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Cadmium (Cd) is a non-essential metal with no known biological function and a broad range of toxic effects in biological systems. We used whole-transcriptome sequencing (RNA-seq) to study the effects of Cd

All cells require Cu as a cofactor, but Cu2+ induces toxicity and oxidative damage. A strict system is thus needed to maintain Cu homeostasis. Using the ZFL zebrafish liver cell line as a model, we studied the cellular responses after exposure to Cu2+, using whole-transcriptome shotgun sequencing (RNA-seq) to screen nearly all transcriptomes in cell samples and identify changes in gene expression. ZFL cells were treated with 100, 200, or 400 μM CuCl2 and harvested after 4 and 24 h. RNA was then extracted and subjected to RNA-Seq and qPCR validation. Exposure to 400 μM CuCl2 for 4 h and 24 h led to the regulation of 5993 and 4235 genes, respectively. In a gene ontology enrichment analysis, Cu2+ exposure enriched the nitrogen compound metabolic process and antioxidant activity but did not significantly affect cellular copper, zinc, iron and calcium ion homeostasis. In a KEGG pathway enrichment analysis, anti-oxidative stress induced the glutathione metabolism pathway. Furthermore, Cu2+ also induced genes related to apoptosis and arrested the cell cycle in the G2 phase. This study was based on the full gene expression profile combined with pathway analysis details, providing a full cellular response picture for Cu.

Two new salts, [NO2BrBzPy]2[M(mnt)2] ([NO2BrBzPy]+= 1-(2′-bromo-4′-nitrobenzyl)pyridinium; mnt2−= maleonitriledithiolate; M = Ni(1), Pd(2)) have been prepared and characterized by elemental analyses, IR, UV, ESI-MS spectra, TG, and single-crystal X-ray diffraction. The results reveal that when the metal ion is changed from Ni(II) to Pd(II), the crystal system, and the dihedral angles between the phenyl and pyridine rings and the C-C-N reference plane of the cation, and the stacking modes of the anions and the cations are evidently different. Some weak interactions such as C–H···Br, C−H···O, C−H···N and C−H···S hydrogen bonds, p or stacking interactions in 1 and 2 play important roles in the molecular stacking and generate a 2D structure.

The self-assembly of [Co(NCS)4]2− anion and substituted benzyltriphenylphosphonium cations [4RBzTPP]+ (R = H(1), NO2(2)) results in the forming of two new hybrid materials, [BzTPP]2[Co(NCS)4](1) and [4NO2BzTPP]2[Co(NCS)4](2). The Co(II) ions of the [Co(NCS)4]2− anions in 1 form a 1D chain through S⋯S interactions with the S⋯S distance of 3.458 A, while the C–H⋯S, C–H⋯O hydrogen bond and p⋯π interaction were found in 2. Magnetic susceptibility measurement in the temperature range 2–300 K shows that 1 exhibits a magnetic coupling interaction from ferromagnetic to antiferromagnetic around 30 K as the temperature is lowered, while 2 shows weak antiferromagnetic coupling behavior.

Two tetrabromocuprate (II) salts with substituted benzyl pyridinium, [BzPy]2[CuBr4](1) and [4NO2BzPy]2[CuBr4](2) ([BzPy]+ = 1-benzylpyridinium; [4NO2BzPy]+ = 1-(4′-nitrobenzy- lpyridinium), were synthesized and characterized by elemental analysis, IR, MS, and single-crystal X-ray diffraction. The two salts comprise a [CuBr4]2−anion and two cations, and the [CuBr4]2−anion exhibits a distorted tetrahedral coordination geometry. The weak interactions such as p…π, π…π, C-H…π, C−H…Br or C−H…O hydrogen bonds play important roles in the stacking and stabilization of the two salts, and give rise to a 3D network structure. In addition, the two salts show good antibacterial activities for colibacillus, aurococcus, bacillus subtilus and bacillus thuringiensis.

Two new tetranuclear copper (II) macrocyclic complexes, [Cu4L(OAc)2(OH)2](ClO4)2·2MeCN 1 and [Cu4L (OAc)2(OH)2](PF6)2(H2O)2 2, have been obtained via condensation of 2,6-diformyl-4-methylphenolate with N,N′-bis(3-aminopropyl)-2-thiophenoethylamine in the presence of copper (II) ions. The complexes were characterized by IR, ES-MS and X-ray diffraction techniques. It shows the similar chair-shaped Cu4O4 core structure for these two macrocyclic complexes, which is composed of two kinds of crystallographically independent Cu(II) ions. The coordination spheres of the Cu(II) ions are distorted square pyramid and approximate square-planar configuration, respectively. In addition, it was found that the crystal structures are stabilized by abundant hydrogen bonds between perchlorate anions and adjacent macrocyclic units for complex 1. The network structure of 2 was maintained by π–π stacking of thiopheno groups and C H···F hydrogen bond interactions between adjacent macrocycles. The variable temperature magnetic susceptibility of complex 1 was measured in the temperature range of 2–300 K. The best fitting with a quasi-butterfly magneto-structural model gave the magnetic exchange parameters of Jbb = −197.6 cm−1, Jwb1 = −60 cm−1 and Jwb2 = 103.5 cm−1.

A new mononuclear nickel(II) complex, [NiL2] (HL = ((2-(5-fluoro-2-hydroxybenzyl)(2-(imidazole-2-yl)ethyl))imine), has been synthesized and characterized by IR, UV–vis and X-ray diffraction technique. The X-ray crystal structure of the complex shows that the coordination environment around Ni(II) ion is an approximate octahedron. Each molecule connects with four adjacent neighbors through strong hydrogen bonding interactions (N–H···O, d(N–O) = 2.687 A and ∠N–H···O = 158.3(1)°), forming a supramolecular network. The interaction of the complex with DNA was monitored using agarose gel electrophoresis. The results show that the complex has DNA cleavage activity. The cyclic voltammogram shows one pair of anodic and cathodic peaks with E1/2 = −1.06 V, assigned to the Ni(II)/Ni(I) couple.

Two molecular materials, [3RBzTPP][Ni(mnt)2] (mnt2− = maleonitriledithiolate, [3RBzTPP]+ = 3-R-benzyltriphenylphosphinium, R = CN(1), F(2)), have been investigated and characterized by elemental analyses, IR, UV spectroscopy, X-ray diffraction and magnetic susceptibility measurements. The [Ni(mnt)2]− anions of 1 and 2 stack into a column through the Ni⋯S or/and S⋯S interactions with a Ni⋯S distance of 3.765 A for 1 and with the Ni⋯S and S⋯S distances of 3.654 A and 3.681 A for 2. The weak C H⋯N, C H⋯F hydrogen bonds and π⋯π stacking interactions result in the forming of a 3D network structure. Magnetic susceptibility measurements in the temperature range 2–300 K show that 1 shows an antiferromagnetic coupling behavior with θ = −9.3 K, and 2 exhibits a spin-gap transition with Δ/kb = 945.0 K around 217 K.

Two new coordination polymers of Robson-type macrocycles, [Cu2L1(μ-ClO4)2]∞ (1) and [Cu2L2(μ-ClO4)2]∞ (2) (where H2L1and H2L2 are the [2+2] condensation products of 2,6-diformyl-4-flurophenol with 1,3-diaminopropane and 2-hydroxy-1,3-diaminopropane, respectively), have been synthesized and characterized. The intriguing feature is that intermolecular perchlorato bridges occur between adjacent copper(II) centers. The cyclic voltammograms of the complexes show that each complex undergoes two pseudo-reversible processes with the half wave potentials, −0.361 V and −0.729 V for 1, and −0.372 V and −0.744 V for 2, respectively. Magnetic susceptibility was measured for 1 and 2 over a temperature range of 2–300 K. The optimized magnetic data were J = −359.6 cm−1, j′ = −30 cm−1 and R = 6.8 × 10−8 for 1 and J = −411 cm−1, j′ = −26 cm−1 and R = 2.4 × 10−7 for 2, respectively. The data reveal antiferromagnetic couplings between the copper(II) ions of intra- and intermolecular units.

The self-assembly of [BzEtPy]+([BzEtPy]+ = benzyl-4-ethylpyridinium) cation and the [Ni(mnt)2]− (mnt2− = maleonitriledithiolate) anion results in the forming of a new molecular solid [BzEtPy][Ni(mnt)2](1), in which the anions and cations stack into columns and the Ni(III) ions form a 1D zigzag alternating chain through Ni···S and π···π interactions between [Ni(mnt)2]− anions with the Ni···Ni distances of 3.886 A and 4.781 A, and the four columns of cations create cubic-like large channel in which the [Ni(mnt)2]− columns are located. Magnetic susceptibility measurements show that 1 exhibits a spin gap transition around 90 K.

Two new molecular solids, [BzPyNH2][Ni(mnt)2](1) and [2-NpCH2PyNH2][Ni(mnt)2](2) (mnt2− = maleonitriledithiolate, [BzPyNH2]+ = 1-benzyl-2-aminopyridinium and [2-NpCH2PyNH2]+ = 1-(2′-naphthylmethylene)-2-aminopyridinium) have been characterized structurally and magnetically. The Ni(Ш) ions of 1 and 2 form a 1D magnetic chain within a [Ni(mnt)2]− column through Ni⋯N or π⋯π interactions. Some weak interactions observed in 1 and 2 give further rise to a 2D structure. The overlapping fashions of the [Ni(mnt)2]− anions are different when the 2-aminopyridine ring was fixed and the phenyl ring changed into the naphthyl ring of the cation. Magnetic susceptibility measurements in the temperature range 2–300 K show that 1 is weak antiferromagnetic coupling, while 2 exhibits a novel and interesting spin-gap transition around 140 K with Δ/kb = 381.4 K.

An ionic pair complex, [FClBzDMAP]2[Pd(mnt)2] (1) , ([FClBzDMAP]+ = [1-(4′-fluoro-2′-chlorobenzyl)-4-dimetylamino pyridinium, mnt2− = maleonitriledithiolate), was synthesized and characterized by elemental analyses, IR, UV-vis spectra, molar conductivities and single crystal diffraction. The crystal belongs to the triclinic system, space group P-1 with cell constants a = 8.3472(8) A, b = 9.3988(9) A, c = 13.5875(14) A, α = 76.676(1)°, β = 86.036(1)°, γ = 71.182(1)°, Z = 1. It is interesting that the [FClBzDMAP]+ cations (C) and the [Pd(mnt)2]2− anions (A) in 1 stack into a 1D alternating CC-A-CC-A-CC column along ab direction, while the cations form a 1D column along bc direction. Some weak interactions such as p … π, π … π, Cl … S, and C─ H … N interactions in the crystal play important roles in the self-assembly process and give rise to a 3D network structure.

Syntheses, structural characterizations, magnetic behaviors and theoretical analyses of two new ion-pair complexes, [IFBzIQl][Ni(mnt)2](1) and [IClBzIQl]2[Ni(mnt)2]2 · MeCN(2) [IFBzIQl][Ni(mnt)2] ([IFBzIQl]+ = 1-(2′-fluoro-4′-iodobenzyl)isoquinolinium, [IClBzIQl]+ = 1-(2′-chloro-4′-iodobenzyl)isoquinolinium, mnt2− = maleonitriledithiolate), have been investigated. In crystal of 1, the [Ni(mnt)2]− anions and the [IFBzIQl]+ cations stack into an alternating column through π⋯π stacking interactions. The anions of both 1 and 2 form a dimer via π⋯π stacking and S⋯S short interactions between the [Ni(mnt)2]− anions. The overlapping mode of two neighboring [Ni(mnt)2]− anions in the dimer is the Ni-ring fashion with a Ni⋯Ni distance of 4.076 A for 1, and ring–ring fashion with the Ni⋯Ni and S⋯S distances being 4.395 and 3.593 A for 2. Some weak interactions such as π⋯π, C⋯N, C–H⋯F or C–H⋯N in 1 and 2 play a crucial role in stacking and stabilizing the crystal lattice, and give a 3D network structure and exchange pathways of the magnetic interaction for 1 and 2. Magnetic susceptibility measurements for 1 and 2 in the temperature range 1.8–300 K show that the overall magnetic behavior indicates the presence of antiferromagnetic interaction, while 2 exhibits an activated magnetic behavior in the high-temperature region (HT) together with a Curie tail in the low-temperature region (LT).

Two new ion-pair complexes, [FBrBzPyN(CH 3 ) 2 ] 2 [Ni(mnt) 2 ] (1) and [FBrBzPyN(CH 3 ) 2 ][Ni(mnt) 2 ] (2) (mnt 2- = maleonitriledithiolate, [FBrBzPyN(CH 3 ) 2 ] + =[1-(4'-fluoro-2'-bromobenzyl)-4-dimethylamino-pyridinium]) have been prepared and characterized by elemental analyses, UV, IR, single crystal X-ray diffraction and magnetic susceptibility. The cations (D) and the anions (A) in 1 stack into a 1 D alternating column (i.e., of type ··· DDADDADD ···) via short S···Br. N···F, C···N interactions, and C-H···Br hydrogen bonds. The cation-cation π···π stacking interactions within the columns give further rise to a 2D network structure. Compound 2 forms a 3D structure in which the Ni(III) ions stack into a uniform 1 D zigzag magnetic chain through Ni···S, Ni···Ni, or π···π interactions with a Ni···Ni distance of 4.024 A. Magnetic susceptibility measurements in the temperature range 2-300 K show that 1 is expected to be diamagnetic, and 2 exhibits an interesting spin-gap transition (Δ/k b = 460.6 K) around 155 K.

Two new salts, [2-NaMePy]2[Ni(i-mnt)2] (1) and [2-NaMe-4-MePy]2[Ni(i-mnt)2] (2) ([2-NaMePy]+ = 1-(2′-naphthylmethyl)pyridinium, [2-NaMe-4-MePy]+ = 1-(2′-naphthylmethyl)-4-methylpyridinium and i-mnt2− = iso-maleonitriledithiolate), have been prepared and characterized by elemental analyses, UV, IR, molar conductivity, and single crystal X-ray diffraction. The anions in 1 form a 1-D chain through short C ··· N interactions between the anions, while the cations in 2 stack a 1-D column via C–H ··· π and π ··· π stacking interactions between the cations. The effect of weak intramolecular interactions such as C–H ··· N, C–H ··· S, C–H ··· Ni hydrogen bonds, and π ··· π stacking interactions between the cations and the anions further generate a 3-D network structure. The change of the molecular topology of the countercation when the 4-substituted group in the pyridine ring is changed from H atom to CH3 group results in different crystal system, space group, and the stacking mode of the cations and anions of 1 and 2.

A new ion-pair complex, bis[1-(4 ′ -nitrobenzyl)-3-cyanopyridinium]-bis(maleonitrile-dithiolate)nickelate(II)(1) ([NO 2 BzCNPy] 2 [Ni(mnt) 2 ]), was synthesized and characterized by elemental analyses, IR, MS spectra and single crystal diffraction. The crystal belongs to the triclinic system, space group P-1 with cell constants a = 9.452(1) A, b = 10.395(2) A, c = 11.117(2) A, α = 96.56(1)°, β = 113.94(1)°, γ = 112.68(1)°, Z = 1. The structure was solved by direct methods and refined to R1 = 0.0415 (wR 2 = 0.0771). The structure analysis reveals that the weak C… N, C-H… π, C-H… O, C-H… N interactions and π… π stacking interactios in the crystal play important roles in the self-assembly process and give rise to a 3D network structure.

New alkaline-earth metal cryptates [ML](ClO4)2 · solvent (M = Ca2+, Sr2+, Ba2+; L = 1,4, 12,15,18,26,31,39,42,43,44-undecaazapentacyclo-[13.13.13.16,10.120,24.133,37]-tetratetraconta-4, 6, 8, 10(44), 11,18,20,22,24(43),25,31,33,35,37(42),38-pentadecaene) were synthesized by [2 + 3] template condensation of tris(2-aminoethyl)amine with 2,6-diformylpyridine and characterized by physical methods. The crystal structure of the calcium cryptate was determined. The central atom is nine coordinate with three pyridyl and six imino nitrogen atoms. The coordination polyhedron can be described as slightly distorted tricapped trigonal prism.

A meso cobalt(II) complex, [Co(II) L2L2′] · 4.25H2O, has been synthesized from heterocyclic Schiff‐base ligand N‐ (2‐pyridyliene)‐2‐pyrimidylamine (L1) with inorganic cobalt(II) Salt, and its coordination of chemistry has also been investigated. Carmine block crystals of [Co(II) L2 L2′] · 4.25H2O were obtained from the filtrate which was resulted from the addition of a hot alcohol solution of N‐ (2‐pyridyliene)‐2‐pyrimidylamine (L1) into the alcohol solution of the CoCl2 · 6H2O. Single‐crystal X‐ray diffraction analysis indicates that it crystallizes in a trigonal system with space group R‐3c, with a=24.820(4), b=24.820(4), c=21.010(4) A, α=90°, β=90°, γ=120°, V=11209(3) A3, Z=36, Mr=533.413, F(000)=5060, Dc=1.439 g/cm3, μ(MoKα)=0.742 mm−1, R=0.0666, and wR2=0.2734 for 2229 reflections with I>2σ (I). The Co atom is coordinated in a elongated octahedral geometry by two O atoms, which produced by partial hydrolysis of N‐ (2‐pyridyliene)‐2‐pyrimidylamine (L1), and four N atoms, among which two N atoms were f...

Three new two-photon absorption chromophores based on a pyrimidine core were synthesized by Aldol condensation in the absence of any organic solvents. Their single-photon spectroscopic characterization as well as their two-photon absorption properties is reported. In addition, strong modulation of single-photon and two-photon fluorescent spectra of these molecules by (de)protonation is also discussed.

Three dimetallic complexes of the unsymmetrical macrocycle (L)2−, [M1M2L]2+ (M1M2 = NiNi, CuZn, CuCd), have been synthesized by cyclocondensation between N,N′-bis(3-formyl-4-n-butylsalicylidene)ethylenediimine and 1,3-diaminopropane in the presence of M 1 2 + and M 2 2 + .The crystal structure of the complex [Ni2L4(H2O)2](ClO4)2 · 0.5CH3OH was determined by X-ray diffraction techniques.The asymmetric unit contains two complete macrocyclic complexes which are nevertheless quite similar to one another.The nickel–nickel separations, bridged by the two phenoxides, are 2.977 A and 2.982 A.In each molecule, the Ni(II) located in the ethylene chain linked site has a square planar geometry whereas the Ni(II) located in the propylene chain linked site has an octahedral environment.The results of ES-MS and cycle voltammograms confirm that Cu–Zn, Ni–Ni form stable complexes with the macrocyclic ligand L, however the complex composed of Cu–Cd was unstable, and easily lost Cd2+ from the complex in methanol solution.The cyclic voltammograms of the complexes show that each complex undergoes a stepwise reduction process, e.g.[Ni2L]2+ with E 1 / 2 1 = - 0.862 V and E 1 / 2 2 = - 1.20 V .Magnetic measurements in the 2–300 K range indicate weak antiferromagnetism for the dinuclear nickel(II) complex with the exchange constantJ = −0.90 cm−1.

Seven lathanide cryptates [LnL](NO)3 · nH2O (n=1–3; Ln=La, Ce, Pr, Sm, Eu, Gd, Tb) were synthesized by the reactions of lanthanide nitrates with free ligand L (L was derived from the (2 + 3) condensation of 2,6-diformyl-pyridine (dfp) with tris-(2-aminoethyl) amine (tren)) and characterized by physical methods. ES-MS spectra show that except for La(III) cryptate, the other six are all stable in solution. The crystal structure of the Eu(III) cryptate showed a tricapped prismatic coordination geometry.

The reactions of a dioxotetraamine Cu(II) complex [Cu(H−2L)] (L is 6-(9-fluorenyl)-1,4,8,11-tetraazaandencane-5,7-dione)with O2 − were investigated by electrochemistry, UV–Vis spectrophotometry and pulse radiolysis, respectively. In DMSO solution, [CuII(H−2L)] was oxidized into [CuIII(H−2L)]+ by O2 −, a consecutive reaction was observed with [CuIII(H−2L)(O2 2−)] − as intermediates (k1=1.71×103 M−1 s−1, k2=1.2×10−2 s−1). The mechanism of O2 − dismutation catalyzed by the complex involved alternate oxidation and reduction of Cu(II) by O2 − and the kcat is 6.07 × 107 M−1 s−1 (pH 7.4).

A new neodymium cryptate [NdL](NO)3·H2O (L = 1,4,12,15,18,26,31,39,42,43,44-undecaazapentacyclo-[13.13.13.16,10.120,24.133,37]-tetratetraconta-4,6,8,10(44)11,18,20,22,24(43),25,31,33,35,37(42),38-pentadecaene) was synthesized by the reaction of free ligand L with neodymium nitrate and characterized by physical methods and X-ray crystallography. It crystallizes in space group with a = 14.623(2), c = 32.682(3) A, Z = 6. Final refinement of the structure gave R = 0.042 and Rw = 0.132 . The crystal structure of Nd(III) cryptate shows a tricapped prismatic structure with coordination number nine.

A new polyoxometalate (H2bpy)2{Eu(H2O)3(PW11O39)}·6H2O 1 constructed from lacunary Keggin frameworks, has been hydrothermally synthesized and characterized by IR and X-ray single crystal diffraction. It is interesting to find that the heteropolyanions are linked to chains, and the chains are further connected into an extensive two dimension (2D) layer structure depending on hydrogen bond.

A novel water-soluble octaazamacrocyclic dinuclear copper(II) complex with tetra-pendant arms, [Cu 2 L] Cl 2 ∙ 5H 2 O, was synthesized by [2+2] condensation between 2, 6-diformyl-4-chlorophenol and N, N, N', N'-tetrakis(2'-aminoethyl)-1, 2-diaminopropane in the presence of Cu(OAc) 2 ·H 2 O. Single-crystal X-ray structural analysis reveals that every copper(II) adopts a trigonal bipyramid coordination configuration. Macrocyclic units are joined together by strong π – π stacking interaction with centroid–centroid distance of 3.658 A. Water pentamers with O–O distances of 2.099–2.841 A are observed in the complex. The activity of superoxide dismutase of the complex has been investigated by the nitro blue tetrazolium method.

The copper(II) complex of a new bis-N4O-hexdentate Schiff-base, in which two N,N′-dimethyl-N-(3-(2′-aminoethylimine)-5-(chlorosalicylamine))-N′-(3-imine-5-chlorosalicylamine) units are connected by an ethylene, was synthesized and structurally characterized in the solid state as a form of pentanuclear single helicate based on the square-planar coordination geometries.

In the asymmetric unit of the title compound, [LuIII(C26H34N6O2)(NO3)2]NO3·0.5H2O·0.25C4H8O2, there are two cations and two anions of the title complex, together with a water molecule and half a molecule of ethyl acetate. The Lu atom exhibits a nine-coordinate distorted tricapped trigonal-prismatic coordination geometry. The water mol­ecule is disordered, with occupation factors of 0.4 and 0.6.