Pan-cancer analysis of NUP155 and validation of its role in breast cancer cell proliferation, migration, and apoptosis.

NUP155 is reported to be correlated with tumor development. However, the role of NUP155 in tumor physiology and the tumor immune microenvironment (TIME) has not been previously examined. This study comprehensively investigated the expression, immunological function, and prognostic significance of NUP155 in different cancer types. Bioinformatics analysis revealed that NUP155 was upregulated in 26 types of cancer. Additionally, NUP155 upregulation was strongly correlated with advanced pathological or clinical stages and poor prognosis in several cancers. Furthermore, NUP155 was significantly and positively correlated with DNA methylation, tumor mutational burden, microsatellite instability, and stemness score in most cancers. Additionally, NUP155 was also found to be involved in TIME and closely associated with tumor infiltrating immune cells and immunoregulation-related genes. Functional enrichment analysis revealed a strong correlation between NUP155 and immunomodulatory pathways, especially antigen processing and presentation. The role of NUP155 in breast cancer has not been examined. This study, for the first time, demonstrated that NUP155 was upregulated in breast invasive carcinoma (BRCA) cells and revealed its oncogenic role in BRCA using molecular biology experiments. Thus, our study highlights the potential value of NUP155 as a biomarker in the assessment of prognostic prediction, tumor microenvironment and immunotherapeutic response in pan-cancer.

Highly enantioselective one-pot sequential synthesis of valerolactones and pyrazolones bearing all-carbon quaternary stereocentres.

Highly enantiopure and bioactive δ-valerolactones and pyrazolones, bearing α-all-carbon quaternary stereocentres, were successfully and sequentially prepared via a one-pot procedure starting from readily available, inexpensive materials, catalysed by a new chiral squaramide under mild reaction conditions. An organocatalytic Michael reaction afforded the valerolactones, while a one-pot Michael-hydrazinolysis-imidization cascade yielded the pyrazolones. This procedure is economically efficient and environmentally benign.

Modulation of the Coordination Environment around the Magnetic Easy Axis Leads to Significant Magnetic Relaxations in a Series of 3d-4f Schiff Complexes.

A series of Salen-type Zn(II)-Dy(III) complexes [L1Zn(II)ClDy(III)(acac)2]·H2O (1), [L1Zn(II)BrDy(III)(acac)2]·H2O (2), [L1Zn(II)(H2O)Dy(III)(acac)2]·CH2Cl2·PF6 (3), [L2Zn(II)(H2O)Dy(III)(acac)2]·PF6 (4), and Co(III)-Dy(III) complexes [L1Co(III)Br2Dy(III)(acac)2]·CH2Cl2 (5), [L2Co(III)Cl2Dy(III)(acac)Cl(MeO)] (6), [L2Co(III)Cl2Dy(III)(acac)Cl(H2O)] (7), and [L2Co(III)Cl2Dy(III)(NO3)2(MeO)] (8) heterobinuclear single-molecule magnets (SMMs) were synthesized and magnetically characterized. These complexes were constructed by incorporating diamagnetic Zn(II) and Co(III) ions with acetylacetone (acac) and compartmental Schiff-base ligands (H2L1 = N, N'-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine; H2L2 = N, N'-bis(2-oxy-3-methoxybenzylidene)-1,2-diaminocyclohexane). In the Zn(II)-Dy(III) (1-4) system, the coordination environments of the Dy(III) ions are nearly identical, but the apical coordination atom to the Zn(II) ion is different. Complexes 1, 2, and 4 displayed no magnetic relaxation in the absence of external magnetic field, but complex 3 displayed more pronounced SMM behavior with a relaxation energy barrier Ueff/ kB 38 K and magnetic hysteresis at 1.8 K. The SMM performances of 5, 6, and 7 were enhanced significantly by incorporating an octahedral Co(III) instead of square-pyramidal Zn(II) and replacing one of acac- group around Dy(III) ion by a neutral O atom, displaying Ueff of 167, 118, and 75 K as well as magnetic hysteresis up to 3.5 K. These studies indicated that the remote diamagnetic Zn(II) and Co(III) ions played a key role, and the SMM properties were very strongly related to the special coordination atoms configuration around Dy(III) ion. When this coordination configuration around was broken as 8 exhibited, however, it resulted in a dramatically decreased SMM performance. From this work, the key factors that significantly affect the SMM performance of these heteronuclear Zn(II)/Co(III)-Dy(III) SMMs are unambiguously presented.

Isopropylmagnesium chloride-promoted unilateral addition of Grignard reagents to ß-diketones: one-pot syntheses of ß-tertiary hydroxyl ketones or 3-substituted cyclic-2-enones.

The regioselective unilateral additions of Grignard reagents to acyclic or cyclic ß-diketones were effectively promoted by sub-stoichiometric amounts of i-PrMgCl to afford ß-tertiary hydroxyl ketones or 3-substituted cyclic-2-enones, respectively. Also, the addition of Grignard reagents to acyclic ß-diketones followed by a reaction with cyclic ß-diketones in a one-pot process was put forward. The reaction mechanism was discussed in detail to explain the high regioselectivity via chemical experiments, hydrogen-deuterium exchange and mass spectrometry.

(Acetyl-acetonato-κO,O')(phthalo-cyaninato-κN)(phen-an-throline-κN,N')erbium(III).

The title complex, [Er(C(32)H(16)N(8))(C(5)H(7)O(2))(C(12)H(8)N(2))], possesses a mirror plane and the asymmetric unit is half of the mol-ecule. The Er(III) cation, lying on the mirror plane, is eight-coordinated by two O atoms from acetyl-acetone, two N (N(phen)) atoms from 1,10-phenanthroline and four isoindole N (N(iso)) atoms from the phthalocyanine ligand in an anti-prismatic geometry. The Er-N distances are in the range 2.376 (5)-2.529 (4) Šand the Er-O distance is 2.272 (3) Å. Notably, the Er-N(iso) bonds are shorter than the Er-N(phen) bonds, but longer than the Er-O bonds.

A salen-type trinuclear Zn2Gd complex.

In the trinuclear title complex, di-µ-acetato-1:2κ(2)O:O';2:3κ(2)O:O'-bis-{µ-6,6'-dimeth-oxy-2,2'-[cyclo-hexane-1,2-diylbis(methanylyl-idene)]diphenolato}-1:2κ(6)O(1),N,N',O(1'):O(6),O(6');2:3κ(6)O(6),O(6'):O(1),N,N',O(1')-2-gadolinium(III)-1,3-dizinc hexa-fluor-idophosphate methanol monosolvate monohydrate, [GdZn2(C22H24N2O4)2(CH3COO)2]PF6·CH3OH·H2O, the two Zn(II) ions are located in the inner N2O2 cavities of two 6,6'-dimeth-oxy-2,2'-[cyclo-hexane-1,2-diylbis(methanylyl-idene)]diphenolate (L) ligands. Both Zn(II) ions are five-coordinated by two O atoms and two N atoms from the L ligand and one O atom of an acetic acid mol-ecule, giving rise to a square-pyramidal geometry around the Zn(II) ions. The Gd(III) ion is nine-coordinated by four O atoms from the outer O2O2 sites of one ligand, and three O atoms from another ligand, in which there is one non-coordinating meth-oxy O atom. Two further O atom from different acetate ligands complete the nine-coordinate environment.

catena-Poly[copper(II)-bis-(µ-2-formyl-6-meth-oxy-phenolato-κO,O:O,O)-[(methanol-κO)sodium]-µ-perchlorato-κO:O'].

In the title heterodinuclear complex, [CuNa(C(8)H(7)O(3))(2)(ClO(4))(CH(3)OH)](n), the Cu(II) ion is five-coordinated by four O atoms from two 2-formyl-6-meth-oxy-phenolate anions and one O atom from a perchlorate anion in a distorted square-pyramidal geometry. The Na(+) ion is six-coordinated by four O atoms from two 2-formyl-6-meth-oxy-phenolate ligands, one O atom of a methanol mol-ecule and one O atom of a perchlorate anion. The perchlorate anions link the Na(+) and Cu(II) ions, forming a chain along [010]. O-H⋯O hydrogen bonds connect the chains. π-π inter-actions are present between the benzene rings [centroid-centroid distances = 3.566 (2) and 3.702 (2) Å]. The O atoms of the perchlorate anion are disordered over two sets of sites, with an occupancy ratio of 0.481 (8):0.519 (8).

Trichlorido{µ-6,6'-dimeth-oxy-2,2'-[cyclo-hexane-1,2-diylbis(nitrilo-methanylyl-idene)]diphenolato}dimethano-l-copper(II)samarium(III).

In the title hetero-dinuclear complex, [CuSm(C(22)H(24)N(2)O(4))Cl(3)(CH(3)OH)(2)], the Cu(II) cation is N,N',O,O'-chelated by a 6,6'-dimeth-oxy-2,2'-[cyclo-hexane-1,2-diylbis(nitrilo-methanylyl-idene)]diphenolate ligand, and one Cl(-) anion further coordinates to the Cu(II) cation to complete the distorted square-pyramidal coordination geometry, while the Sm(III) cation is chelated by four O atoms from the same ligand, and is further coordinated by two methanol mol-ecules and two Cl(-) anions in an bicapped trigonal-prismatic geometry. Intra- and inter-molecular O-H⋯Cl hydrogen bonds are present in the structure.

[Preliminary establishment of an unsupervised quantification model of Ki-67 proliferation index based on local variable threshold method].

PURPOSE: To develop an effective machine learning method for estimation of Ki-67 cell proliferation index. METHODS: Oral squamous cell carcinoma(OSCC) slices were selected for Ki-67 immunohistochemical staining. The digital pathology images were obtained through whole-slide imaging technology. Variable threshold method based on local statistics was applied to preprocess the images, aiming at reducing the noise in the images. Adaptive threshold method was used to remove the irrelevant light-colored background area in the image, retaining the nucleus part. A threshold method in space was applied to differentiate brown from blue content. Finally, the proliferation index was estimated and compared with manual and the color deconvolution method by paired sample t test and spearman correlation coefficients with SPSS 24.0 software package. RESULTS: A new nucleus detection and classification method was established, which can process pathologic images of different sizes, and effectively detect immunohistochemical brown positive cells and blue negative cells. There was no significant difference between this algorithm and manual counting（P＞0.05）, but the speed was faster. The calculation efficiency advantage was more obvious when processing a large image, and the detection result of Ki-67 proliferation index was better than the commonly used color deconvolution method（P＜0.05）. CONCLUSIONS: The automatic nucleus quantitative analysis method developed in this study can analyze Ki-67 staining of the nucleus in OSCC cells efficiently and calculate the proliferation index, which can be used for auxiliary diagnosis in pathology.

{µ-6,6'-Dimeth-oxy-2,2-[propane-1,3-diylbis(nitrilo-methanylyl-idene)]diphenolato}trinitratocopper(II)dysprosium(III) methanol monosolvate.

In the title heterodinuclear salen-type complex, [CuDy(C(19)H(20)N(2)O(4))(NO(3))(3)]·CH(3)OH, the copper(II) ion is tetra-coordinated by two imino N atoms [Cu-N = 1.961 (4) and 1.968 (4) Å] and two phenolate O atoms [Cu-O = 1.931 (3) and 1.938 (3) Å] in a planar geometry. The ten-coordin-ate Dy(III) ion is ligated by six O atoms of three nitrate groups and four O atoms from the ligand [Dy-O = 2.368 (3)-2.601 (3) Å]. In the crystal, complex mol-ecules and solvent mol-ecules are linked by inter-molecular O-H⋯O hydrogen bonds.

Chlorido{2,2'-[propane-1,3-diylbis(nitrilo-methyl-idyne)]diphenolato-κO,N,N',O'}manganese(III).

In the title complex, [Mn(C(17)H(16)N(2)O(2))Cl], the Mn(III) ion is coordinated by two O [Mn-O = 1.719 (2) and 1.813 (2) Å] and two N [Mn-N = 1.824 (2) and 1.931 (2) Å] atoms from the tetra-dentate Schiff base ligand and a chloride anion [Mn-Cl = 2.9634 (16) Å] in a square-pyramidal geometry. In the ligand, the two benzene rings form a dihedral angle of 68.06 (5)°.

{2,2'-[6,6'-Dimethoxy-cyclo-hexane-1,2-diylbis(nitrilo-methyl-idyne)]diphenolato-κO,N,N',O}cobalt(II) monohydrate.

In the title complex, [Co(C(22)H(24)N(2)O(4))]·H(2)O, the Co(II) atom is in an almost square-planar coordination environment involv-ing two O and two N atoms from the Schiff base ligand. A water mol-ecule cocrystallizes with the coordination compound and may be held in the crystal by O-H⋯O hydrogen bonds. Heteroatomic π-π ring inter-actions may be present between symmetry-related complexes, with centroid-centroid distances of 3.5661 (8) Å.

{6,6'-Dimethoxy-2,2'-[cyclo-hexane-1,2-diylbis(nitrilo-methyl-idyne)]diphenolato-κO,N,N',O}iron(II) monohydrate.

In the title complex, [Fe(C(22)H(24)N(2)O(4))]·H(2)O, the Fe(II) center is four-coordinated by two O and two N atoms from 2,2'-[6,6'-dimethoxy-cyclo-hexane-1,2-diylbis(nitrilo-methyl-idyne)]diphen-olate (L) ligands in a distorted square-planar geometry. Uncoordinated water and FeL mol-ecules are paired via inter-molecular water-meth-oxy O-H⋯O hydrogen bonds.

(Acetone-2κO){µ-6,6'-dimeth-oxy-2,2'-[propane-1,2-diylbis(nitrilo-methyl-idyne)]diphenolato-κ1:2O,O,O,O:O,N,N',O}tris-(nitrato-1κO,O')copper(II)samarium(III).

In the title heteronuclear complex, [CuSm(C(19)H(20)N(2)O(4))(NO(3))(3)(CH(3)COCH(3))], the Cu(II) ion is five-coordinated by two O and two N atoms from the 6,6'-dimeth-oxy-2,2'-[propane-1,2-diylbis(nitrilo-methyl-idyne)]diphenolate ligand (L) and by an O atom from the acetone mol-ecule in a square-pyramidal geometry. The Sm(III) ion is ten-coordinated by six O atoms from the three nitrate ligands and four O atoms from the L ligand. In L, the C atoms of the diamino-propane fragment are disordered over two positions in a 0.674 (10):0.326 (10) ratio.

Bis[µ-1,1'-(ferrocene-1,1'-di-yl)bis(butane-1,3-dionato)]di-µ-methanol-diiron(II).

The asymmetric unit of the title compound, [Fe(4)(C(9)H(8)O(2))(4)(CH(3)OH)(2)], contains one half-mol-ecule located on a twofold rotational axis. In the mol-ecule, the two Fe(II) ions bridged by two coordinating methanol mol-ecules are separated by 3.1286 (7) Å. Two crystallographically independent methanol mol-ecules are situated on a twofold rotational axis; all attached H atoms are rotationally disordered between two equal orientations.

High local coordination symmetry around the spin center and the alignment between magnetic and symmetric axes together play a crucial role in single-molecule magnet performance.

A tetradentate 8-hydroxyquinoline-based acyl hydrazone ligand (HL1 = 8-hydroxyquinoline-2-carboxaldehyde-(aminourea)hydrochloride) was elaborately used to construct a mononuclear dysprosium complex DyCl3HL1·CH3OH (1) with a nearly ideal pentagonal bipyramid coordination geometry (D5h) surrounding the Dy(iii) ion to achieve the significant performance of single-molecule magnets (SMMs). Meanwhile, the isolated high local symmetry center was successfully kept intact and further bridged to a series of double bipyramid systems by two phenolic oxygen atoms of the acyl hydrazone ligands (HL1 and HL2 = 8-hydroxyquinoline-2-carboxaldehyde-(benzoyl)hydrazine), with the formulae [Dy2Cl4(L1)2(CH3OH)2]·4C5H5N (2) and [Dy2Cl4(L2)2]·2CH3CN (3). In addition, the monodentate co-ligand anion was replaced by a larger sterically hindered ligand and a bidentate monovalent ß-diketonate anion to generate [Dy2(tfo)4(L2)2(EtOH)2] (4), [Dy2(tta)4(L2)2(EtOH)2]·2(EtOH) (5) and [Dy2(dbm)4(L2)2(EtOH)2] (6) (tfo = trifluoromethanesulfonic acid, dbm = dibenzoylmethane, tta = 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione) with eight-coordinate geometry. Strikingly, the dynamic magnetic measurements revealed that complexes 1-3 did not display the expected significant SMM performance albeit they had high local symmetry. In combination with ab initio calculation, the alignment of the coordination symmetric axis and the magnetic easy axis dominates the molecular magnetic anisotropy, and the magnetic easy axis could be modulated by the distribution of coordination atoms with different electrostatic properties.

From zero-dimensional to one-dimensional chain N-oxide bridged compounds with enhanced single-molecule magnetic performance.

A series of dinuclear dysprosium complexes bridged by pyridine-NO ligands with formula [Ln2(BTA)6(pyNO)2] (1Dy, Ln = Dy, 1Y, Ln = Y and 1Gd, Ln = Gd) (BTA = benzoyltrifluoroacetone, pyNO = pyridine-N-oxide) were structurally and magnetically characterized. The X-ray crystallographic analyses of the structures revealed that the NO group serves as the effective bridge to link two Dy(iii) centers and the periphery ß-diketonate (BTA) ligands complete the rest of the coordination sphere. The dynamic magnetic measurements revealed that complex 1Dy displayed significant zero-field single-molecule magnetic (SMM) behaviour with 72 K energy barrier and 2.5 K hysteresis temperature. In order to extend this dinuclear system, double N-oxide bridged ligand 4,4'-bpdo(4,4'-bipyridine-N,N'-dioxide) was used, and consequently, a series of one-dimensional chain complexes possessing repeated [Ln2(BTA)6(pyNO)2] units were synthesized with formula [Ln2(BTA)6(4,4'-bpdo)]n·2EtOH (2Dy, Ln = Dy, 2Y, Ln = Y and 2Gd, Ln = Gd). The AC magnetic susceptibility measurements revealed that complex 2Dy exhibited significant zero-field slow magnetic relaxation behavior with a higher effective energy barrier of 87 K and a hysteresis temperature of 3 K than 1Dy albeit the separation between the repeated units is large.

Dinuclear Dy2 Single-Molecule Magnets: Functional Modulation on the Bridging Ligand and Different Relaxation Performances within the Single-Crystal to Single-Crystal System.

Crystal structures, single-molecule magnetic behavior, and ab initio calculations of four new phenoxo-bridged dinuclear dysprosium complexes and their gadolinium(III) analogues are explored. Complexes [Dy2 (DMOMP)2 (DBM)4 ]2 ⋅CHCl3 (1; DMOMP=1-methyl-3,5-dimethoxy-4-hydroxybenzene, DBM=1,3-diphenylpropane-1,3-dione); [Dy2 (DMOAP)2 (DBM)4 ]2 ⋅CHCl3 (2; DMOAP=syringaldehyde); Dy2 (DMOEP)2 (DBM)4 (3; DMOEP=methyl syringate); and solvent-free Dy2 (DMOMP)2 (DBM)4 (4), which is obtained by the transformation of single crystal into single crystal from 1, have nearly identical core structures and only differ in the substituents at the para position of the phenol moieties of the bridging ligand. In this system, the electronic effects are efficiently implemented to significantly modify the ligand field strength and exchange coupling by modulating the substituents on the phenol backbone. The effective energy barrier (Ueff ) of magnetization reversal is improved significantly to fivefold magnitude, at most, and the hysteresis temperature up to 3.5 K by deliberately using the electron-withdrawing substituent to replace the electron-donating one. The origin of the two relaxation processes in 1 is mostly attributed to the existence of two molecules in one unit, which is illuminated by means of the transformation of single crystal into single crystal.

A mild and efficient ultrasound-assisted synthesis of diaryl ethers without any catalyst.

Diaryl ethers have been prepared by a mild and efficient S(N)Ar reaction by coupling of various phenols including that having a electron-withdrawing group with activated fluoroarenes using sonication in good to excellent yields at very low temperature (58 degrees C) under catalyst-free.

Organocatalytic Enantioselective Cross-Aldol Reaction of o-Hydroxyarylketones and Trifluoromethyl Ketones.

The enantioselective cross-aldol reaction between o-hydroxyacetophenones and trifluoromethyl ketones catalyzed by chiral thiourea organocatalysts is reported. Gram-scale synthesis of the cross-aldol product was carried out, with no decrease in the yield and enantioselectivity. Furthermore, the cross-aldol products thus prepared were used in the preparation of medicinally interesting 3,5-diaryl-5-trifluoromethyl-2-isoxazoline and ß-trifluoromethyl-ß-tertiary hydroxy acid ester with high yield and enantiopurity.