银离子促进神经传导素分子内氢原子转移和C-C键解离反应

色氨酸、酪氨酸和组氨酸是三种基本的氨基酸,也是大脑营养代谢中重要神经传导素的前驱体。本文利用自制的反射式时间飞行质谱仪结合磁控溅射束源和下联管式反应器,在气相条件下研究了这三个氨基酸与银离子的相互作用,揭示了这些有机小分子在银离子的存在下容易解离并产生碎片和产物重组的现象,并利用密度泛函理论计算,阐明了其中的反应机制。研究发现,银离子能促进氢原子转移,进而影响竞争性的C_(α)-C_(β)和C_(β)-C_(γ)键解离反应。本研究丰富了对这类神经传导素分子基本规律与性质的精准认识,从而有助于深入理解生物体内类似生理过程的化学机制。

苯和苯胺在深紫外光照射下的电离和解离

本文利用自主研制的反射式飞行时间质谱仪结合177.3 nm深紫外激光研究了苯和苯胺分子的光电离与光解离过程.质谱实验发现苯在177.3 nm皮秒激光作用下发生高效电离并观测到不对称C-C键解离形成的以C4H3^+为主的较小碎片峰.相比之下,苯胺的深紫外光电离中主要产生一个C5H6^+·离子自由基和一个较小丰度的C6H6^+·碎片,分别对应于CNH分子和NH自由基的去除.结合第一性原理计算,诠释了苯和苯胺这两个仅有一个氨基差异的分子光解离路径,揭示苯和苯胺分子中氢原子转移对于C-C或C-N键断裂的关键重要作用.

Effects of iron and humic acid on competition between Microcystis aeruginosa and Scenedesmus obliquus revealed by HPLC analysis of pigments

Iron is a vital micronutrient for growth of bloom-forming Microcystis aeruginosa and competition with other algae,and its availability is affected by humic acid.The effect of iron and humic acid on growth and competition between M.aeruginosa and Scenedesmus obliquus was assessed.The results showed the growth of M.aeruginosa and S.obliquus in mono-cultures was inhibited by humic acid at low iron concentrations(0.01 mg/L);the maximum inhibition ratios were 67.84%and 38.31%,respectively.The inhibition of humic acid on the two species was significantly alleviated when iron concentrations were 1.00 mg/L,with the maximum inhibition rate reduced to 5.82%for M.aeruginosa and to 23.06%for S.obliquus.S.obliquus was the dominant species in mixed cultures,and the mutual inhibition between M.aeruginosa and S.obliquus at low iron concentration was greater than that at high iron concentration.The inhibition of S.obliquus on M.aeruginosa was reduced at low iron concentrations;it increased at high iron concentrations,as concentrations of humic acid rose.

How ligand coordination and superatomic-states accommodate the structure and property of a metal cluster:Cu_(4)(dppy)_(4)Cl_(2)vs.Cu_(21)(dppy)_(10)with altered photoluminescence

We have synthesized two copper nanoclusters(NCs)with a protection of the same ligand diphenylphosphino-2-pyridine(C_(17)H_(14)NP,dppy for short),formulated as Cu_(4)(dppy)_(4)Cl_(2)and Cu21(dppy)10,respectively.The former one bears a distorted tetrahedron Cu4 core with its six edges fully protected by chlorine and dppy ligands,while the latter presents a symmetric Cu_(21)core on which ten dppy molecules function as monolayer protection via well-organized monodentate or bidentate coordination.Interestingly,the Cu_(4)(dppy)_(4)Cl_(2)cluster exhibits a strong yellow emission at∼577 nm,while Cu_(21)(dppy)_(10)displays dual emissions in purple(∼368 nm)and green(∼516 nm)regions respectively.In combination with TD-DFT calculations,we demonstrate the origin of altered emissions and unique stability of the two copper nanoclusters pertaining to the ligand coordination and metallic superatomic states.

Matrine attenuates oxidative stress and cardiomyocyte apoptosis in doxorubicin-induced cardiotoxicity via maintaining AMPKα/UCP2 pathway

Oxidative stress and cardiomyocyte apoptosis are involved in the pathogenesis of doxorubicin(DOX)-induced cardiotoxicity. Matrine is well-known for its powerful anti-oxidant and anti-apoptotic capacities. Our present study aimed to investigate the effect of matrine on DOX-induced cardiotoxicity and try to unearth the underlying mechanisms. Mice were exposed with DOX to generate DOX-induced cardiotoxicity or normal saline as control. H9 C2 cells were used to verify the effect of matrine in vitro.DOX injection triggered increased generation of reactive oxygen species(ROS) and excessive cardiomyocyte apoptosis, which were significantly mitigated by matrine. Mechanistically, we found that matrine ameliorated DOX-induced uncoupling protein 2(UCP2) downregulation, and UCP2 inhibition bygenipin could blunt the protective effect of matrine on DOX-induced oxidative stress and cardiomyocyte apoptosis. Besides, 50-AMP-activated protein kinase α2(Ampkα2) deficiency inhibited matrine-mediated UCP2 preservation and abolished the beneficial effect of matrine in mice. Besides, we observed that matrine incubation alleviated DOX-induced H9 C2 cells apoptosis and oxidative stress level via activating AMPKα/UCP2, which were blunted by either AMPKα or UCP2 inhibition with genetic or pharmacological methods. Matrine attenuated oxidative stress and cardiomyocyte apoptosis in DOX-induced cardiotoxicity via maintaining AMPKα/UCP2 pathway, and it might be a promising therapeutic agent for the treatment of DOX-induced cardiotoxicity.

Chlorine-passivated superatom Al37clusters for nonlinear optics

Utilizing a facile top-down synthetic procedure, here we report the finding of a chlorine-passivated Al_(37) superatom cluster. It is demonstrated that the presence of electrophilic groups, severing as protecting ligands, alters the valence electron count of the metallic core and stabilize the as-prepared aluminum clusters especially when even-numbered chlorine atoms are located at equilibrium positions. Following the discussion regarding their reasonable stabilities, we illustrate the feasible reaction pathways in forming such chlorine-passivated Al_(37) superatom clusters which bear delocalized superatomic orbitals with five valence 3P^5 electrons shifting to the chlorine ligands indicative of a closed electron shell 2F^(14) of the metal core. The successful synthesis of such chlorine-protected aluminum clusters evidences the compatibility of general theory of cluster chemistry in both gas phase and wet chemistry. Such simple-ligand-protected aluminum clusters exhibit reverse-saturated-absorption(RSA) nonlinear optical property pertaining to electronic transitions within the discrete energy states of cluster materials.

Small gold clusters catalyzing oxidant-free dehydrogenation of glycerol initiated by methene hydrogen atom transfer

Developing oxygen-free methodology for the conversion of alcohols to carbonyls is essentially important because it suppresses the over-oxidation of alcohols to carboxylic acids and enables the production of energetic hydrogen.Here we report a finding of feasible oxidant-free dehydrogenation of glycerol over chemically-pure Au clusters synthesized by a green chemistry method named as laser ablation in liquid(LAL).As results,glycerol is dehydrogenated to form glyceraldehyde which undergoes subsequent dehydrogenation to hydroxymethyl glyoxal.For this,reaction dynamics calculations find interesting dehydrogenation reaction pathways with a low-energy barrier of transition state initiated by hydrogen atom transfer from methene,which differs from the general reaction mechanism based on hydroxyl.Furthermore,it is interesting that the presence of additionalààOH group molecules especially H2O can effectively lower the energy barrier in the activation of the OààH and CààH bonds in glycerol.This principle is also applicable to the oxidant-free dehydrogenation of methanol and ethanol,helping to fully understand the catalytic mechanism of alcohols conversion chemistry.

Ligand accommodation causes altered reactivity of silver clusters with iodomethane:superatomic stability of Ag_(9)I_(2)^(+)in mimicking XeF_(2)

Exploring metal cluster reactivity with alkyl halides enables to understand the related chemical mechanism of metal surfaces in terms of active sites.Here we report a study of Ag_(n)^(+)(n=1-27)clusters reacting with iodomethane by a flow tube apparatus in tandem with a customized triple quadrupole mass spectrometer.Strong even/odd alternation of the Ag_(n)^(+)is observed in their reactions with CH_(3)I,where silver clusters with even-number,Ag_(2n)^(+),find favorable products of Ag_(2n)I_(1,3)^(+)series,while the Ag_(2n−1)^(+)clusters form Ag_(2n−1)I_(2,4)^(+)products.Interestingly,Ag_(9)^(+)shows up with prominent mass abundance but allows for the formation of Ag_(9)I_(2)^(+),which finds an echo with the formation of Ag_(10)I_(3)^(+).We illustrate the enhanced stability of Ag_(9)I_(2)^(+)and Ag_(10)I_(3)^(+)by showing their significantly enlarged highest occupied molecular orbital(HOMO)-lowest unoccupied molecular orbital(LUMO)gaps and balanced charge distribution compared with the bare metal clusters,respectively.Also elucidated,is the superatomic nature of these bare and iodinated silver clusters,especially Ag_(9)I_(2)^(+)which mimics the rare-gas compound XeF_(2).This study expands a vivid example of special and general superatoms,and enriches the general knowledge on how a ligand stabilizes a metal cluster.

Pure Metal Clusters with Atomic Precision for Nanomanufacturing

Advances in cluster science have enabled the preparation of atomically precise metal clusters with one to a hundred atoms under controllable expansion conditions.After introducing typical gas-phase cluster preparation and reaction apparatuses,this work summarized recent progress in preparing pure metal clusters of single-atom resolution,including neutral and ionic ones,with typical examples of Al,V,Nb,Fe,Co,Ni,Rh,Pt,Ag,Cu,and Pb.With the development of soft-landing deposition technology,the size-selective pure metal clusters with strict atomic precision and predictive property will benefit nanomanufacturing down to atomic and near-atomic scales.This work serves as a modest motivation to stimulate the interest of scientists focusing on interdisciplinary subjects.

Formation of Al^(+)(C_(6)H_(6))_(13):The Origin of Magic Number in Metal-Benzene Clusters Determined by the Nature of the Core

The identification of highly abundant,“magic”spe-cies in the mass spectra of clusters have proven to be valuable in nanoscience,leading to the discovery of new stable species such as fullerenes and the elec-tronic shell structures of metallic clusters.