New evidence of the emergence of the East Asian monsoon in the early Palaeogene.

Previous palaeoenvironmental reconstructions have implied that East Asia was dominated by a zonal climate pattern during the Eocene, with an almost latitudinal arid/semiarid band at ~ 30° N. However, this long-standing model has recently been challenged by growing body of multidisciplinary evidence. Some studies indicated that central China was characterized by climatic fluctuations between humid and drier conditions during the Early Eocene, akin to the present East Asian monsoon (EAM) regime. Using palynological assemblages in the Tantou Basin, central China, we quantitatively reconstructed climate changes from the Late Palaeocene to Early Eocene to better understand climate change in central China. Palynological assemblages revealed that the coniferous and broad-leaved mixed forest in this area received no less than 800 mm of annual precipitation and experienced a climate change from warm and wet to relatively cool and dry. According to palaeoclimate curves, a sudden climate change occurred in the Early Eocene, with the mean annual temperature and precipitation decreasing by 5.1 °C and 214.8 mm, respectively, and the climate became very similar to the present climate, which is controlled by the monsoon. Therefore, this significant climate change during the Early Eocene may signal the emergence of the EAM in East Asia.

Analysis of Pulse Signals Based on Array Pulse Volume.

OBJECTIVE: To collect and analyze multi-dimensional pulse diagram features with the array sensor of a pressure profile system (PPS) and study the characteristic parameters of the new multi-dimensional pulse diagram by pulse diagram analysis technology. METHODS: The pulse signals at the Guan position of left wrist were acquired from 105 volunteers at the Shanghai University of Traditional Chinese Medicine. We obtained the pulse data using an array sensor with 3×4 channels. Three dimensional pulse diagrams were constructed for the validated pulse data, and the array pulse volume (APV) parameter was computed by a linear interpolation algorithm. The APV differences among normal pulse (NP), wiry pulse (WP) and slippery pulse (SP) were analyzed using one-way analysis of variance. The coefficients of variation (CV) were calculated for WP, SP and NP. RESULTS: The APV difference between WP and NP in the 105 volunteers was statistically significant (6.26±0.28 vs. 6.04±0.36, P=0.048), as well as the difference between WP and SP (6.26±0.28 vs. 6.07±0.46, P=0.049). However, no statistically significant difference was found between NP and SP (P=0.75). WP showed a similar CV (4.47%) to those of NP (5.96%) and SP (7.58%). CONCLUSION: The new parameter APV could differentiate between NP or SP and WP. Accordingly, APV could be considered an useful parameter for the analysis of array pulse diagrams in Chinese medicine.

Emergent Periodic and Quasiperiodic Lattices on Surfaces of Synthetic Hall Tori and Synthetic Hall Cylinders.

Synthetic spaces allow physicists to bypass constraints imposed by certain physical laws in experiments. Here, we show that a synthetic torus, which consists of a ring trap in the real space and internal states of ultracold atoms cyclically coupled by Laguerre-Gaussian Raman beams, could be threaded by a net effective magnetic flux through its surface-an impossible mission in the real space. Such a synthetic Hall torus gives rise to a periodic lattice in real dimensions, in which the periodicity of the density modulation of atoms fractionalizes that of the Hamiltonian. Correspondingly, the energy spectrum is featured by multiple bands grouping into clusters with nonsymmorphic-symmetry-protected band crossings in each cluster, leading to swaps of wave packets in Bloch oscillations. Our scheme allows physicists to glue two synthetic Hall tori such that localization may emerge in a quasicrystalline lattice. If the Laguerre-Gaussian Raman beams and ring traps were replaced by linear Raman beams and ordinary traps, a synthetic Hall cylinder could be realized and deliver many of the aforementioned phenomena.

Lewis Acid Catalyzed Tandem 1,4-Conjugate Addition/Cyclization of in Situ Generated Alkynyl o-Quinone Methides and Electron-Rich Phenols: Synthesis of Dioxabicyclo[3.3.1]nonane Skeletons.

A versatile Lewis acid catalyzed tandem cyclization of in situ generated alkynyl o-quinone methides ( o-AQMs) with electron-rich phenols has been developed on the basis of the mode involving an intermolecular 1,4-conjugate addition/6-endo cyclization/1,3-aryl shift/intramolecular 1,4-conjugate addition cascade. This reaction provides a new method for expeditious assembly of synthetically and biologically interesting tetracyclic bridged dioxabicyclo[3.3.1]nonane skeletons featuring a congested bridgehead oxa-quaternary stereocenter.

Two-dimensional frameworks formed by pentagonal bipyramidal cobalt(ii) ions and hexacyanometallates: antiferromagnetic ordering, metamagnetism and slow magnetic relaxation.

We herein report the syntheses, structures, and magnetic properties of two isostructural two-dimensional (2D) coordination polymers based on a pentagonal bipyramidal CoII unit [Co(TODA)]2+ and two hexacyanometallates, namely [MIII(CN)6]2[CoII(TODA)]3·9H2O (M = Cr (1), Co (2), TODA = 1,4,10-trioxa-7,13-diazacyclopentadecane). Structure analyses show that both complexes have 2D honeycomb structures where the [Co(TODA)]2+ units are bridged by the [MIII(CN)6]3- groups through three cyano groups in the facial positions. Magnetic investigation reveals ferromagnetic coupling between the CrIII and CoII centres through cyanides in 1. Due to the antiferromagnetic interaction between the layers, compound 1 exhibits an antiferromagnetic ordering below 11.4 K, and shows a metamagnetic phase transition under an external dc field. Due to the disorder of the TODA ligands, compound 1 shows a spin glass behavior, which leads to slow magnetic relaxation in 1. A butterfly-shaped hysteresis loop at 1.8 K can be observed with a coercive field of 720 Oe, which is quite large for cyano-bridged Cr-Co molecular magnets. For compound 2 containing the diamagnetic [CoIII(CN)6]3- unit, field-induced slow magnetic relaxation was also verified, which makes compound 2 a rare example of an SIM assembled in a 2D network. An easy-plane magnetic anisotropy with a positive D value (29.9 cm-1 by PHI and 26.5 cm-1 by Anisofit2.0) was deduced for hepta-coordinated CoII centers. These results show the efficiency of the strategy of combining cyanometallates and pentagonal bipyramidal precursors for novel molecular magnetic materials.

A novel octa-nuclear 32-membered zirconocene macrocycle based on the aromatic selenite.

A novel macrocyclic zirconocene(iv) aromatic selenite [(CpZr)8L16]·2(Cp4Zr2(µ-O)Cl2) (complex 1) (Cp = cyclopentadienyl anion; L = 4-fluorobenzeneseleninic acid) was prepared by the reaction of bis(cyclopentadienyl)zirconium dichloride with 4-fluorobenzeneseleninic acid and characterized by elemental analysis, infrared spectroscopy, 1H, 13C NMR spectroscopy, ESI-MS, XRD and X-ray diffraction. The structure analysis shows that complex 1 is a centrosymmetric 32-membered macrocycle containing an eight-nuclear zirconocene. In this complex, the 4-fluorobenzeneseleninic acid ligands adopt bidentate mode in coordinating to zirconium, which play a bridging role in the formation of a macrocycle. The title compound is a rare example of aromatic selenic acid-based zirconocene derivatives. Furthermore, the preliminary in vitro anti-tumor activity of complex 1 has also been studied toward breast cancer cell lines (MDA-MB-231) and human cervix cell lines (HeLa). The results indicate that complex 1 shows higher activity compared with the ligand and bis(cyclopentadienyl)zirconium dichloride.

Probing the Effect of Axial Ligands on Easy-Plane Anisotropy of Pentagonal-Bipyramidal Cobalt(II) Single-Ion Magnets.

We herein reported the synthetic, structural, computational, and magnetic studies of four air-stable heptacoordinated mononuclear cobalt(II) complexes, namely, [CoII(tdmmb)(H2O)2][BF4]2 (1), [CoII(tdmmb)(CN)2]·2H2O (2), [CoII(tdmmb)(NCS)2] (3), and [CoII(tdmmb)(SPh)2] (4) (tdmmb = 1,3,10,12-tetramethyl-1,2,11,12-tetraaza[[3](2,6)pyridino[3](2,9)-1,10-phenanthrolinophane-2,10-diene; SPh- = thiophenol anion). Constrained by the rigid pentadentate macrocyclic ligand tdmmb, the CoII centers in all of these complexes are in the heptacoordinated pentagonal-bipyramidal geometry. While the equatorial environments of these complexes remain very similar to each other, the axial ligands are systematically modified from C to N to O to S atoms. Analyses of the magnetic data and the ab initio calculations both reveal large easy-plane magnetic anisotropy (D > 0) for all four complexes. While the experimentally obtained D values do not show any clear tendency when the axial coordinated atoms change from C to N to O atoms (complexes 1-3), the largest value is for the heavier and softer S-atom-coordinated complex 4. Because of significant magnetic anisotropy, all four complexes are field-induced single-ion magnets. This work represents a delicate modification of the magnetic anisotropy by tuning the chemical environment of the metal centers.

[Spatial Variability and Distribution Pattern of Soil Organic Matter in a Mollisol Watershed of China].

Spatial variability of soil organic matter and its distribution pattern are the hot issues of soil scientific research. Selecting Haigouhe watershed as the study area, this paper mainly focused on the spatial variability, distribution pattern and its impact factors of SOM in the surface soil by classical statistics, Geo-statistics and "3S" technology. The results showed that: compared with the other black soil areas, the SOM content in Haigouhe watershed was a little lower, there was a spatial autocorrelation, and a moderate variability. Random factors, such as human activities, cultivation measures and so on, had little impact on the spatial variation, while the structural factors had a dominant function, and there was a remarkable spatial anisotropy of SOM. The SOM content reduced gradually from east to west with the familiar changes of height, so the co-kriging interpolation, selecting elevation as the co-variate, was employed to improve the accuracy. The spatial variability of SOM and its distribution pattern in Haigouhe watershed were greatly affected by topography and land use but weakly influenced by traffic, villages and other social factors. The surrounding environment of the samples would increase the uncertainty of spatial variability and interpolation of SOM and it cannot be ignored in future studies. In summary, it was a significant scientific research to analyze the spatial variability, distribution pattern of SOM and its main impact factors in a mollisol hilly watershed of China.

Syntheses, structures and anti-tumor activity of four new organotin(iv) carboxylates based on 2-thienylselenoacetic acid.

With the 2-thienylselenoacetic acid ligand, four new organotin complexes, [Me3Sn(O2CCH2SeC4H3S-o)]n (), [(Ph3Sn)6(O2CCH2SeC4H3S-o)6] (), [(Me2Sn)4(µ3-O)2(O2CCH2SeC4H3S-o)4] (), and [(PhSn)6(µ3-O)6(O2CCH2SeC4H3S-o)6] (), have been synthesized and characterized by X-ray crystallography, elemental analysis, FT-IR and NMR ((1)H, (13)C, and (119)Sn) spectroscopy. The structure analysis indicates that complex adopts a 1D infinite zig-zag chain structure, while complex shows a centrosymmetric hexanuclear 24-membered macrocycle. In contrast, complex and complex display ladder and drum structures, respectively. Examination of the non-covalent intermolecular contacts in complex reveals the existence of the C-HO and C-Hπ interactions, which play an important function in the supramolecular construction. These compounds are rare examples of selenium carboxylic acid-based organotin derivatives. Furthermore, the anti-tumor activity of complexes has also been studied. Importantly, the anti-proliferative properties and possible mechanism of complex are preliminarily investigated. The results demonstrate that complex could induce apoptotic cell death via accumulation of ROS and collapse of the mitochondrial membrane permeabilization (MMP).

Syntheses and magnetic properties of a pyrimidyl-substituted nitronyl nitroxide radical and its cobalt(ii) complexes.

A new bis-bidentate nitronyl nitroxide radical with a pyrimidyl substituent group and two Co(ii) complexes of this ligand were synthesized and characterized. Field-induced single-molecule magnet behavior was firstly observed in the nitronyl nitroxide radical-bridged complexes.

Chiral d-Wave Superfluid in Periodically Driven Lattices.

A chiral d-wave superfluid is a preliminary example of interacting topological matter. However, unlike s-wave superfluids prevalent in nature, its existence requires a strong d-wave interaction, a criterion that is difficult to access in ordinary systems. There is no experimental observation of such unconventional superfluid at the moment. Here, we present a new principle for creating a two-dimensional (2D) chiral d-wave superfluid using periodically driven lattices. Because of an imprinted 2D pseudospin-orbit coupling, where the sublattice index serves as the pseudospin, the s-wave interaction between two hyperfine spin states naturally creates a chiral d-wave superfluid. This scheme can be directly implemented in current experiments.

[Analysis of porphyrin photosensitizers using HPLC method].

Photodynamic therapy (PDT), because of its good targeting, minimal invasion, and safety, is becoming a very active area in cancer prevention and treatment, in which the photosensitizers have proved to be the core element for PDT. We developed a new HPLC method for analyzing porphyrin photosensitizers using Shiseido Capcell PAK C18 (150 mm x 4.6 mm, 5 µm) as the column at 30 °C, methanol-1% aqueous solution of acetic acid as the mobile phase in a flow rate of 1.0 mL · min(-1) in a gradient elution mode, and the detection wavelength at 380 nm. This method, showing good specificity, precision, accuracy and robusty via methodology validations, can be applied to the purity test and assay of porphyrin photosensitizers, and has played a key guide role in the R&D of the new porphyrin photosensitizer--sinoporphyrin sodium.

Spin Crossover in [Fe(2-Picolylamine)3](2+) Adjusted by Organosulfonate Anions.

Three mononuclear spin crossover (SCO) compounds [Fe(2-pic)3]·A2·Solv (A = m-ABS(-), Solv = MeOH, 1; A = p-ABS(-), 2; A = OTf(-), 3) were prepared and characterized magnetically and structurally (2-pic = 2-picolylamine, m-HABS = m-aminobenzenesulfonic acid, p-HABS = p-aminobenzenesulfonic acid, HOTf = trifluoromethanesulfonic acid). Single-crystal X-ray analyses show that they are constructed from the charge-assisted hydrogen bonds between the 2-pic donors and the organosulfonate acceptors, forming the hydrogen-bonded three-dimensional networks for 1 and 2 and one-dimensional columns for 3. While the [Fe(2-pic)3](2+) cations in compounds 1 and 2 are in the meridional (mer-) configuration, it has a facial (fac-) configuration in complex 3. Magnetic susceptibility measurements revealed the SCO transitions and the SCO properties in all three complexes are quite different. Compound 1 undergoes an abrupt SCO with critical temperatures T1/2↓ = 100 K and T1/2↑ = 103 K, while compound 2 exhibits a gradual SCO with T1/2 = 218 K. Compound 3, with the fac-configuration, has an abrupt SCO transition accompanied by the structural phase transition with critical temperatures T1/2↓ = 333 K and T1/2↑ = 343 K. The SCO transitions were further confirmed by the detailed structural analyses of the coordination environments of the Fe(II) centers in both spin states and also by differential scanning calorimetry. Compared to the famous [Fe(2-pic)3]·A2·Solv compounds in the literature, compound 2 has the highest transition temperature for the mer-[Fe(2-pic)3](2+)-containing compounds, while compound 3 represents the first example of the structurally characterized compound of the fac-[Fe(2-pic)3](2+) motif showing SCO behavior. These results show that the organosulfonate anions are very promising to adjust the hydrogen-bonded structures of the SCO compounds and improve the SCO properties of those structures.

Spin crossover behaviour in one-dimensional Fe(II) compounds based on the [M(CN)4](2-) (M = Pd, Pt) units.

Four one-dimensional heterobimetallic coordination polymers {Fe(pic)2[M(CN)4]}n (M = Pd(II) () and Pt(II) (), pic = 2-picolylamine), and {Fe(pypz)2[M(CN)4]}n (M = Pd(II) () and Pt(II) (), pypz = 2-(1H-pyrazol-3-yl)pyridine) have been synthesized and characterized by infrared spectroscopy, X-ray diffraction, magnetic measurements and differential scanning calorimetry (DSC). Single-crystal X-ray analyses show that all the compounds are 1D neutral zigzag chain structures in which the planar [M(CN)4](2-) anion acts as a µ2-bridging ligand, and the two pic/pypz molecules as chelating coligands. Examination of the intermolecular contacts in compounds reveals the existence of the hydrogen bonding interactions involving the hydrogen donor groups of the pic and pypz ligands and the nitrogen atoms of the non-bridging cyanide groups of the [M(CN)4](2-) anions. Weak π-π interactions were also found to be important for the formation of the 3D structures of compounds and . The SCO properties of all compounds were confirmed by the detailed structural analyses of the coordination environments of the Fe(II) centres, DSC analyses, and magnetic susceptibility measurements. Compounds and exhibit complete SCO behaviour with very narrow thermal hysteresis loops centred near the room temperature (T1/2↓ = 270 K and T1/2↑ = 272 K for and T1/2↓ = 272 K and T1/2↑ = 274 K for ), whereas and exhibit abrupt SCO at 186 and 180 K, respectively. Compared to the mononuclear species of the pic and pypz ligands, the SCO temperatures are adjusted by the different ligand field strength of the [M(CN)4)](2-) units. The cooperativity from both the coordination bonds and supramolecular interaction leads to the observation of the hysteresis loops in the Fe-pic systems and the abrupt SCO transition in the Fe-pypz systems. Furthermore, the light-induced excited-spin-state trapping (LIESST) effect was observed for .

Syntheses, structures, and magnetic properties of three new cyano-bridged complexes based on the [Mn(CN)6](³â») building block.

With three pentadentate macrocyclic ligands, three new [Mn(CN)6](3-) based complexes, [Mn(L(N3O2))(H2O)]2[Mn(CN)6](ClO4)·3H2O (1), {[Mn(L(N5))]3[Mn(CN)6]2}n (2) and {[Mn(L(N5Me))]3[Mn(CN)6]2}n·10nH2O (3) (L(N3O2) = 2,13-dimethyl-6,9-dioxa-3,12,18-triazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene, L(N5) = 2,13-dimethyl-3,6,9,12,18-pentaazabicyclo-[12.3.1]octadeca-1(18),2,12,14,16-pentaene, L(N5Me) = 2,6-bis[1-(2-(N-methylamino)ethylimino)ethyl]-pyridine), have been synthesized and characterized structurally and magnetically. The structure of 1 was found to be a linear Mn2(II)Mn(III) trinuclear cluster with two Mn(II) capping groups and one Mn(III) ion connected via two trans-cyano groups. In contrast, compounds 2 and a3 re cyano-bridged 2D networks. Magnetic investigation revealed antiferromagnetic coupling between the Mn(III) and Mn(II) ions via the bridging cyanide groups. Complex 1 showed paramagnetic behavior down to 2.0 K with no sign of SMM behavior. The magnetic coupling constant of J = -1.63 cm(-1) with the Hamiltonian H = -2J(S(Mn(III))·SMn(II)1 + SMn(III)·S(Mn(II)2)) was obtained from the fitting of the magnetic susceptibility. For 2 and 3, ferrimagnetic ordering was observed with magnetic phase transition temperatures (Tc) being 7.5 K and 7.0 K, respectively. These compounds are rare examples of a small number of [Mn(CN)6](3-) based magnetic materials.

Spin canting, metamagnetism, and single-chain magnetic behaviour in a cyano-bridged homospin iron(II) compound.

Spin canting, antiferromagnetic ordering, metamagnetism and single-chain magnetism were verified in a cyano-bridged Fe(II) compound synthesized from the pentagonal bipyramidal Fe(II) starting material in the presence of excessive BF4(-) anions.

Cation-dependent magnetic ordering and room-temperature bistability in azido-bridged perovskite-type compounds.

A series of end-to-end azido-bridged perovskite-type compounds [(CH3)nNH4-n][Mn(N3)3] (n = 1-4) were synthesized and characterized. Structural phase transitions indicating the general lattice flexibility were observed and confirmed by the crystal structures of different phases. These materials show cation-dependent magnetic ordering at up to 92 K and magnetic bistability near room temperature.