Ligand engineering to achieve synergistic properties in a 2D bilayer supertetrahedral chalcogenide cluster-based assembled material.

Incorporating functional organic linkers into supertetrahedral chalcogenolate cluster-based materials is an effective synthetic strategy to expand structural diversity and generate tunable optical and photoelectric properties arising from synergistic effects. Herein, a mixed ligand engineering approach was adopted to design a supertetrahedral cluster-based assembled material [(Cd6Ag4(SPh)16(TPPA)(BPE)0.5)·2DMF]n (denoted as SCCAM-3) with a 2D bilayer architecture and broader visible-light absorption. Interestingly, SCCAM-3 demonstrates a long-lived afterglow at 83 K and efficient photocatalytic activity for degrading tetracycline in water.

Rapid genotyping of 32 insertion/deletion panel for human identification using fluorogenic probes-based multiplex real-time PCR.

BACKGROUND: Insertion and deletion (InDel) polymorphisms have considerable potential in the field of forensic genetics because of their low mutation rate and small amplicons. At present, InDel polymorphisms detection based on the technique of capillary electrophoresis is the main technique used in forensic DNA laboratory. However, this method is complicated and time-consuming, and is not suitable for rapid on-site paternity and personal identification. Next-generation sequencing analysis of InDels polymorphisms requires expensive instruments, large upfront reagent and supply costs, computational requirements and complex bioinformatics, increased the time to obtain results. Thus, there is an urgent need to establish a method to provide reliable, rapid, sensitive and economical genotyping for InDels. METHOD: A rapid InDels (32 InDels) panel was established using fluorogenic probes-based multiplex real-time PCR with microfluidic test cartridge and portable real-time PCR instrument. Then, we performed several validation studies including concordance, accuracy, sensitivity, stability, species specificity. RESULTS: It showed that the complete genotypes could be obtained from ≥100 pg of input DNA and from a series of challenging samples with high accuracy and specificity within 90 min. CONCLUSION: This method provides a rapid and cost-effective solution for InDels genotyping and personal identification in portable format.

Bifunctional Supertetrahedral Chalcogenolate Cluster-Based Assembly Materials Constructed by a Photoactive Ligand.

The assembly of supertetrahedral chalcogenolate clusters (SCCs) and multifunctional organic linkers could lead to the formation of tunable structures and synergistic properties. Two SCC-based assembled materials (SCCAM-1 and -2) constructed by a triangular chromophore ligand, tris(4-pyridylphenyl)amine, were successfully synthesized and characterized. The SCCAMs demonstrate unusually long-lived afterglow at low temperatures (83 K) and efficient activities for the photocatalytic degradation of organic dye in water.

Syntheses, Crystal Structures and Xanthine Oxidase Inhibitory Activity of Aroylhydrazones.

A series of hydrazones, (E)-N'-(4-hydroxy-3-methoxybenzylidene)-4-nitrobenzohydrazide (1), (E)-4-(dimethylamino)-N'-(4-hydroxy-3-methoxybenzylidene)benzohydrazide (2), N'-(2-hydroxy-5-methylbenzylidene)-4-nitrobenzohydrazide (3) and 2-fluoro-N'-(2-hydroxy-5-methylbenzylidene)benzohydrazide (4), were prepared and structurally characterized by elemental analysis, IR and 1H NMR spectra, and X-ray single crystal determination. The xanthine oxidase inhibitory activities of the compounds were investigated. Among the compounds, N'-(3-methoxybenzylidene)-4-nitrobenzohydrazide (1) showed the strongest activity. Docking simulations were performed to insert the compounds into the crystal structure of xanthine oxidase at the active site and to investigate the probable binding modes.

Synthesis, Biological Evaluation, and Molecular Docking Studies of Hydrazones as Novel Xanthine Oxidase Inhibitors.

A series of hydrazones, 2-cyano-N'-(4-diethylamino-2-hydroxybenzylidene)acetohydrazide (1), N'-(5-bromo-2-hydroxy-3-methoxybenzylidene)-3-chlorobenzohydrazide monohydrate (2·H2O), N'-(2-hydroxy-3-methylbenzylidene)-4-nitrobenzohydrazide (3), and N'-(2-hydroxy-3-trifluoromethoxybenzylidene)-4-nitrobenzohydrazide (4), were prepared and structurally characterized by elemental analysis, IR and 1H NMR spectra, and single crystal X-ray determination. Xanthine oxidase inhibitory activities of the compounds were studied. Among the compounds, 2-cyano-N'-(4-diethylamino-2-hydroxybenzylidene)acetohydrazide shows the most effective activity. Docking simulation was performed to insert the compounds into the crystal structure of xanthine oxidase at the active site to investigate the probable binding modes.

Optimization and performance evaluation of double-stranded probe in real-time PCR.

BACKGROUND: TaqMan probe-based real-time PCR (qPCR/RT-qPCR) has been widely used in various fields because of its high sensitivity and specificity. However, TaqMan probes are associated with a relatively higher background signal, and hence negatively affect the detection results. METHODS: Double-stranded probes (DSPs) were designed for the high sensitive detection of hepatitis B virus (HBV) DNA and severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) RNA using qPCR/RT-qPCR. Old DSPs (ODSPs) consist of different lengths of positive and negative strands with complementary oligonucleotides. We systematically optimized ODSPs length, the free energy of hybridization (ΔG) between complementary oligonucleotides, and the length of sticky ends, and the novel DSPs performances were evaluated in comparison with other types of probes. RESULTS: By using similar length positive and negative strands, controlling ΔG between complementary oligonucleotides to approximately -30 kcal/mol, and maintaining the sticky end length at 4-6 nt, the analytical performances of DSPs were significantly improved. Compared with other types of probes, DSPs are advantageous in fluorescence signal intensity and sensitivity. CONCLUSION: DSPs can further improve the detection sensitivity and the detection rate of low-concentration samples in molecular diagnosis.

Synthesis, Crystal Structures and Catalytic Property of Dioxidomolybdenum(VI) Complexes with Tridentate Hydrazones.

New dioxidomolybdenum(VI) complexes with the formula [MoO2L(MeOH)], derived from N'-(5-chloro-2-hydroxy-benzylidene)-2-methylbenzohydrazide (H2L1) and N'-(3,5-dichloro-2-hydroxybenzylidene)-2-methylbenzohydrazide (H2L2) were prepared. Crystal and molecular structures of the complexes were determined by single crystal X-ray dif-fraction method. Both complexes were further characterized by elemental analysis and FT-IR spectra. Single crystal X-ray structural studies indicate that the hydrazones L1 and L2 coordinate to the MoO2 cores through the enolate oxygen, phenolate oxygen and azomethine nitrogen. The Mo atoms in both complexes are in octahedral coordination. Catalytic properties for epoxidation of styrene by the complexes using PhIO and NaOCl as oxidant have been studied.

Syntheses, X-Ray Single Crystal Structures and Biological Activities of Cobalt(III) Complexes with Reduced Schiff Base Ligands.

A new mononuclear cobalt(III) complex, [Co(HL1)2]Cl (1), derived from the reduced Schiff base 2,2'-((ethane-1,2-diylbis(azanediyl))bis(methylene))diphenol (H2L1), and a new dinuclear cobalt(III) complex, [Co2(L2)2]∆2H2O (2), derived from the reduced Schiff base 6,6'-(2-hydroxypropane-1,3-diyl)bis(azanediyl)bis(methylene)bis(2-bromo-4-chlorophenol) (H2L2), were synthesized and characterized by infrared and electronic spectroscopy, and single crystal X-ray diffraction techniques. The ligands were synthesized first, and then bound to the Co(III) centre. Compound 1 contains a mononuclear [Co(HL1)2]+ cation and a chloride anion. The cationic moiety possesses crystallographic inversion center symmetry. Compound 2 contains a dinuclear [Co2(L2)2] molecule and two water hydrate molecules. The Co atoms in the complexes are in octahedral coordination. Both complexes showed potential antimicrobial activity.

Synthesis, Crystal Structures and Antimicrobial Activity of Oxidovanadium(V) Complexes with Hydrazone and Pyrone Ligands.

A pair of oxidovanadium(V) complexes, [VOLL1] (1) and [VOLL2] (2), where L is the dianionic form of the hydrazone ligand N'-(5-chloro-2-hydroxybenzylidene)pivalohydrazide (H2L), L1 and L2 are the deprotonated forms of 3-hydroxy-2-methyl-4H-pyran-4-one (HL1; maltol) and 2-ethyl-3-hydroxy-4H-pyran-4-one (HL2; ethyl maltol), respectively, have been prepared and characterized by elemental analyses, IR and UV-Vis spectroscopy, and single-crystal X-ray crystallographic determination. The V atoms in the complexes are in octahedral coordination, with the hydrazone ligand coordinated to the V atoms through the phenolate O, imino N and enolate O atoms, and with the pyrone ligands coordinated to the V atoms through two O atoms. The effect of the compounds on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans was studied.

Synthesis, Crystal Structures and Catalytic Oxidation of Manganese(III) Complexes Derived from Salen-Type Schiff Base N,N'-Bis(5-nitrosalicylidene)ethane-1,2-diamine.

Two mononuclear Schiff base manganese(III) complexes, [MnL(N3)(OH2)]·CH3OH (1) and [MnL(NCS)(OH2)] · H2O (2), where L is the dianionic form of N,N'-bis(5-nitrosalicylidene)ethane-1,2-diamine, have been prepared and characterized by elemental analysis, IR and UV-Vis spectroscopy and single crystal X-ray diffraction. The Mn atom in each complex is in an octahedral coordination. Molecules of the complexes are linked through intermolecular hydrogen bonds. Catalytic properties for epoxidation of styrene by the complexes using PhIO and NaOCl as oxidant have been studied.

Synthesis, Structures and Antimicrobial Activities of Two Cobalt(II) Complexes [Co(L1)2(OH2)2] and [Co(L2)2].

A new cobalt(II) complex, [Co(L1)2(OH2)2] (1), was prepared by the reaction of 3-bromo-5-chlorosalicylaldehyde (HL1) with cobalt nitrate in methanol. Reaction of 1 with cyclopropylamine in methanol afforded the Schiff base cobalt(II) complex, [Co(L2)2] (2), where L2 is the deprotonated form of 2-bromo-4-chloro-6-(cyclopropyliminomethyl)phenol (HL2). The complexes have been characterized by elemental analyses, IR spectroscopy, and single-crystal X-ray diffraction. The L1 ligand coordinates to the Co atom through the phenolate O and carbonyl O atoms, while the L2 ligand coordinates to the Co atom through the phenolate O and imino N atoms. The Co atom in complex 1 adopts octahedral coordination and that in complex 2 adopts tetrahedral coordination. The effect of the free ligands and the cobalt complexes on the antimicrobial activities against Staphylococcus aureus, Escherichia coli, and Candida albicans was studied.

Synthesis, Crystal Structure, and Catalytic Property of Dioxomolybdenum(VI) Complex Derived from 4-Bromo-N'-(4-diethylamino-2-hydroxybenzylidene) benzohydrazide.

A novel dioxomolybdenum(VI) complex, [MoO2L(MeOH)], where L is the anion of 4-bromo-N'-(4-diethylamino-2-hydroxybenzylidene)benzohydrazide, has been synthesized and characterized by physico-chemical methods and single crystal X-ray determination. In the complex the Mo atom is in octahedral coordination, with three donor atoms of the hydrazone ligand, two oxo groups, and one methanol O atom. The complex exhibits catalytic property for the sulfoxidation reactions. In the presence of the complex a 93% conversion of the sulfide to the corresponding sulfoxide was observed within 60 min and the 100% conversion was achieved after 2 h.

catena-Poly[[[(3,5-dimethyl-1H-pyrazole)-copper(II)]-µ-{N-[1-(2-oxidophen-yl)ethyl-idene]-l-valinato}] methanol monosolvate].

The asymmetric unit of the title compound, {[Cu(C(13)H(15)NO(3))(C(5)H(8)N(2))]·CH(3)OH}(n), contains two complex mol-ecules and two solvent mol-ecules. Each Cu(II) ion is in a distorted square-pyramidal coordination with one N and two O atoms from the Schiff base ligand and one N atom from the heterocycle in the basal positions and one carboxyl-ate O atom from a neighbouring ligand in the apical position. The apical Cu-O bonds are much longer than the basal Cu-O and Cu-N bonds. The carboxyl-ate groups of the Schiff base ligands bridge the Cu(II) ions, forming helical chains along [100]. The crystal packing is stabilized by inter-molecular O-H⋯O and N-H⋯O hydrogen bonds.

{N,N-Dimethyl-N'-[1-(2-pyrid-yl)ethyl-idene]propane-1,3-diamine}bis(thio-cyanato-κN)-copper(II).

In the title complex, [Cu(NCS)(2)(C(12)H(19)N(3))], the Cu(II) atom is five-coordinated in a square-pyramidal geometry defined by one pyridine N, one imine N, and one amine N atom of the tridentate Schiff base ligand and two N-bonded thio-cyanate ions (one of the latter occupying the apical site). The three bridging C atoms and the two terminal C atoms of the Schiff base are disordered over two sets of sites, with occupancies of 0.465 (2) and 0.535 (2).

catena-Poly[[{2-[(2-hy-droxy-eth-yl)imino-meth-yl]-6-meth-oxy-phenolato}copper(II)]-µ-thio-cyanato].

In the title thio-cyanate-bridged polynuclear copper(II) complex, [Cu(C(10)H(12)NO(3))(NCS)](n), the Cu atom is five-coordinated in a square-pyramidal geometry, with one phenolato O, one imino N and one hy-droxy O atom of a Schiff base ligand and one thio-cyanato N atom defining the basal plane, and with one thio-cyanato S atom occupying the apical position. In the crystal structure, pairs of adjacent complex mol-ecules are linked through inter-molecular O-H⋯O hydrogen bonds into dimers. The dimers are further linked via Cu⋯S inter-actions, forming two-dimensional layers parallel to the bc plane.

Bis{2-[3-(dimethyl-ammonio)-propyl-imino-methyl-κN]-6-meth-oxy-phenolato-κO}bis-(thio-cyanato-κN)nickel(II).

The asymmetric unit of the title complex, [Ni(NCS)(2)(C(13)H(20)N(2)O(2))(2)], consists of two half-mol-ecules, both of which are completed by crystallographic inversion symmetry (Ni(2+) site symmetry = in both cases). Both metal ions are six-coordinated in distorted trans-NiO(2)N(4) geometries arising from two N,O-bidentate Schiff base ligands and two N-bonded thio-cyanate ions. The mol-ecular conformations are reinforced by two intra-molecular N-H⋯O hydrogen bonds.

(2,2'-Bipyridine-κN,N'){N-[2-oxido-5-(phenyl-diazen-yl)benzyl-idene-κO]glycinato-κN,O}copper(II).

In the title compound, [Cu(C(15)H(11)N(3)O(3))(C(10)H(8)N(2))], the Cu(II) atom is five-coordinated in a distorted square-pyramidal CuN(3)O(2) geometry. The basal positions are occupied by three donor atoms from the tridentate Schiff base ligand and by one N atom from the 2,2'-bipyridine ligand. The axial position is occupied by the other N atom of the 2,2'-bipyridine ligand. The crystal structure is consolidated by weak C-H⋯O hydrogen bonds. In addition, π-π inter-actions between adjacent pyridine rings (centroid-centroid distances = 3.238 and 3.313 Å) may also stabilize the crystal packing.

Benzyl 3-(10-oxo-9,10-dihydrophenanthren-9-ylidene)dithiocarbazate.

In the title compound, C(22)H(16)N(2)OS(2), the phenanthrene ring is nearly perpendicular to the phenyl ring, making a dihedral angle of 87.2 (2)°. Intra-molecular N-H⋯O inter-actions are present. In the crystal structure, the mol-ecules are linked through inter-molecular C-H⋯O inter-actions. The crystal structure is also stabilized by C-H⋯π inter-actions and weak π-π contacts [centroid-centroid distance = 3.36 (6) Å].

Aqua-{N-[1-(2-oxidophen-yl)ethyl-idene]-l-serinato}copper(II) monohydrate.

In the title compound, [Cu(C(11)H(11)NO(4))(H(2)O)]·H(2)O, each Cu(II) ion is four-coordinated by one N and two O atoms from the tridentate Schiff base ligand, and by one O atom from the coordinated water mol-ecule in a distorted square-planar geometry. Inter-molecular O-H⋯O hydrogen bonds link complex mol-ecules and solvent water mol-ecules into flattened columns propagated in [100].

(1H-Imidazole-κN) {N-[1-(2-oxidophenyl-κO)ethyl-idene]-l-phenyl-alaninato-κN,O}copper(II).

In the title compound, [Cu(C(17)H(15)NO(3))(C(3)H(4)N(2))], the Cu(II) atom is four-coordinated by two O atoms and the N atom of the tridentate Schiff base ligand, and one N atom from the imidazole ligand in a distorted square-planar geometry. In the crystal structure, mol-ecules are linked into dimers by inter-molecular N-H⋯O hydrogen bonds.