PDX3. Glypican 3 (GPC3)-CAR T cells efficiently suppressed tumor growth in PDX3 and impressively eradicated tumor cells from PDX1 and PDX2, in which GPC3 proteins were highly expressed. Conclusion GPC3-CAR T cells were capable of effectively eliminating tumors in PDX model of HCC. Therefore, GPC3-CAR T cell therapy is a promising candidate for HCC treatment.

The existence and identification of leukemia-initiating cells in adult acute B lymphoblastic leukemia (B-ALL) remain controversial. We examined whether adult B-ALL is hierarchically organized into phenotypically distinct subpopulations of leukemogenic and non-leukemogenic cells or whether most B-ALL cells retain leukemogenic capacity, irrespective of their immunophenotype profiles. Our results suggest that adult B-ALL follows the stochastic stem cell model and that the expression of CD34 and CD38 in B-ALL is reversibly and not hierarchically organized. Electronic supplementary material The online version of this article (doi:10.1186/s13045-016-0310-1) contains supplementary material, which is available to authorized users.

From a methyl-substituted thieno[2,3-b]thiophene dicarboxylate, three types of three-dimensional (3-D) microporous lanthanide-based metal-organic frameworks, {[Ln(DMTDC)1.5(H2O)2]·DEF}n (type I, Ln = Eu 1, Tb 2), {[Ln(DMTDC)1.5(H2O)2]·0.5DMF·0.5H2O}n (type II, Ln = Gd 3, Dy 4, Er 5), and {[Ln4(DMTDC)6(DMF)2]·0.5DMF·1.5H2O}n (type III, Ln = Er 6) (H2DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid, DEF = N,N'-diethylformamide, DMF = N,N'-dimethylformamide), have been solventhermally synthesized. Types I and II are isostructural, which exhibit 1-D triangular channels constructed by double-stranded rod-shaped {Ln(CO2)2}n chains. Type III demonstrates an intriguing framework with triple-stranded rod-shaped {Ln(CO2)3}n chains arranged along the (1,1,0) and (1,-1,0) axes and possesses two kinds of triangular channels along two axes, respectively. Immobilization of the Lewis basic sites of thiophene groups induced gas adsorption and sensing properties into these microporous frameworks. Complexes 5(Er) and 6(Er) display moderate adsorption properties toward N2 and CO2, and the Qst of CO2 are as high as 36.3 and 34.8 kJ mol(-1), respectively. Complexes 1(Eu) and 2(Tb) exhibit sensing properties toward nitrobenzene, acetone, and the Cu(2+) ion in both DMF and aqueous solution. Complex 3(Gd) shows a significant magnetocaloric effect with ΔSm = 24.3 J·kg(-1)·K(-1) at 3.0 K and 7 T. Complex 4(Dy) exhibits slow magnetic relaxation with the energy barrier Δ/kB of 48.29 K.

Six transition metal compounds [Cu(H2L)(CH3COO)]·H2O (1), [Cu(H2L)(CH3COO)] (2), [Cu(H2L)](ClO4)·CH3OH (3), 2[Cu(H2L)2] (4), [Co(H2L)2](NO3)·2CH3OH (5), and [Ni(H2L)](NO3) (6) were synthesized by reactions of the Schiff base ligand H3L (1-{[2-(2-hydroxyethyl amino)ethylimino]methyl}naphthalen-2-ol) with the corresponding metal salts and characterized by single crystal X-ray diffraction, elemental analysis, IR and UV/Vis spectroscopy and TG analysis. All compounds are mononuclear molecules, in which the Schiff base ligand exhibits diverse coordination modes and conformations. The N–H···O, O–H···O, and C–H···O inter- and intramolecular hydrogen bonding interactions link these molecules into multidimensional network supramolecular structures.

Three porous (3,24)-connected rht-type metal-organic frameworks (MOFs), [Cu(3)L(H(2)O)(3)]·xsolvents (H(6)L(OH) = 4,4',4"-(hydroxysilanetriyl)tris(triphenyl-3,5-dicarboxylic acid), SDU-6; H(6)L(Me) = 4,4',4"-(methylsilanetriyl)tris(triphenyl-3,5-dicarboxylic acid), SDU-7; H(6)L(iBu) = 4,4',4"-(isobutylsilanetriyl)tris(triphenyl-3,5-dicarboxylic acid), SDU-8), have been successfully prepared from [Cu(2)(COO)(4)] paddlewheel SBUs (secondary building units) and C(3)-symmetric Si-based hexatopic carboxylatelinkers. All porous MOFs are constructed from 3D packing of nanosized cuboctahedral, truncated tetrahedral, and truncated octahedral cages. SDU-6-8 differ only in the functionality of the central Si atom of the hexacarboxylate ligands with hydroxyl, methyl, and isobutyl groups, respectively. Gas adsorption measurements of activated MOFs suggested that decoration of the cage walls with strong polar groups can enhance the adsorption capacities for N(2), H(2), and CH(4). SDU-6 with -OH as the functional group possesses high CH(4) uptake (172 cm(3) cm(-3) at 35 bar), which is very close to DOE target of 180 cm(3) cm(-3).

In this work, Bi2WO6 with complex morphologies, namely, flower-like, pancake-like, and tubular shapes have been controllably synthesized by a facile solvothermal process. The as-obtained samples are systematically investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). The effects of solvents on the morphologies of Bi2WO6 nanostructures are systematically investigated. According to the time-dependent experiments, a two-step growth mode basing on Ostwald ripening process and self-assembly has been proposed for the formation of the flower-like and pancake-like Bi2WO6 nanostructures. The photocatalytic properties of Bi2WO6 nanostructures are strongly dependent on their shapes, sizes, and structures for the degradation of rhodamine B (RhB) under visible-light irradiation. The deduced reasons for the differences in the photocatalytic activities of these Bi2WO6 nanostructures are further discussed.

The reaction of CoCl2 · 6H2O, mpkoH (methyl 2-pyridyl ketone oxime), NEt3, and NaN3 in a 1 : 1 : 2 : 1 molar ratio affords a linear trinuclear complex, [ CoII(mpko)4(N3)4(H2O)2] (1). Complex 1 has been characterized by single-crystal X-ray diffraction, elemental analysis, and infrared spectrum. Three cobalt ions are in the center of distorted octahedra, which are connected by two μ-1,1 azides and two oxime oxygen atoms to form a linear trinuclear structure. Discrete units of 1 are connected to form a stable 3-D supramolecular network by C–H···O and C–H···N weak interactions. Variable temperature magnetic susceptibility measurements reveal that 1 exhibits antiferromagnetic behavior.

A novel supermolecular building blocks (SBBs) based metal–organic framework (MOF), with formula [Zn7(TMBHB)2·2NO3·5DMF·4CH3CH2OH·6H2O]n (SDU-1), was constructed from C3-symmetric trimethyl substituted 3,3′,3″,5,5′,5″-benzene-1,3,5-triylhexabenzoic acid (H6TMBHB). Notably, the SDU-1 consists of two kinds of rare secondary building units (SBUs), [Zn2(COO)3] and [Zn2(COO)4], which are linked by TMBHB to form cubic and trisoctahedral SBBs, respectively. TOPOS software analysis of SDU-1 indicates that two alternative simplifications based on different SBBs can produce (3,24)-connected rht or (4,12)-connected ftw topologies. Compared with a recently reported Zn-BHB (H6BHB = 3,3′,3″,5,5′,5″-benzene-1,3,5-triylhexabenzoic acid) MOF, the structural dissimilarity between them was caused by the steric hindrance of three methyl groups, which makes three isophthalate units on TMBHB nearly perpendicular to the central phenyl ring, giving TMBHB a nonplanar conformation. The photoluminescence behavior of SDU-1 was also d...

Crystallization of a Schiff base with nickel acetate in different solvents yields a tetranuclear (dicubane-like [Ni4O4] core with two missing vertices) and a hexanuclear cluster ([Ni6O6] core with two nickel(II) ions attached to a [Ni4O4] cubane through oxygen bridges). Metal centers within these clusters exhibit ferromagnetic and antiferromagnetic coupling interactions, respectively.

Effect of the concentration of water-soluble polyanion (sodium carboxymethylcellulose, NaCMC) on the interaction between a cationic surfactant (1-dodecyl-3-methylimidazolium bromide, C12mimBr) and NaCMC in aqueous solution has been studied by isothermal titration microcalorimetry (ITC), conductivity, surface tension, and rheological measurements. From the surfactant/polymer interacting enthalpy, it can be deduced that the electrostatic attraction between the cationic surfactant and anionic polyelectrolyte causes an endothermic process, and the C12mimBr monomers binding to the NaCMC chains to form micelle-like aggregates through hydrophobic interaction is an exothermic process. Increasing the NaCMC concentration causes the interaction between C12mimBr and NaCMC to decrease, and the characteristic surfactant concentrations, including the critical aggregation surfactant concentration (CAC), the surfactant concentration to form free micelles (Cm), and the saturation concentration of surfactant on the NaCMC ch...

Five novel compounds, {[Ni(PA)(bpe)(H2O)2]·DMF}n (1), {[Zn(PA)(bpe)]·DMF}n (2), {[Zn(PA)(bpe)]·2DMF·CH3OH}n (3), {[Cd2(PA)2(bpe)2(H2O)]·3.5H2O}n (4), {[Ni2(PA)2(bpp)2(H2O)3]·2DMF}n (5), based on pamoic acid (H2PA) (bpe = 1,2-bi(4-pyridyl)ethane, bpp = 1,3-bi(4-pyridyl)propane) have been synthesized. In such a system, both the PA2– anion ligand and dipyridyl ligands act as bipodal linkers, connecting the metal centers in square or tetrahedral geometries into 4-connected topologies with different entangled modes: 3-fold interpenetrating CdSO4 net (65.8) (1), roto-translational [2 + 2] interpenetrating diamond pseudosupramolecular isomers (2 and 3), 3-fold interpenetrating (6.74.8)(64.7.8) (4) and (6.85)(64.82) net with both 2-fold interpenetrating and self-penetrating characters (5), respectively. The formation of unique penetrating frameworks was investigated in detail. Gas adsorption and photoluminescent properties of the compounds have also been explored.

Six complexes based on a flexible tripodal ligand H3TTTA (2,2′,2″-[1,3,5-triazine-2,4,6-triyltris(thio)]tris-acetic acid) have been hydrothermally synthesized and structurally characterized. X-ray single-crystal diffractions reveal that they have rich structural chemistry: mononuclear, [Zn(HTTTA)(2,2′-bpy)(H2O)3]n (1); dimeric metallamacrocycle, [Zn(HTTTA)(2,2′-bipy)(H2O)]n (2) and [Cd(HTTTA)(2,2′-bipy)(H2O)·H2O]n (3); two-dimensional networks with binodal (3,6)-connected CdI2 topology based on linear trinuclear M3(μ2–CO2)4(μ2–CO2)2 SBUs (Secondary Building Units), [M3(TTTA)2(2,2′-bipy)2(H2O)m·nH2O]n (M=Zn·4, m=0, n=4; Cd·5 and Mn·6, m=2; n=2). The value of pH and the metal ions has large influences on the resulting structures. The flexible tricarboxylic acid exhibits four coordination modes from monodentate to μ6-bridge. Fluorescence and magnetic properties of the complexes have also been investigated in details.

Five novel Cu(II) metal–organic coordination polymers, [(CuL1)n] (1), [ Cu 2 L 2 2 ( Py ) 4 ] (2), [Cu(HL3)(DMF)2] (3), [ Cu 6 L 4 3 ( Py ) 6 · H 2 O ] n (4), [ Cu 6 L 4 3 ( Py ) 8 ( C 10 H 8 N 2 ) 2 · 8 CH 3 OH ] n (5) (H2L1 = N-2-hydroxy-naphthaldehyde-1-alkenyl-o-amino acid, H2L2 = N-2-hydroxy-naphthaldehyde-1-alkenyl-m-amino acid, H2L3 = N-2-hydroxy-naphthaldehyde-1-alkenyl-o-amino-terephthalic acid), have been synthesized and characterized by IR, elemental analysis, UV spectroscopy and single-crystal X-ray diffraction analyses. Complex 1 possesses helical chain structure, which are further assembled to form three-dimensional frameworks by π⋯π stacking interactions. Complex 2 and 3 exhibit dimeric and monomeric structure. Complex 4 is a novel two-dimensional layer structure based on two kinds of binuclear Secondary Building Units (SBUs), Cu2O2 and Cu2(CO2)4. Complex 5 exhibits a distorted zigzag chain by the alternate connectivity of L and bpy molecules. This result shows that the position of carboxylate groups play an important role in the formation of supramolecular networks.

A simple yet novel method, isothermal titration microcalorimetry (ITC), was employed to determine the enthalpy change of salt-induced wormlike micelle formation. The observed changes in molar enthalpy of 1-hexadecyl-3-methylimidazolium bromide (C16mimBr), sodium tosylate (NaTos) and sodium salicylate (NaSal) in aqueous solutions have been measured. The transformation enthalpy change from spherical micelle to wormlike micelle (ΔHtra) has been obtained from the simulation method based on the microcalorimetric data. Then the enthalpy change of wormlike micelle formation (ΔHw) was obtained using a suitable cycle which was closed by the enthalpy change of micelle formation (ΔHm) and the transformation enthalpy change (ΔHtra). The value of ΔHw indicated that the wormlike micelle formation in C16mimBr/NaTos system was exothermic while it was endothermic in C16mimBr/NaSal system. The planar structure of the salicylate anion and the π–π interaction between the salicylate anion and the aromatic headgroup of C16mimBr may attribute to this difference. Moreover, the technique presented here to obtain ΔHw could be extended to other salt-induced wormlike micelle systems.

Spongy CuO was successfully synthesized via direct pyrolysis of Cu3(btc)2 (btc = benzene-1,3,5-tricarboxylate) microporous metal-organic framework (MOF) in a horizontal tube furnace in the air, in which the Cu3(btc)2 was used as the Cu source and complexing molecule precursor. The as-prepared products were characterized by a series of techniques including XRD, SEM, EDX, TEM, and SAED. Results from SEM showed that the as-prepared spongy CuO with average diameter altering from 10 to 20 μm consists of nanosheets with average edge length in the range of 80–200 nm and thickness of about 30 nm, which was also confirmed by TEM analysis. The XRD and SAED results showed that a purity phase of CuO was obtained after pyrolysis. It was also found that the reaction temperature played a key role in the formation of spongy CuO microstructures. The spongy material could be found potential application in various fields such as catalysis, absorption, and gas sensing.

Two coordination polymers with the same ligand but different metal ion [Cd(C4H4O6)] n (1) and [Mn2(C4H4O6)2(H2O)] n (2) (C4H4O6 = tartrate dianion) have been synthesized. Compound 1 exhibits novel (4, 4)-connected 3-D network with (4.6.84)4(4.62.82.10)(4.62.83)(4.63.82)4(4.85)2 topology, Cd centers are connected by η6, μ4-mode tartrate ligands. For compound 2, Mn centers are link by η6, μ4-mode and η5, μ3-mode tartrate ligands to form (4, 3)-connected 3-D network with (4.82)(4.84.10) topology. Additionally, 1 displays an intense luminescent emission and 2 displays weak antiferromagnetic coupling. Two coordination polymers with the same ligand but different metal ion [Cd(C4H4O6)]n (1) and [Mn2(C4H4O6)2(H2O)] n (2) (C4H4O6 = tartrate dianion) have been synthesized. Compound 1 exhibits novel (4, 4)-connected 3-D framework with (4.6.84)4(4.62.82.10)(4.62.83)(4.63.82)4(4.85)2 topology. Compound 2 exhibits (4, 3)-connected 3-D network with (4.82)(4.84.10) topology.

Five new complexes, [Co3(HL1)2(Py)8]·4CH3OH (1), [Ni3(HL1)2(Py)4]2·2DMF (2), [Co3(H2L2)2(Py)8]·2NO3 (3), [Ni2(HL2)(Py)6] (4) and [Cu4(HL2)2(Py)4]·4DMF (5) (H4L1 = N-propionyl-4-hydroxysalicylhydrazide, H44-hopshz; H5L2 = N-(3-carboxy-cis-2-propenoyl)-4-hydroxysalicylhydrazide, H54-hocpshz) have been obtained from two N,N′-diacylhydrazide ligands and characterized by elemental analysis, FT-IR, X-ray diffraction and antimicrobial activities. These di-, tri-, and tetrameric complexes are connected into three-dimensional supramolecular architectures with interesting topologies through O–H⋯O, C–H⋯O and C–H⋯π interactions. 1–3 are linear trimeric complexes with the ligands triply-deprotonated. Topological analysis indicates that they exhibit 2D (4,4), 3D (6,8)-connected (3349526)(3441257647) and 8-connected (42563) net, respectively. 4 and 5 possess dimeric and tetrameric structures, which are extended into 7-connected (33413536) and 4-connected (4,4) net, respectively.

A novel mixed-valent tetranuclear manganese complex, [MnII2MnIII2(dophe)2(DMSO)7(H2O)] (H5dophe = di-[5-(2-oxyphenyl)-pyrazole]-3-hydroxamic ether) was prepared and characterized through X-ray crystallography, elemental analysis and IR spectra. The molecule contains a linear [MnII2MnIII2N8O2] core with two dinuclear N N bridged subunits connected by two μ2-O atoms. Two dophe5 − ligands are located opposite to each other. Magnetic studies indicate the dominance of intramolecular antiferromagnetic interactions.

In the coordination compound poly[diaqua(mu(2)-4,4'-bipyridine)(mu(2)-4-carboxylatocinnamato)nickel(II)], [Ni(C(10)H(6)O(4))(C(10)H(8)N(2))(H(2)O)(2)](n), both the 4-carboxylatocinnamate and 4,4'-bipyridine (4,4'-bpy) ligands act as bidentate bridges, connecting the Ni(II) centres in an octahedral coordination geometry into a two-dimensional (4,4) layer. Each layer polycatenates two other identical layers, thus giving a rare 2D --> 3D polycatenating network (2D and 3D are two- and three-dimensional, respectively), with a mutually parallel arrangement of the layers. The chiral 4,4'-bpy ligands link the Ni(II) centres into chiral chains, thus introducing chirality into the layer and the resulting 3D network.

In the title coordination compound, catena-poly[[[bis[diaquacadmium(II)]-mu(2)-trans-1,2-bis(4-pyridyl)ethene]bis{mu(2)-2,2'-[(5-carboxymethoxy-m-phenylene)dioxy]diacetato}] trans-1,2-bis(4-pyridyl)ethene solvate dihydrate], {[Cd(2)(C(12)H(10)O(9))(2)(C(12)H(10)N(2))(H(2)O)(4)].C(12)H(10)N(2).2H(2)O}(n), (I), each Cd(II) centre adopts a pentagonal-bipyramidal coordination geometry. The incompletely deprotonated 2,2'-[(5-carboxymethoxy-m-phenylene)dioxy]diacetate (TCMB) ligands and trans-1,2-bis(4-pyridyl)ethene (bpe) ligands both act as bidentate bridges, linking the Cd(II) centres into one-dimensional ladders, which are connected into an undulating two-dimensional (6,3) layer through O-H...N hydrogen bonds between the carboxylate groups of the TCMB ligands and the N atoms of the uncoordinated bpe ligands. Each undulating layer polycatenates two other identical layers, exhibiting the unusual combination of both 2D --> 2D parallel and 2D --> 3D parallel interpenetration (2D and 3D are two- and three-dimensional, respectively).

A mixed-type of azametallacrown based on a flexible pentadentate N-propionyl ligand was reported, which exhibits not only the completely different arrangement of the metal centers but also diversely geometric configurations of the N-terminal ligands, and this complex can further assemble into a novel 3-D supramolecular structure using two different aza18-MC-6 as secondary building units (SBUs) via the intermolecular C–H⋯π, π–π and C–H⋯O interactions. Temperature-dependent magnetic susceptibility measurements of the title complex indicate that the complex presents significantly antiferromagnetic coupling among metal centers.

Successful immunotherapy of chronic hepatitis B virus (HBV) infection is expected to be characterized by enhanced activation of immune responses. Combining the specificity of hepatitis B core antigen (HBcAg) cytotoxic T lymphocyte (CTL) epitope, the cell-penetrating property of human immunodeficiency virus-1 (HIV)-Tat peptide, and the adjuvanticity of CpG oligodeoxynucleotides (CpG ODNs) may elicit strong immune responses and therapeutic effects in HBV infection. We synthesized a fusion peptide containing HBcAg18-27 CTL epitope and HIV-Tat(49-57) peptide. The fusion peptide was intramuscularly injected to HBV transgenic mice with CpG ODN as adjuvant at 2-week intervals three times. The percentages of CD3(+), CD4(+) and CD8(+) cells in spleen lymphocytes and the levels of circulating interferon (IFN)-gamma and interleukin (IL)-2 were determined for the evaluation of immune responses and the levels of serum HBV DNA and the expression of hepatitis B surface antigen (HBsAg) and HBcAg in liver tissue were determined for the assessment of therapeutic effects. Our results showed that the synthesized fusion peptide adjuvanted with CpG ODN could induce significant increase of the percentages of CD3(+), CD4(+) and CD8(+) cells and the levels of IFN-gamma and IL-2, indicating the strong immune responses, and reduced HBV DNA levels and decreased expression of HBsAg and HBcAg in liver tissue, suggesting the therapeutic effects. Collectively, our study supports that HBcAg18-27 CTL epitope fused to HIV-Tat(49-57) peptide adjuvanted with CpG ODN may be a promising strategy for immunotherapy of chronic HBV infection.

Cell-based therapies have been employed with conflicting results. Whether direct injection of ex-vivo expanded autologous marrow stromal cells (MSCs) would improve the function of ischemic myocardium and enhance angiogenesis is not well defined. In a porcine model of chronic ischemia, MSCs were isolated and cultured for 4 weeks. Sixteen animals were random divided into two groups to receive either direct intramyocardial injection of autologous MSCs, or equal volumes and injections sites of saline. Cine MRI and epicardial echocardiography were performed just prior to the injections and again 6 weeks later at the time of sacrifice at which point tissue was also analyzed. Myocardial function as assessed by regional wall thickening (as measured by dobutamine stress echocardiograms) demonstrated a 40.9% improvement after cell treatment of the ischemic zone (p = 0.016) whereas the saline treated animals only had a 3.7% change (p = 0.82) compared to baseline. The left ventricular ejection fractions of MSC group showed 19.5% improvement from baseline 35.9 ± 3.8% to 42.9 ± 5.8% (p = 0.049). Increased vascularity was found in the MSC group compared to controls (0.80 ± 0.30 vs 0.50 ± 0.19 capillary/myocyte ratio, p = 0.018). Direct injection of autologous MSCs promotes angiogenesis and enhances the functional improvements following chronic myocardial ischemia. This suggests that the angiogenesis engendered by cell treatment may be physiologically meaningful by improving the contractility of ischemic myocardium.

Background and Aims Because of the extremely low neoplastic progression rate in Barrett's esophagus, it is difficult to diagnose patients with concomitant adenocarcinoma early in their disease course. If biomarkers existed in normal squamous esophageal epithelium to identify patients with concomitant esophageal adenocarcinoma, potential applications would be far-reaching. The aim of the current study was to identify global gene expression patterns in normal esophageal epithelium capable of revealing simultaneous esophageal adenocarcinoma, even located remotely in the esophagus. Methods Tissues comprised normal esophageal epithelia from 9 patients with esophageal adenocarcinoma, 8 patients lacking esophageal adenocarcinoma or Barrett's, and 6 patients with Barrett's esophagus alone. cDNA microarrays were performed, and pattern recognition in each of these subgroups was achieved using shrunken nearest centroid predictors. Results Our method accurately discriminated normal esophageal epithelia of 8/8 patients without esophageal adenocarcinoma or Barrett's esophagus and of 6/6 patients with Barrett's esophagus alone from normal esophageal epithelia of 9/9 patients with Barrett's esophagus and concomitant esophageal adenocarcinoma. Moreover, we identified genes differentially expressed between the above subgroups. Thus, based on their corresponding normal esophageal epithelia alone, our method accurately diagnosed patients who had concomitant esophageal adenocarcinoma. Conclusions These global gene expression patterns, along with individual genes culled from them, represent potential biomarkers for the early diagnosis of esophageal adenocarcinoma from normal esophageal epithelia. Genes discovered in normal esophagus that are differentially expressed in patients with vs. without esophageal adenocarcinoma merit further pursuit in molecular genetic, functional, and therapeutic interventional studies.

The title polymer Ag(I) complex was synthesized through the reaction of 2,4-diamino-6-methyl-1,3,5-triazine(dmt) and Ag2SO4. X-ray structure analysis shows that the crystal structure of title complex consists a infinite 1-D polymer chains with novel metallamacrocycles, which are cross-linked to each other by four types of hydrogen bonds, resulting in the formation of a new 3-D open network with large channels.

We previously reported that a high degree of age-related methylation was found in both the dysplastic and nondysplastic mucosa of patients with ulcerative colitis (UC). Whether this translates into hypermethylation in UC-associated cancers (UC-Cs) is not known.We evaluated the methylation status of 11 genes (MINT1, 2, 31, hMLH1, p16, p14, MGMT, HPP1, SFRP1, ERalpha, and LINE-1) in 48 UC-Cs, 21 UC-associated dysplasias, and 69 sporadic colorectal cancers (S-CRCs) using a quantitative bisulfite pyrosequencing analysis.Methylation levels in UC-Cs were lower than S-CRCs for all the genes except MGMT. A methylation index based on the average of Z-scores, for type C (cancer-specific genes: MINT1, MINT2, MINT31, hMLH1, p16, and p14) was -.97 in UC-Cs and .92 in S-CRCs (P = .009). That of type A (age-related genes: HPP1, SFRP1, and ERalpha) was -1.97 in UC-Cs and 1.24 in S-CRCs (P.001). We observed a significant difference in the incidence of CpG island methylator phenotype between UC-Cs and S-CRCs (8 of 48 [17%] and 26 of 69 [38%]; P = .022). UC-associated dysplasias had significantly higher methylation of type A gene than UC-Cs (Z-score: .07 and -1.97, respectively; P.001). By contrast, global DNA methylation measured using a LINE-1 assay was significantly higher in UC-Cs than in S-CRCs (58.2% vs 51.0%, P.001).DNA methylation alterations are uncommon in UC cancers. Given that both genetic and epigenetic changes are common in UC mucosa and dysplasias, we speculate that the genetic changes lead to a more aggressive clinical course than epigenetic changes.

Penile malignancies are rare in developed countries. The authors present a case of a penile urethral mesenchymal tumor occurring in a 51-year-old Caucasian male and displaying light microscopic, immuno- histochemical, and ultrastructural features suggestive of a pacemaker cell type, combined with a lack of diagnostic features of any other established tumor category. The immunohistochemical profile was intensely positive for vimentin, PKC h, and NSE and weakly positive to nonreactive for CD34 and smooth muscle actin, and entirely negative for CD117 (c-kit), S-100, and other markers. C-kit and PDGFRA gene analysis showed no mutations. Electron microscopy revealed tumor cells with plentiful cyto- plasm and cytoplasmic processes=filopodia, both filled with intermediate filaments and occasional solitary focal densities. There were also prominent smooth endoplasmic reticulum cisternae, caveolae, neurosecretory gran- ules, particularly concentrated in cytoplasmic processes, and synaptic-type structures. Poorly formed basal lamina, gap junctions, and intercellular collagen aggregates, consistent with skeinoid-type fibers, were also noted. Interstitial cells with potential pacemaker function have been recently described in the lower urinary tract, including the urethra, and this tumor may be related to this cellular phenotype.

It has been a challenge to decipher the in situ ligand reaction mechanism in assembly processes, involving metals and ligands. The present study shows two crystalline mixed-ligand Cu(II) coordination polymers isolated by controlled in situ ligand reactions under the same hydrothermal conditions. Two closely related examples provide a precious chance to access the in-depth mechanistic issues surrounding in situ reactions. The solid structure of 1 demonstrated that maleic acid was completely transformed to malic acid, whereas when fumaric acid was used in the same reaction conditions, an incomplete transformation from fumaric acid to malic acid was observed in the solid structure of 2. Compound 1 exhibits a 3D 6-connected sni network based on a binuclear copper(ii) secondary building unit, whereas the 3D network of 2 is classified to a (6,8)-connected topology network. The difference in steric hindrance between maleic acid and fumaric acid dictates the degree of the in situ nucleophilic addition reaction. The comparison of synthesis and final solid structures indicates that the one-step nucleophilic addition mechanism for in situ generated malic acid under the current reaction conditions of 1 is plausible. The magnetic sensitivity measurements of 1 demonstrated that overall antiferromagnetic coupling exists between Cu1 and Cu2 ions and between Cu3 and Cu4 ions. Furthermore, the obtained 1 can be an active catalyst for the solvent-free silylcyanation of aromatic aldehydes under mild conditions.

Background & Aims: Gene silencing via promoter hypermethylation is a central event in the pathogenesis of cancers. To identify novel methylation targets in colon cancer, we conducted a genome-wide, microarray-based, in silico, and epigenetic search. Methods: Complementary DNA microarray experiments were first performed to identify genes down-regulated in primary colon cancers and up-regulated in colon cancer cell lines after global DNA demethylation by 5-aza-2′-deoxycitidine. Candidate methylation targets were then identified by combining these microarray data with in silico genetic and functional searches. Candidate genes recognized by these searches were further investigated for promoter hypermethylation in colon cancer using methylation-specific polymerase chain reaction. Results: We identified 51 novel and 3 known candidate methylation targets. Subsequent epigenetic analysis revealed that primary colon cancers demonstrated frequent methylation of somatostatin (SST, 30 of 34 cases, 88%) and the substance P precursor gene tachykinin-1 (TAC1; 16 of 34 cases, 47%). TAC1 methylation intensity was significantly higher in Dukes A/B than in Dukes C/D cancers (P = .01). SST methylation intensity was significantly higher in low-level microsatellite instability (MSI-L) than in non-MSI-L cancers (P = .02). Methylation was associated with messenger RNA down-regulation for both SST and TAC1. Furthermore, we isolated 5 additional novel promoter methylation targets: NELL1, AKAP12, caveolin-1, endoglin, and MAL. Conclusions: These data strongly suggest that SST and TAC1 are involved in colon carcinogenesis. Further studies are now indicated to elucidate mechanisms underlying their involvement in colon cancer and their values as clinical biomarkers. NELL1, AKAP12, caveolin-1, endoglin, and MAL are also promising tumor suppressor gene candidates deserving of further study.

Four novel cadmium(II) coordination polymers, [Cd3(TCMB)2(4,4-bipy)(H2O)16]n (1), [Cd3(TCMB)2(bpe)(H2O)13]n (2), [Cd3(TCMB)2(bpe)2(H2O)4]n (3), and [Cd3(TCMB)2(dpp)2(H2O)3]n (4), [TCMB = 1,3,5-tris(carboxymethoxy)benzene, 4,4-bipy = (4,4-bipyridine), bpe = 1,2-bis(4-pyridyl)ethane, dpp = 1,3-bis(4-pyridyl)propane] have been hydrothermally synthesized by the self-assembly of the flexible tripodal acid TCMB and Cd(OAc)2·2H2O with pyridyl-containing ligands possessing different flexibilities. Single-crystal X-ray diffraction analysis reveals that the four polymers exhibit novel frameworks due to diverse coordination modes and different conformations of the flexible TCMB as well as pyridyl-containing ligands. Complex 1 shows a unique twofold parallel interpenetrating 2D honeycomb network structure with an unusual 63 topology, in which two different large hexagonal rings are arranged alternately, with extraordinarydimensions of ca. 22.172(6) × 12.947(2) A (A) and 17.233(2) × 12.947(2) A (B) based on the distances of the atoms at the opposite positions of the rings. Complex 2 is almost isostructural to complex 1, except that the bidentate bpe ligands bridge the cadmium centers in an anti conformation, rendering the network more flexible. Complex 3 features a 3D network with one of the scarce eight-connected (46, 614, 88)(43)2 topologies based on the rare CdI2-type layer constructed from secondary building units (SBUs) of rare [Cd3(CO2)4]2- isosceles triangle cadmium clusters. Complex 4 possesses distorted CdI2-type layers constructed from unprecedented ten-connected Cd3 clusters which are linked by more flexible dpp ligands in a trans-gauche (TG) conformation in (4,4) networks, leading to another 3D framework of the unusual (418, 624, 83)(43)2 topology. Such an arrangement represents the highest connected topology presently known for the frameworks. Among them, complex 1 displays photoluminescent properties at 460 nm due to the ligand-to-metal charge transfer (LMCT).

Objective: Mortality due to esophageal adenocarcinoma has risen markedly, but the molecular mechanisms underlying this carcinogenesis are still incompletely understood. Findings from loss of heterozygosity (LOH) studies have suggested that the long arm of chromosome 4 might harbor tumor suppressor genes relevant to esophageal adenocarcinoma. Methods: We performed LOH analysis of 4q in esophageal adenocarcinomas. Regions of LOH were further evaluated by studying two candidate tumor suppressor genes, hCDC4 and CARF, located within them. Results: 54% of the adenocarcinomas examined showed allelic deletion. LOH was observed in 53, 40, 32, 38, and 27% of tumors at positions D4S1554 (the locus of CARF), D4S1572, D4S1548, D4S2934, and D4S3021, respectively. An area of allelic deletion (spanning 3 million bases) was identified at 4q31.1–3 in 37% of tumors. This region harbors a candidate tumor suppressor gene: hCDC4. However, sequencing of the coding regions of CARF and hCDC4 at 4q35 and 4q31, respectively, did not identify mutations. Conclusions: Our findings demonstrate frequent LOH in esophageal adenocarcinoma at several loci including a novel area of allelic deletion at 4q31.1–3. The results imply that mutational or other alterations at these loci may be involved in the pathogenesis of esophageal adenocarcinoma. Candidate tumor suppressor genes located within these regions merit further study.

Patients with Barrett's esophagus (BE) are at increased risk of developing esophageal adenocarcinoma (EAC). Clinical neoplastic progression risk factors, such as age and the length of the esophageal BE segment, have been identified. However, improved molecular biomarkers predicting increased progression risk are needed for improved risk assessment and stratification. Using real-time quantitative methylation-specific PCR, we screened 10 genes (HPP1, RUNX3, RIZ1, CRBP1, 3-OST-2, APC, TIMP3, p16, MGMT, p14) for promoter hypermethylation in 77 EAC, 93 BE, and 64 normal esophagus (NE) specimens. A subset of genes manifesting significant differences in methylation frequencies between BE and EAC was then analysed in 20 dysplastic specimens. All 10 genes except p14 were frequently methylated in EACs, with RUNX3, HPP1, CRBP1, RIZ1, and OST-2 representing novel methylation targets in EAC and/or BE. p16, RUNX3, and HPP1 displayed increasing methylation frequencies in BE vs EAC. Furthermore, these increases in methylation occurred early, at the interface between BE and low-grade dysplasia (LGD). To demonstrate the silencing effect of hypermethylation, we selected the EAC cells BIC1, in which the HPP1 promoter is natively methylated, and subjected them to 5-aza-2'-deoxycytidine (Aza-C) treatment. Real-time RT-PCR indicated increased HPP1 mRNA levels after 3 days of Aza-C treatment, as well as decreased levels of methylated HPP1 DNA. Hypermethylation of a subset of six genes (APC, TIMP3, CRBP1, p16, RUNX3, and HPP1) was then tested in a retrospective longitudinal study of 99 BE and nine LGD specimens obtained from 53 BE patients undergoing surveillance endoscopy. Only high-grade dysplasia (HGD) or EAC were defined as progression end points. Two patient groups were compared: eight progressors (P) and 45 nonprogressors (NP), using Cox proportional hazards models to determine the relative progression risks of age, BE segment length, and methylation events. Multivariate analyses revealed that only hypermethylation of p16 (odds ratio (OR) 1.74, 95% confidence interval (CI) 1.33-2.20), RUNX3 (OR 1.80, 95% CI 1.08-2.81), and HPP1 (OR 1.77, 95% CI 1.06-2.81) were independently associated with an increased risk of progression, whereas age, BE segment length, and hypermethylation of TIMP3, APC, or CRBP1 were not independent risk factors. In combined analyses, risk was detectable up to, but not earlier than, 2 years preceding neoplastic progression. Hypermethylation of p16, RUNX3, and HPP1 in BE or LGD may represent independent risk factors for the progression of BE to HGD or EAC. These findings have implications regarding risk stratification, early EAC detection, and the appropriate endoscopic surveillance interval for patients with BE.

The activin type II receptor (ACVR2) gene is a putative tumor suppressor gene that is frequently mutated in microsatellite-unstable colon cancers (MSI-H colon cancers). ACVR2 is a member of the transforming growth factor (TGF)-β type II receptor (TGFBR2) family and controls cell growth and differentiation. SMAD proteins are major intracellular effectors shared by ACVR2 and TGFBR2 signaling; however, additional shared effector mechanisms remain to be explored. To discover novel mechanisms transmitting the ACVR2 signal, we restored ACVR2 function by transfecting wild-type ACVR2 (wt-ACVR2) into a MSI-H colon cancer cell line carrying an ACVR2 frameshift mutation. The effect of ACVR2 restoration on cell growth, SMAD phosphorylation, and global molecular phenotype was then evaluated. Decreased cell growth was observed in wt-ACVR2 transfectants relative to ACVR2-deficient vector-transfected controls. Western blotting revealed higher expression of phosphorylated SMAD2 in wt-ACVR2 transfectants versus controls, suggesting cells deficient in ACVR2 had impaired SMAD signaling. Microarray-based differential expression analysis revealed substantial ACVR2-induced overexpression of genes implicated in the control of cell growth and tumorigenesis, including the activator protein (AP)-1 complex genes JUND, JUN, and FOSB, as well as the small GTPase signal transduction family members, RHOB, ARHE, and ARHGDIA. Overexpression of these genes is shared with TGFBR2 activation. This observed similarity between the activin and TGF-β signaling systems suggests that activin may serve as an alternative activator of TGF-β effectors, including SMADs, and that frameshift mutation of ACVR2 may contribute to MSI-H colon tumorigenesis via disruption of alternate TGF-β effector pathways.

The activin type II receptorgene (ACTRII) is mutated in 58.1% of microsatellite-unstable (MSI-H) colorectal cancers and is a close relative of the TGFbeta-1 type II receptor, which is known to be involved in both MSI-H and non-MSI-H colorectal carcinogenesis. We therefore sought to determine whether ACTRII was involved in non-MSI-H colorectal cancers. We evaluated ACTRII inactivation by allelic deletion, loss of mRNA expression, or somatic mutation in 51 non-MSI-H colon cancers. Loss of heterozygosity (LOH) at the ACTRII locus (2q23.1) was found in 9 (17.6%) of 51 primary tumors. Loss of ACTRII mRNA expression was seen in one (14.3%) of the seven LOH-positive primary tumors from which total RNA was available. We also performed DNA sequencing analysis of tumors showing LOH. One LOH-positive primary tumor exhibited a novel germline missense sequence alteration (amino acid substitution, 117 Ile to Phe) that was not found in 23 additional normal individuals, implying that this alteration is not a frequent polymorphism. We conclude that ACTRII is probably involved in both non-MSI-H and MSI-H colorectal carcinogenesis, but more frequently in the latter subgroup.

In order to identify and contrast global gene expression profiles defining the premalignant syndrome, Barrett's esophagus, as well as frank esophageal cancer, we utilized cDNA microarray technology in conjunction with bioinformatics tools. We hybridized microarrays, each containing 8000 cDNA clones, to RNAs extracted from 13 esophageal surgical or endoscopic biopsy specimens (seven Barrett's metaplasias and six esophageal carcinomas). Hierarchical cluster analysis was performed on these results and displayed using a color-coded graphic representation (Treeview). The esophageal samples clustered naturally into two principal groups, each possessing unique global gene expression profiles. After retrieving histologic reports for these tissues, we found that one main cluster contained all seven Barrett's samples, while the remaining principal cluster comprised the six esophageal cancers. The cancers also clustered according to histopathological subtype. Thus, squamous cell carcinomas (SCCAs) constituted one group, adenocarcinomas (ADCAs) clustered separately, and one signet-ring carcinoma was in its own cluster, distinct from the ADCA cluster. We conclude that cDNA microarrays and bioinformatics show promise in the classification of esophageal malignant and premalignant diseases, and that these methods can be applied to small biopsy samples.

Two CuII-based MOFs have been constructed by synergistic assembly involving the mixed-ligand synthetic strategy and the solvent effect. Compound 1 is a 3D structure and represents a cds topology, while compound 2 displays a rare structure built by three distinct {Cu4} clusters as SBUs. Moreover, the magnetic properties of 2 have been thoroughly investigated.