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π–π stacking interactions and C–H⋯X (X = O, F) interactions formed by counteranions help to enhance the rigidity of these structures and further improve their luminescence quantum yields.

Five novel mononuclear [Cu(Bphen)(bdppmapy)]X complexes showing photoluminescence were synthesized. The same diphosphine ligand and diimine ligand and different Cu(I) salts were used in the one-pot synthesis of complexes 1–5. These complexes are listed as follows: [Cu(Bphen)(bdppmapy)]CF3SO3 (1), [Cu(Bphen)(bdppmapy)]BF4·0.268CH3OH (2), [Cu(Bphen)(bdppmapy)]ClO4 (3), [Cu(Bphen)(bdppmapy)]I·CH3OH (4) and [Cu(Bphen)(bdppmapy)]Br·2CH3OH (5) (Bphen = 4,7-diphenyl-1,10-phenanthroline, bdppmapy = N,N-bis((diphenylphosphino)methyl)-2-pyridinamine). IR, NMR, elemental analysis, single-crystal X-ray diffraction analysis, UV-vis, fluorescence spectroscopy and terahertz time-domain absorption spectroscopy (THz-TDS) were used to characterize 1–5. Their crystal structures have been elucidated by X-ray crystallography and their photophysical properties have been investigated in detail. These five complexes have a similar coordination center, while their space stacked structures are different, from a 0D dimeric structure to a 3D supramolecular structure. Photophysical studies and density functional theory calculations (DFT) show that the luminescence properties of these five complexes are mainly ascribed to metal-to-ligand charge transfer (MLCT). Among these five complexes, 1 emits luminescence with the highest quantum yield of 36.96% and a lifetime of 11.90 μs at ambient temperature. Different counter-anions lead to the distinction of QYs, maybe due to the influence of weak forces. Terahertz time-domain absorption spectroscopy was used to characterize these ligands and complexes in the range of 0.2–2.4 THz.

Six Cu(i) complexes, [Cu(2,3-f)(bdppmapy)]BF4 (1), [Cu(2,3-f)(bdppmapy)]ClO4 (2), [Cu(2,3-f)(bdppmapy)]CF3SO3 (3), [Cu(imidazo[4,5-f])(bdppmapy)]BF4 (4), [Cu(imidazo[4,5-f])(bdppmapy)]ClO4 (5), and [Cu(imidazo[4,5-f])(bdppmapy)]CF3SO3·MeOH (6·MeOH) (bdppmapy = N,N-bis[(diphenylphosphino)methyl]-2-pyridinamine, 2,3-f = pyrazine[2,3-f][1,10]-phenanthroline, and imidazo[4,5-f] = 1H-imidazo[4,5-f][1,10]-phenanthroline), have been synthesized to explore the effects of counteranions on their crystal structures, photophysical properties, and terahertz (THz) spectra. Time-dependent density functional theory (TD-DFT) shows that the luminescence performance of these complexes is attributed to the metal-to-ligand charge transfer (MLCT) in combination with ligand-to-ligand charge transfer (LLCT). In complexes 1-3, the characteristic peak at 1.4 THz is mainly related to the C-Hπ interaction formed by the H atom on the 4#/5# position of 2,3-f and the benzene ring from the bdppmapy on the adjacent asymmetric unit. The common C-Hπ interaction enhances the rigidity of the structure and has non-negligible influence on the photoluminescence quantum yields (PLQYs): the stronger the C-Hπ interaction is, the higher the quantum yield (QY) is. In complexes 4-6, similar absorption peaks (1.10-1.30 THz) are mainly related to the C-Hπ interactions, and strong absorption peaks (1.50-1.90 THz) are affected by the typical hydrogen bonds N-HF/O and O-HO. These results show that some weak interactions can be characterized by THz time-domain spectroscopy (THz-TDS). So, the THz spectroscopy method would make it possible to tune some of the weak interactions in complex structures to regulate the luminescence of materials.

Nine novel copper(I) complexes with diphosphine and diimine ligands, namely [Cu(dpq)(xantphos)]BF4 (1), [Cu(dpq)(xantphos)]I (2), [Cu(dpq)(dppp)]BF4 (3), [Cu(dppz)(dppp)]BF4 (4), [Cu(dppz)(dppp)]I (5), [Cu(dppz)(pop)]I (6), [Cu(dpq)(pop)]I (7), [Cu(dpq)(pop)]Br (8), [Cu(dpq)(pop)]SCN (9) (dpq = pyrazino[2,3-f][1,10]phenanthroline, dppz = dipyrido[3,2-a:2′,3′-c]phenazine, xantphos = 9,9-dimethyl-4,5-bis(diphenylphosphanyl)xanthene, dppp = 1,3-bis(diphenylphosphino)propane, pop = 1,1′-[(Oxydi-2,1-phenylene)]bis[1,1-diphenylphosphine]), were characterized by single crystal X-ray diffraction, IR, elemental analysis, 1H NMR, 31P NMR, fluorescence spectra and terahertz time domain spectroscopy (THz-TDS). These nine complexes were synthesized by the reactions of copper salts, diimine ligands and various of P-donor ligands through one-pot method. Single crystal X-ray diffraction reveals that complex 9 is of a simple mono-nuclear structure while complexes 6 and 7 are of dimer structures. For complex 8, hydrogen bonds and C H⋯π interactions lead to the formation of a 1D infinite chain structure. Interestingly, complexes 1–5 show novel 2D or 3D network structures through C H⋯π interactions. In addition, complexes 1–3 and 6–9 exhibit interesting fluorescence in the solid state at room temperature. Among the nine complexes, complex 1 shows the highest quantum yield up to 37% and the lifetime of 1 is 6.0 μs. The terahertz (THz) time-domain spectra of these complexes were also studied.

Nine new copper(I) complexes bearing 1,3-bis(diphenylphosphino)propane (dppp) and 4,7-diphenyl-1,10-phenanthroline (batho) or 2,9-dimethyl-1,10-phenanthroline (neo) have been synthesized and characterized. Single crystal X-ray diffraction analysis reveals that complexes 1–4 and 6–9 are mononuclear with similar structures, while complex 5 is a binuclear structure. They display absorption around 280 nm and 410 nm, and the intensive emission in the range of 520–620 nm in the solid state occurring with lifetimes on the μs timescale indicates phosphorescence. Our TD-DFT calculations show that emission from the lowest excited triplet state T1 is of 3MLCT nature. This study manifests that these simple and long-lifetime Cu(I) systems may exhibit a similar, but more complex excited state behavior than the systems previously appreciated.

In this paper, a series of mononuclear/binuclear Cu(I) complexes, [CuI(dpq)(PPh3)2](CF3SO3)·CH3OH (1a), [CuI(dppz)(PPh3)2](CF3SO3)·CH3OH (1b), [CuI2(dpq)2(dppm)2](CF3SO3)2 (2a), [CuI2(dppz)2(dppm)2](CF3SO3)2 (2b), [CuI(dpq)(dppp)](CF3SO3)·CH3OH (3a), [CuI(dppz)(dppp)](CF3SO3)·CH3OH (3b), [CuI(dpq)(POP)](CF3SO3)·CH3OH (4a), [CuI(dppz)(POP)](CF3SO3)·CH3OH (4b), [CuI(dpq)(xantphos)](CF3SO3) (5a), and [CuI(dppz)(xantphos)](CF3SO3) (5b) {dppm = 1,1-bis(diphenylphosphino)methane; dppp = 1,3-bis(diphenylphosphino)propane; POP = bis[2-(diphenylphosphino)phenyl]ether; xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; dpq = pyrazino[2,3-f][1,10]-phenanthroline; dppz = dipyrido[3,2-a: 2′,3′-c]phenazine} have been synthesized and characterized by using IR, NMR, elemental analysis, terahertz (THz) time-domain absorption spectroscopy, UV-vis and fluorescence spectroscopy methods as well as single crystal X-ray diffraction analysis. The single crystal X-ray diffraction results indicated that the immediate geometry around each central Cu(I) in the above complexes is a distorted tetrahedron with the central metal atom being coordinated by the two phosphorus atoms of the phosphine ligands and two nitrogen atoms of the bidentate N-containing heterocyclic ligand moieties. It is found that complexes 1a–5a and 5b show photoluminescence in the solid state at room temperature with the highest quantum yield up to 0.5519, and the increased conjugation in the diimine ligands leads to emission reduction along with a red-shift in the emission maxima. Detailed photo-physical studies and density functional theory calculations (DFT) of these complexes have revealed that their lowest energy absorptions and emissions are ascribed to metal-to-ligand charge transfer (MLCT) excited states. The above results indicate that conjugation effects of N-heteroaromatic ligands play a significant role in the emission properties of mononuclear/binuclear Cu(I) complexes. For the first time, terahertz time-domain spectroscopy is applied for qualitatively understanding the photophysical properties of complexes, revealing that terahertz time-domain spectra are sensitive to the weak interaction between the ligands, especially the diimine ligands, and terahertz spectra are strongly correlated with photoluminescence quantum yields of the complexes.

There are several studies on the use of RNA interference (RNAi) for gene function analysis in fungi. However, most studies on filamentous fungi are based on in vitro-transcribed or -synthesized small interfering RNA (siRNA), and only a few have reported the use of vector-based RNAi. Here we want to develop and evaluate a new vector-based RNAi method using the mouse U6 promoter to drive short hairpin RNA (shRNA) expression in the filamentous fungi. Molecular techniques were employed to develop and evaluate a new vector-based RNAi method using the mouse U6 promoter to drive short hairpin RNA (shRNA) expression in the filamentous fungus Blakeslea trispora. We characterized the mouse U6 promoter and utilized it for the expression of shRNA in B. trispora. Using real-time polymerase chain reaction and western blotting analyses, we confirmed the decrease in the mRNA and protein expression of carRA, respectively, in cells transformed with the mouse U6 promoter-driven shRNA expression vector. This indicated that the shRNA was transcribed from the mouse U6 promoter and correctly processed into siRNA and that the mouse U6 promoter exhibited transcription ability in the filamentous fungi. The results suggest that the mouse U6 promoter that drives the expression of shRNA vectors may serve as a novel tool for RNAi induction in filamentous fungi.

The synthesis of four heteroleptic dinuclear Cu(i) complexes bearing tetraphosphine and diimine ligands was reported. Complexes 1-3 were successfully obtained through microwave synthesis while complex 4 was synthesized through traditionally stirring at room temperature. These complexes are listed as follows: [Cu2(Dpq)2(dppeda)](ClO4)2·1.5CH2Cl2 (1), [Cu2(neo)2(dppeda)](ClO4)2·1.3CH2Cl2·1.7C4H10O (2), [Cu2(batho)2(dppeda)](ClO4)2·C4H10O (3), and [Cu2(batho)2(dpppda)](ClO4)2·3CH2Cl2 (4) {(Dpq = pyrazino[2,3-f][1,10]phenanthroline, batho = 4,7-diphenyl-1,10-phenanthroline, neo = 2,9-dimethyl-1,10-phenanthroline, dppeda = N1,N1,N2,N2-tetrakis[(diphenylphosphino)methyl]-1,2-ethanediamine, and dpppda = N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamine}. Their crystal structures have been elucidated by X-ray crystallography and their photophysical properties have been investigated in detail. Photophysical studies and time domain density functional theory (TD-DFT) calculations show that the luminescence performance of these four complexes is ascribed to metal-to-ligand charge transfer (MLCT) mixed with ligand-to-ligand charge transfer (LLCT), and complex 2 shows green emission at 574 nm with the highest quantum yield of up to 52.80%. In addition, the research of photoluminescence properties under the guidance of terahertz spectroscopy technology leads to the preliminary discovery of a correlation between crystal packing and luminescence. It is found that the terahertz spectrum and absorption peak are strongly interdependent on C-Hπ and ππ interactions, and the external weak interactions have negative effects on the luminescence performance. Herein, we predict that the terahertz spectroscopy analysis establishes a bridge between weak interactions (C-Hπ and ππ interactions) and the photoluminescence properties, and puts forward a problem that should be noticed in designing Cu(i) complexes.

Two new γ-lactone derivatives, evodinoids A (1) and B (2), along with a new essential oil (3) were isolated from the nearly ripe fruits of Tetradium ruticarpum. The structures of these isolations were determined by 1D and 2D NMR, HR-ESI-MS and ECD data analysis. In addition, the cytotoxic effect of compounds 1−3 was evaluated against human cancer cells A498, A549, HepG-2, MCF-7 and SHSY-5Y, which displayed no significant cytotoxicity (IC50 > 100 μM).

Six new silver(I) complexes with diphosphine ligands and 1,10-phenanthroline derivatives are named by [Ag2(dppe)(dicnq)2](CF3SO3)2 (1), [Ag2(dppp)2(dicnq)2](CF3SO3)2 (2), [Ag2(dppb)2(dicnq)2](CF3SO3)2 (3), [Ag(DPEphos)(dicnq)]CF3SO3 (4), {[Ag(dppe)(dmp)](CF3SO3)·(CH3OH)·(H2O)}n (5), [Ag2(dppp)2(dmp)2](CF3SO3)2·(H2O) (6), (dppe = 1,2-bis(diphenylphosphino)ethane, dppp = 1,3-bis(diphenylphosphino)propane, dppb = 1,4-bis(diphenylphosphino)butane, DPEphos = bis[2-(diphenylphosphanyl)phenyl]ether, dmp = 2,9-dimethyl-1,10-phenanthroline, dicnq = 6,7-dicyanodipyridoquinoxaline) were characterized by IR and X-ray diffraction. Further fluorescence spectroscopy, photocatalytic properties and terahertz time-domain spectra (THz-TDS) were performed on 2–6. Complexes 1–3 and 6 were binuclear, while 4 was mononuclear. Complex 5 was a coordination polymer, displaying a one-dimensional infinite chain. Moreover, complexes 1, 2 and 4 were assembled via several pairs of C H⋯π interactions to 1D–3D supramolecular architectures. The emission peaks of the complexes 2–4 all exhibit a large degree of red shift, which may be tentatively attributed to the intraligand transition. Compounds 2–6 represented the first examples of Ag(I) complexes bearing both diphosphine and diimine ligands that exhibit high, efficient photocatalytic abilities for dye degradation under UV light and show good stability toward photocatalysis.

The reactions of diphosphine ligands and nitrogen-containing ligands with Cu(I) salts in the mixed solvents of methanol (MeOH) and dichloromethane (CH2Cl2) generated the corresponding complexes, {[Cu(dppbe)(Bphen)](ClO4)·2CH3OH}n (1), {[Cu2(dppe)(dmp)2(CN)2]·2CH3OH}n (2), {[Cu2(dppb)(dmp)2I2]·2CH3OH}n (3), [Cu(POP)(C16H6N6)]I (4), {[Cu(POP)(C16H6N6)](SCN)}n (5), [Cu(xantphos)(bpy)](ClO4) (6) and {[Cu(xantphos)(bpy)](CF3SO3)}n (7) {dppbe = 1,2-bis(diphenylphosphanyl)benzene, dppe = 1,2-bis(diphenylphosphino)ethane; dppb = 1,4-bis(diphenylphosphino)butane, POP = bis[2-(diphenylphosphino)phenyl]ether, xantphos = 4,5-bis (diphenylphosphio)-9,9-dimethylxanthene, Bphen = 4,7-diphenyl-1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, C16H6N6 = [2,3-f]-pyrazino-[1,10]phenanthroline-2,3-dicarbonitrile, bpy = 2,2′-bipyridine}. These complexes were all characterized by single-crystal X-ray crystallography, elemental analysis, IR, 1H NMR spectroscopy, luminescence and THz spectroscopy. Complexes 1 and 2 consist of 1D infinite zigzag chain structures which are linked by hydrogen bonds, while complexes 3, 5 and 7 have 2D topological architectures which are connected by hydrogen bonds, complex 4 has an annular structure and complex 6 is a mononuclear structure. The types of hydrogen bonds, choice of solvents and coordination modes of the ligands are of importance in defining the structural and topological features of the resulting networks. Furthermore, complexes 1–7 exhibit interesting luminescence in the solid state at room temperature. Complexes 1–3 can act as yellow luminophores, complex 4 acts as a red luminophore, complex 5 acts as an orange luminophore and complexes 6–7 act as green luminophores. Their terahertz spectra show more accurate characteristics of their structures.

Five new phenylpropanoid amides, including N-trans-feruloyl-N′-cis-feruloyl-cadaverine (1), N,N′-trans-diferuloyl-3-oxo-cadaverine (2), N-trans-feruloyl-N′-cis-feruloyl-3-hydroxy-cadaverine (3), N,N′-cis-diferuloyl-3-hydroxy-cadaverine (4), N-trans-p-coumaroyl-N′-trans-feruloyl-3-hydroxy-cadaverine (5), were isolated from Alisma orientalis together with four known analogues. Their structural elucidations were conducted by using 1D and 2D NMR and HRESIMS spectroscopic analyses. The isolated compounds were assayed for their inhibitory activities against HCE-2, anti-oxidant effects, and their protective effects on H2O2-induced damage in human dopaminergic neuroblastoma cells (SH-SY5Y). Compounds 3, 6, and 7 displayed moderate anti-oxidant activities with IC50 values in the range of 36.9–40.7 μM. Compound 5 showed significant protective activity, while compounds 1, 2, 4, 7, and 8 showed moderate protective activities.

Eight silver (I) complexes with P-donor ligands [triphenylphosphine (PPh3), bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe) and 1,4-bis(diphenylphosphino)butane(dppb)] and mercaptan ligands [3-amino-5-mercapto-1,2,4-triazole (H2AMTA), 2-amino-5-mercapto-1,3,4-thiadiazole (HAMTD), 2-mercapto-6-nitrobenzothiazole (HMNBT) and 2-mercapto-5-methyl-benzimidazole (HMMBD)] named by [Ag2(PPh3)4(HAMTA)2]n (1), [Ag3(dppm)3(AMTD)2]2(BF4)2·(dppm) (2), [Ag3(dppm)3(AMTD)2]2(ClO4)2·(dppm) (3), [Ag4(dppm)4(MNBT)2](SO4)·(H2O) (4), [Ag4(dppe)4(HAMTA)2(AMTA)] (5), [Ag2(dppb)2(HAMTD)2](CF3SO3)2·2(CH3OH) (6), [Ag2(dppb)2(HMNBT)2](CF3SO3)2 (7) and {[Ag(dppb)(HMMBD)2](CF3SO3)·2(CH3OH)·(H2O)}n (8) are characterized by X-ray diffraction, NMR and fluorescence spectroscopy. Complexes 1 and 8 show 2D network structure. Complexes 2–5 are multi-nuclear clusters. Complexes 6–7 are of di-nuclear structure. In complex 7, the offset π⋯π interactions between the neighboring benzene rings help to form the 1-D infinite chain. All the emission peaks of these complexes are attributed to ligands-centered [π–π∗] transitions.

Seven lanthanide complexes [Ln(OPPh3)3(NO3)3] (1–3) (OPPh3 = triphenylphosphine oxide, Ln = Nd, Sm, Gd), [Dy(OPPh3)4(NO3)2](NO3) (4), [Ln(OPPh3)3(NO3)3]2 (5–7) (Ln = Pr, Eu, Gd) were synthesized by the reactions of different lanthanide salts and OPPh3 ligand in the air. These complexes were characterized by single-crystal X-ray diffraction analysis, elemental analysis, IR and fluorescence spectra. Structure analysis shows that complexes 1–4 are mononuclear complexes formed by OPPh3 ligands and nitrates. The asymmetric units of complexes 5–7 consist of two crystallographic-separate molecules. Complex 1 is self-assembled to construct a 2D layer-structure of (4,4) net topology by hydrogen bond interactions. The other complexes show a 1D chain-like structure that was assembled by OPPh3 ligands and nitrate ions through C–H···O interactions. Solid emission spectra of compounds 4 and 6 are assigned to the characteristic fluorescence of Tb3+ (λem = 480, 574 nm) and Eu3+ (λem = 552, 593, 619, 668 nm).

Biocatalysis of capsaicin (1) was performed by Penicillium janthinellum AS 3.510. Nine metabolites including four new compounds were afforded, and their structures were elucidated as (8S)-trans-8-hydroxy-8-hydroxymethyl-N-vanillyl-6-nonenamide (2), 6-hydroxy-8-methyl-N-vanillyl-7-nonenamide (3), trans-8-methoxy-8-methyl-N-vanillyl-6-nonenamide (4), 6-methoxy-8-methyl-N-vanillyl-7-nonenamide (5), dihydrocapsaicin (6), ω-1-hydroxydihydrocapsaicin (7), ω-1-hydroxycapsaicin (8), ω-hydroxycapsaicin (9), N-(4-hydroxy-3-methoxybenzyl)-5-[3-(propan-2-yl)oxiran-2-yl]pentanamide (10) by 1D and 2D NMR and HRESIMS spectra. The biotransformation processes include hydroxylation, methylation, reduction, and epoxylation.

Sixteen lanthanide–diphosphate complexes [LnL2(H2O)4Cl]Cl2 (Ln = La3+ for 1, Ln = Ce3+ for 2), [LnL2(H2O)4]Cl3·6H2O (Ln = Nd3+ for 3, Ln = Sm3+ for 4, Ln = Eu3+ for 5, Ln = Gd3+ for 6, Ln = Tb3+ for 7, Ln = Dy3+ for 8, Ln = Er3+ for 9), {[LaL2(H2O)4Cl]Cl2}2 (10), [PrL2(OH)2(H2O)Cl] [PrL2(H2O)4Cl]Cl2 (11), [LaL2(H2O)5Cl]Cl2·2H2O (12), [YbL2(H2O)3Cl]Cl2·H2O (13), [NdL2(H2O)3Cl]Cl2·3H2O (14), [HoL2(H2O)Cl2]Cl·H2O (15), [Sc2L2(H2O)4(OH)2]Cl4·4H2O·2CH3OH (16) (L = tetrakis(O-isopropyl)methylenediphosphonate) have been synthesized by the reaction of lanthanide chlorides and L ligand in the solvent of acetonitrile (with ethanol or DMF) at room temperature. The title complexes were characterized by IR, elemental analysis, single-crystal X-ray diffraction analysis, thermal analysis, 1HNMR and 31PNMR spectroscopy. Complexes 1–15 are mononuclear complexes and complex 16 is a binuclear cluster complex. Complex 12 is the intermediate of complex 1. Complexes 11–13 display a one-dimensional chain formed by hydrogen bonds and the structures of complexes 14, 16 can be simplified as two-dimensional mesh 63 topology formed by hydrogen bonds. In those lanthanide complexes, the lanthanide ion with an atomic number smaller than Pr element tends to form a nine-coordinated structure and that with the atomic number larger than Pr element tends to form an eight or lower number-coordinated structure. Pr element has two kinds of coordination situations, with coordination numbers of nine or eight. The terahertz (THz) time-domain spectra of these complexes were also studied.

C54H52Ag2B2F8P4, triclinic, P1̄ a = 11.4869(4) Å, b = 12.9118(5) Å, c = 19.6858(6) Å, α = 100.8240(10)°, β = 102.185(2)°, γ = 110.470(3)°, V = 2562.31(15) Å3, Z = 2, R gt(F) = 0.0263, wR ref(F 2) = 0.0666, T = 293(2) K.

C61H52Ag2N2O6P2, orthorhombic, P212121 (no. 19), a = 14.4634(11) Å, b = 17.7866(18) Å, c = 20.5509(19) Å, V = 5286.8(8) Å3, Z = 4, R gt(F) = 0.0424, wR ref(F 2) = 0.0997, T = 298(2) K.

Alisma orientalis is a well-known traditional Chinese medicine with diuretic, hypopietic, hypolipemic, and antiatherosclerotic activities. In the present study, we investigated triterpenoids from the rhizome of A. orientalis , identifying four new alisol derivatives, namely, Alismanol M ( 1 ), Alismanol Q ( 2 ), Alismanol O ( 3 ) and Alismanol P ( 4 ). The structures of these compounds were characterized using detailed spectroscopic analysis (UV, HRESIMS, 1D and 2D NMR data including HSQC, HMBC, 1 H– 1 H COSY, and NOESY). These four new alisol derivatives were all protostane triterpenoids, belonging to a group of tetracyclic triterpenes. A 17, 23- or 20, 24-five-membered oxide ring is the primary structural characteristic of these alismanols ( 1 – 4 ). Furthermore, in vitro bioassays demonstrated that the isolated compounds could not inhibit nitric oxide production in LPS-induced macrophages.

Six novel lanthanide complexes [LnL(Phen)Cl3]n (1–6) (Ln = Sm, Eu, Gd, Tb, Dy, Ho) (L = tetraethyl ethylenebisphosphonate, Phen = 1,10-phenanthroline) have been synthesized through a simple one-pot reaction. Complexes 1–6 are of 1D infinite chain structure. The C H∙∙∙π interactions and the bridging action of L ligand lead to the formation of 3D network structures for 1–6. Emission spectra of complexes 1, 2, 4 and 5 show characteristic emission peaks of Sm3+, Eu3+, Tb3+ and Dy3+, respectively. Quantum yield of 2 is up to 37% while that of 4 reaches 31% in solid state, so they can be used as potential luminescent materials.

Direct reactions under ambient conditions among copper/silver salts, diimine ligands and diphosphine ligands were carried out at different rations, generating nine novel Cu(I)/Ag(I) complexes, [Cu(Dpq)(dppp)](ClO4) (1), [Cu(Dppz)(dppp)](ClO4) (2), [Cu(Dpq)(POP)](ClO4) (3), [Cu(Dppz)(POP)](ClO4) (4), [Cu(Dpq)(xantphos)](ClO4)·0.843CH2Cl2 (5), [Cu(Dppz)(xantphos)](ClO4)·2CH2Cl2 (6), [Ag(Dpq)(xantphos)](ClO4) (7), [Ag(Dpq)(xantphos)](CF3SO3) (8), [Ag(Dpq)(POP)](CF3SO3) (9). {Dpq = pyrazino[2,3-f][1,10]phenanthroline, Dppz = dipyrido[3,2-a:2′,3′-c]phenazine, POP = 1,1′-[(Oxydi-2,1-phenylene)]bis[1,1-diphenylphosphine], xantphos = 9,9-dimethyl-4,5-bis(diphenylphosphanyl)xanthene, dppp = 1,3-bis(diphenylphosphine)propane). Their crystal structures have been determined by single crystal X-ray diffraction and they were characterized by IR, UV, elemental analysis, fluorescence spectra, 1H NMR and 31P NMR spectroscopy. All above nine Cu(I)/Ag(I) complexes have intriguing crystal stacking structures. Complexes 3, 9 are of 1D infinite chain structures formed by C–H⋯π interactions between each adjacent molecule while complexes 1, 2, 5, 6, 8 are of 2D network structures because of hydrogen bonds, C–H⋯π interactions and π⋯π interactions. However, complex 4 is complicated three-dimensional structure formed by C–H⋯π interactions. Some of the complexes exhibit obvious luminescence in the solid state, and interesting photoluminescence phenomenon are explained in detail. Among these six Cu(I) complexes, complex 5 shows the highest quantum yield up to 17.2%, which is due to the large steric hindrance of xantphos ligand. For these three Ag(I) complexes, complex 8 displays the highest quantum yield of 19.5%. In addition, the terahertz time-domain spectrum (THz-TDS) of these complexes has been investigated in detail leading to the preliminary discovery of correlation between terahertz spectra and crystal packing of complexes.

Bufalin was a typical bioactive bufadienolide, existed in the traditional Chinese medicine Chan Su with the high content of 1-5%. The in vivo metabolites (1-5) of bufalin were prepared by various chromatographic techniques from the bile samples of SD rats, which were administrated with bufalin orally. Their structures were determined on the basis of the widely spectroscopic data, including HRESIMS, 1D-, and 2D NMR. And 1-3, 5 were new compounds. In the in vitro cytotoxicity assay, metabolites (1-5) showed weaker cytotoxic effects than bufalin against human cancer cell lines A549 and H1299, which indicated that the metabolism was a significant pathway for the detoxification of bufalin. Structures analyses indicated that metabolites 1-5 were hydroxylated derivatives of bufalin. This study suggested that Phase I metabolism catalyzed by CYP450 enzymes was one of the metabolic ways of bufalin, which may promote the excretion of bufalin.

Alisol G, also named 25-anhydroalisol A, is a major triterpene obtained from dried rhizomes of Alisma orientalis. This paper investigated the transformation of alisol G by fungi and evaluated the hCE2 inhibitory effects of the transformed products. By screening whole cells of 10 strains of filamentous fungi, Penicillium janthinellum AS 3.510 exhibited a special capability to transform alisol G. Four metabolites were obtained, which were determined to be new compounds on the basis of spectroscopic data, including UV, 1D- and 2D-NMR, and HRESIMS. In addition, in an in vitro bioassay, metabolites 1–4 showed significant hCE2 inhibitory activities with IC50 values of 6.81, 16.66, 3.38, and 6.33 μM, respectively.

Two new protostane-type triterpenoids, 17-epi alisolide (1) and 24-epi alismanol D (2), were isolated from Alisma orientalis together with one known compound. Their structural elucidations were conducted by NMR, UV and HRESIMS spectroscopic analyses, and comparison with the literature data. All the isolated compounds were evaluated for inhibitory effects on HCE-2. Compound 2 displayed moderate inhibitory activity against HCE-2 with IC50 value of 23.1 μM.

Imperation analogs have the furanocoumarin skeleton, with the isopentenyl group, which displayed significant bioactivities. The biotransformation of furanocoumarins imperation, isoimperation and phellopterin (1-3) by fungi has been proved to be an efficient method for the structural modification. Ten transformed furanocoumarin analogs were obtained by fungal biotransformation, including one new highly oxygenated furanocoumarin (4c). Aspergillus niger AS 3.739 displayed selectively transformed capability toward furanocouamrins (1-3) with one or two major products. So, seven hydroxylation and hydrolysis derivatives have been prepared efficiently. Additionally, the biotransformation of phellopterin gave multiple products (4a, 4b, 4c) by Cunninghamella blakesleana AS 3.970. The biotransformation time-courses of furanocoumarins have been established, which suggested the preferred incubation time. The bioactivities of furanocoumarin analogs have been investigated in an in vitro bioassay. And, furanocoumarins 1-3, 2a, and 2c displayed moderate anti-osteoporosis activities using MCET3-E1 cell line at the concentrations of 1, 10, and 100 μM.

Different proportions of polyamidoamine (PAMAM) dendrimer were blended with poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) resin in chloroform for film casting. Differential scanning calorimetry and scanning electron microscopy were employed to characterize the PHBV/PAMAM composite films upon stretching and tangential breaking. The results indicated that with the addition of PAMAM dendrimer, the glass transition temperature of the PHBV/PAMAM composite films became more distinct, indicating that the blends had a greater toughness than pure PHBV. The calculated crystallinity values indicated that the crystallinity of the PHBV/PAMAM blends was lower than that of PHBV (0.09–56.18 % vs. 73.18 %, respectively). Moreover, the mechanical performance tests indicated that the addition of PAMAM dendrimer considerably increased the tangential breaking strength of PHBV from 24.08 kN/m to as high as 62.03 kN/m, whereas the tensile strength remained basically unchanged. The optimal toughening effect was observed with a PAMAM dendrimer content of 3.0 phr.

Volatile constituents and phenols of Gynura bicolor DC grown under three different CO2 levels of ambient (450 μmol mol−1) and elevated (1200, 2000 μmol mol−1) and three LED light conditions of WL (white light), RB20 (red/blue = 8/2) and RB40 (red/blue = 6/4) were investigated to improve efficient production of bioactive compounds in this vegetables under controlled environment. Results showed that increased CO2 caused a significant decrease in volatile terpenoids from G. bicolor DC leaves as compared with ambient CO2 at any light treatments. Plants grown under ambient CO2 with RB20 LED lighting had the highest yield of volatile terpenoids. In addition, CO2 elevation from 450 to 1200 improved the production of phenols (including anthocyanins, flavonoids and phenolics), while increasing CO2 from 1200 to 2000 appeared to negate such promotion. Furthermore, phenols contents were promoted by RB20 as compared with WL light treatment, whereas those were not further improved when increasing blue lights up to 40% (RB40). Our results indicated that the better choices for G. bicolor DC to produce more volatile terpenoids and phenols under controlled environment were at ambient and elevated CO2 levels with RB20 LED lighting condition, respectively.

Resibufogenin (RB), a major bioactive bufadienolide, has the potential anticancer activity. In the present work, biotransformation of RB by Actinomucor elegans AS 3.2778 yielded five products, namely 3-oxo-resibufogenin (1), 3-epi-resibufogenin (2), 3-epi-12-oxo-hydroxylresibufogenin (3), 3α-acetoxy-15α-hydroxylbufalin (4), and 3-epi-12α-hydroxylresibufogenin (5), respectively. Among them, metabolites 3 and 4 are previously unreported. The chemical structures of metabolites 1-5 were fully elucidated on the basis of 2D NMR and HR-MS. The highly stereo- and regio-specific isomerization, hydroxylation, and esterification reactions were observed in the biotransformation process of RB by A. elegans. Their cytotoxicities against A549 and H1299 cells were evaluated.

In this paper, the microbial transformation of resibufogenin by Curvularia lunata AS 3.4381 was investigated, and four transformed products were isolated and characterized as 3-epi-resibufogenin (2), 12α-hydroxy-3-epi-resibufogenin (3), 12-oxo-16β-hydroxy-3-epi-resibufogenin (4), and 12β,15-epoxy-3-epi-bufalin-14,15-ene (5). Among them, 4 and 5 are new compounds, and isomerization, hydroxylation, and oxidation reactions in microbial transformation process were observed. Additionally, the cytotoxicities of transformed products (2-5) were also investigated.

Microbial biotransformation of acetyl-11-keto-boswellic acid by Cunninghamella elegans AS 3.1207 was carried out, and totally four transformed products were isolated. On the basis of the extensive spectral data, their structures were characterized as 7β-hydroxy-11-keto-boswellic acid (1), 7β,30-dihydroxy-11-keto-boswellic acid (2), 7β,16α-dihydroxy-3-acetyl-11-keto-boswellic acid (3), and 7β,15α,21β-trihydroxy-3-acetyl-11-keto-boswellic acid (4), respectively. Among them, products 1 and 2 are the new compounds.

Osthole ( 1 ) as a natural product, has the potent anti-osteoporosis activity. In the present paper, a scaled-up biotransformation of 1 by Mucor spinosus AS 3.3450 was carried out for improving its activities and water-solubility. Nine metabolites were obtained in the biotransformation process of 1 , and their structures were elucidated as 4′-hydroxyl-osthole ( 2 ), osthenol ( 3 ), osthenol-7-O- β - d -glucoside ( 4 ), 5′-hydroxyl-osthole ( 5 ), 5′-hydroxyl-2′,3′-dihydro-osthole ( 6 ), 2′,3′-dihydroxyl-osthole ( 7 ), 2′-ketone-3′-hydroxyl-osthole ( 8 ), 2′-acetoxy-3′-hydroxy-osthole ( 9 ) and 2′-hydroxyl-isoothole ( 10 ), on the basis of extensive spectral data including 2 D NMR and MS spectroscopy. Among them, metabolites 6 and 8 were new. The hydroxylation, dehydrogenation, demethylation and glycosylation reactions of 1 by M. spinosus AS 3.3450 were reported in the present study. And anti-osteoporosis activities of all products were also evaluated by using MC3T3-E1 cells.

In this paper, microbial transformation of kurarinone (1) by Cunninghamella echinulata AS 3.3400 was investigated and four transformed products were isolated and identified as 6″-hydroxykurarinone (2), 4″,5″,8″-trihydroxynorkurarinone (3), norkurarinone (4), and kurarinone-7-O-β-glucoside (5), respectively. Among them, 3 and 5 are new compounds, and the rare glycosylation in microbial transformation was observed. In addition, the cytotoxicities of transformed products (2-5) were also investigated.

Two new silver(I) complexes [Ag2(μ-dppb)2(CF3SO3)2] (1) and {[Ag2(dppb)3](CF3SO3)2•(4,4′-bipy)•(CH3CN)2}n (2) (dppb = bis(diphenylphosphino)butane, 4,4′-bipy = 4,4′-bipyridine) which contain dppb and trifluoromethanesulfonate anions have been synthesized and characterized by IR, X-ray crystallography, 1H NMR, 31P NMR spectroscopy and luminescence. Complex 1 and 4,4′-bipy reacted in the solution CH3CN to get complex 2. In the reaction, the 14-membered ring [Ag2(μ-dppb)2] of complex 1 is opened to form the “honeycomb” (6, 3) network structure of complex 2. In 2, each [Ag6(μ-dppb) 6] 6+ ring hosts two counterions, one 4,4′-bipy and two acetonitrile guest molecules.

Possible clinical diagnosis biomarkers of diabetes were proposed using proteomics and bioinformatics methods through the preliminary study on the formaldehyde-human serum albumin crosslinkage. Using LC/MS techniques, the experiment on in vivo cross-linking reaction of formaldehyde with pure protein or plasma protein revealed that the cross-linking reaction of human serum albumin and forrmaldehyde would occur and the concentrations of some normal peptides would change. A group of significant peptides of human serum albumin were selected. As the results of in vivo cross-linking reaction, Non-enzymatic glycosylation modification of HSA were observed in diabetic. The same change of the concentrations of some peptides happened. The above-mentioned results were demonstrated with the hematoplasmas of normal people and diabetics.

Biotransformation of deoxyandrographolide (1) by Fusarium graminearum AS 3.4598 was investigated in this paper. And five transformed products of 1 by F. graminearum AS 3.4598 were obtained. Their chemical structures were characterized as 3-oxo-8α,17β-epoxy-14-deoxyandrographolide (2), 3-oxo-14-deoxyandrographolide (3), 3-oxo-17,19-dihydroxyl-8,13-ent-labdadien-15,16-olide (4), 1β-hydroxyl-14-deoxyandrographolide (5), and 7β-hydroxyl-14-deoxyandrographolide (6) by spectral methods including 2D NMR. Among them, products 2, 4, and 5 are new.

The capabilities of twenty strains of filamentous fungi (from 9 genera) to transform deoxyandrographolide (1) were screened. And eleven derivatives of 1 transformed by Cunninghamella echinulata AS 3.3400 were isolated. Their chemical structures were identified by spectral methods including 2D NMR. Among them, 3-oxo-7α-hydroxy-14-deoxyandrographolide (2), 3-oxo-8β,17α-epoxy-14-deoxyandrographolide (3), 8α-formyl-14-deoxyandrographolide (4), 8β-methoxyl-17α-hydroxyl-14-deoxyandro-grapholide (5) and 3α,17,19-trihydroxyl-7,13-ent-labdadien-15,16-olide (6), are new compounds. And their structure–activity relationships (SAR) were also discussed.

Preparative high-speed counter-current chromatography (HSCCC) was successfully applied to purify phenylpropanoids from the stem and root bark of Daphne giraldii Nitsche, a traditional Chinese medicine. Their structures were identified on the basis of 1H NMR and 13C NMR technology. The two-phase solvent system composed of n-hexane–ethyl acetate–methanol–water (2: 3: 0.5: 4, v/v/v/v) was selected for HSCCC. A total of 8.0 mg woonenoside XI (1) and 18.0 mg daphnetin (2) were obtained in one-step separation from 200 mg of the crude extract with purity of 96.0 and 99.1%, respectively, as determined by LC. And the major compound (2) showed antithrombotic activity in vitro.

Five hydroxylated derivatives of glycyrrhetinic acid by Mucor polymorphosporus were isolated. Among them, 6beta, 7beta-dihydroxyglycyrrhentic acid (2) and 27-hydroxyglycyrrhentic acid (3) are new compounds. Their chemical structures were identified by spectral methods including 2D-NMR.

The capabilities of 24 strains of filamentous fungi (from 11 genera) to transform dehydroandrographolide ( 1 ) were screened. The highly region-specific hydroxylation of 1 at C-9 by Cunninghamella echinulata AS 3.3400 was observed. Five products were obtained, and they were identified as 9β-hydroxydehydroandrographolide ( 2 ), 3-oxo-hydroxydehydroandrographolide ( 3 ), 3-oxo-9β-hydroxydehydroandrographolide ( 4 ), 7α-hydroxydehydroandrographolide ( 5 ) and 8β,17α-epoxydehydroandrographolide ( 6 ), respectively. Among them, products 2 , 4 and 5 were novel compounds.

Two new transformed sesquiterpenes of alantolactone by Mucor polymorphosporus were obtained. They were characterized as 3beta-hydroxy-11betaH-eudesm-5-en-8beta,12-olide (2) and 3beta,11alpha-dihydroxy-eudesm-5-en-8beta,12-olide (3), on the basis of spectral methods including 2D NMR. And product 3 was an unusual hydroxylation derivative of alantolactone at C-11.

A liquid chromatographic method was applied to determine trifolirhizin, kushenol K, kushenol L, kushenol N, kushenol X, kurarinone, norkurarinone, isokurarinone and kushenol A in the roots of Sophora flavescens, namely Kushen in China. The samples were separated on a YMC-C18 column (250 × 4.6 mm, 5 μm) with a gradient of methanol and 0.3% aqueous acetic acid (v/v) at a flow rate of 0.8 mL min−1 and detected at 295 nm. The complete separation was achieved within 45 min for the nine major flavonoids. All calibration curves expressed good linearity (r 2 > 0.999) within the test range. The recovery of this method was 92.3–106.9%. The assay was successfully applied to the quantification of nine flavonoids in 26 samples of Kushen. The results indicated that this developed LC assay could be readily utilized as a quality control method for the Chinese herb medicine Kushen.

A new ent-labdane diterpenoid lactone with a new natural product was isolated from Andrographis paniculata. Their structures were elucidated on the basis of spectral evidences including 2D NMR.

A new lavandulyl flavonoid was isolated from the rhizome of Sorphora flavescens. The structure of new compound was elucidated on the basis of spectral methods including 2D NMR. And it showed potent cytotoxic activity against Hela ceils with IC50 of 1.1 μmol/L.

The biotransformation of osthole (1) by Alternaria longipes was carried out, and five transformed products were obtained in the present research work. Based on their extensive spectral data, the structures of these metabolites were characterized as 4'-hydroxyl-osthole (2), 4'-hydroxyl-2',3'-dihydroosthole (3), 2',3'-dihydroxylosthole (4), osthole-4'-oic acid methyl ester (5), and osthole-4'-oic acid glucuron-1-yl ester (6), respectively. Among them, products 5 and 6 were new compounds.

In this paper, microbial transformation of norkurarinone (1) by Cunninghamella blakesleana AS 3.970 was investigated and seven transformed products were isolated and characterized as kurarinone (2), 4″,5″-dihydroxykurarinone (3), 6″-hydroxyl-2′-methoxyl-norkurarinone 7-O-β-d-glucoside (4), 6″-hydroxyl-norkurarinone 4′-O-β-d-glucoside (5), 4″,5″-dihydroxynorkurarinone (6), 7-methoxyl-norkurarinone (7), and 7-methoxyl-4″,5″-dihydroxynorkurarinone (8), respectively. Among them, 3–5 are new compounds, and the glycosylation reaction in microbial transformation process was reported rarely. In addition, the cytotoxicities of transformed products (1–8) were also investigated.