Biological Intelligence of Rare Earth Elements in Animal Cells

Recent progress in bioinorganic chemistry studies of rare earth elements (REE) in animal cells was outlined, and the definition of REE′s biological intelligence as well as their mechanism were also explained. The migration of REE from weathering rocks to the environment is accelerated by various anthropogenic activities, which can eventually result in the entrance of REE into animal and human bodies via food chain. REE can be found in body tissues such as brain, blood, muscle as well as bone. Based on their geochemical properties, REE in low dose show their unique biological intelligence by intervening in the process of signal transduction and its regulation, arteriosclerosis and blood clotting prevention, anticancer, and the promotion of cellular defense enzymes′ activities, nucleic acid metabolism enzymes as well as ATPases, etc. The meaning of REE′s biological intelligence refers to physicochemical properties-based capability to choose the targets (e.g., biometals) in biomolecules for the chelation or replacement of REE, and change the structures and functions of biomolecules, and consequently impact or control the biological functions or behaviors in living organisms. The regulation of various cellular processes caused by REE is mainly via antagonism or replacement of essential target biometals like calcium or via chelation of organic molecules, thereby embodying the unparalleled biological intelligence of REE. Additionally, the dosage effect of REE was also discussed from the angles of yin-yang dichotomy, bioavailability, entropy and evolution. In order to make full use of REE′s biological intelligence in the application for medicine, more detailed studies concerning dosage effect of REE and REE bioaccumulation in organisms should be conducted in future research.

Biological Function of REE in Plants & Microbes

Rare earth elements （REE） and their compounds years. The bioinorganic chemical research of REE during the are widely applied in agronomic and medical fields for many past few years indicates that REE play important roles in the promotion of photosynthetic rate as well as root absorption, regulation of hormone and nitrogen metabolism, and suppression of microbes, etc. The metallic or non-metallic targets of key biomolecule in various physiological processes can be chosen by REE for the chelation or replacement, which enables REE to regulate the biological functions or behaviors of those biomolecule and consequently leads to significant embodiment of biological function of REE in plants and microbes. Overdose of REE, however, shows an inhibitory effect on living organisms. Therefore, this paper proposes two suggestions that will be available in the extension of full use of REE＇s biological function. One is to obey the dose law of REE and control REE concentrations within a safe range. The other is to further test the bioaccumulation and long-period influence of REE on organisms.

Preparation, Structure and Electrochemical Property of a Pyrazole-substituted Diiron Dithiolate Complex

A pyrazole-substituted diiron dithiolate complex [Fez（p-pdt）（CO）5（3,5-Me2Pz）] （1, 3,5-MezPz = 3,5-dimethylpyrazole） was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substitution of aU-carbonyl complex [Fe2（μ-pdt）（CO）6] with 3,5-Me2Pz. The molecular structure was confirmed by MS, IR, 1H NMR, elemental analysis and single-crystal X-ray analysis. Complex 1 crystallizes in the triclinic system, space group PI with a = 9.108（7）, b = 9.743（8）, c = 11.192（9）A, a = 109.235（5）, fl = 101.914（9）, y = 96.605（6）. In CH3CN solution, reversible transformation between 1 and the acetonitrile-substituted species [Fe2（p-pdt）- （CO）5（NCCH3）] was detected by both IR and cyclic voltammetry （CV）. The electrochemical proton reduction catalyzed by 1 in the presence of acetic acid was also studied in CH2C12.

A New Pyridine-substituted Azadithiolate 2Fe2S Complex Related to the Active Site of[FeFe]-hydrogenase

A new 2Fe2 S complex[（2-C5H4N）N（μ-CH2S）2Fe2（CO）6]（1） related to the active site of[FeFe]-hydrogenase was obtained by treating（HS）2Fe2（CO）6 with（pyridin-2-ylazanediyl）dimethanol.Protonation occurred at the pyridine nitrogen atom when two equivalents of HBF4·OEt2acid were added to the toluene solution of 1,leading to the formation of[（2-C5H4NH）N（μ-CH2S）2Fe2（CO）6]·BF4·OEt2（1H~＋）,whose molecular structure was further established by singlecrystal X-ray analysis.Complex 1 crystallizes in the monoclinic system,space group P21/n with α=7.728（3）,b = 11.825（4）,c = 17.888（6） A,β= 92.968（5）°,while complex 1H~＋ crystallizes in the triclinic system,space group P1 with a = 7.672（4）,b = 10.382（5）,c = 16.480（10） A,α=106.575（13）,β= 93.18（3）,γ=104.262（17）°.

Ultrasound-active ReCORM-AIEgen for gas and sonodynamic therapy of mycobacterium biofilms

Bacterial infection is the leading cause of many severe inflammation diseases. The development of novel and effective therapeutic approaches to counter bacterial infections, especially for drug-resistant bacteria, is essential. Herein, we have successfully developed an ultrasound-active tricarbonyl rhenium(Ⅰ) complex with tetraphenylethylene(TPE) modification(RePyTPE) for CO gas therapy and sonodynamic therapy of bacterial infections. RePy-TPE produced reactive oxygen species and released CO under ultrasound irradiation. In addition, RePy-TPE showed aggregation-induced emission in water due to the introduction of TPE, which enhanced the yield of ^(1)O_(2) generation in a biological aqueous solution. The produced ^(1)O_(2) and released CO killed mycobacterium smegmatis(M. smegmatis) and Escherichia coli(E. coli), as shown by bacterial membrane damage and biofilm elimination. Furthermore, ultrasound-active RePy-TPE perturbed the purine metabolism of the bacteria, which disturbed the biosynthesis of DNA and energy metabolism, eventually reducing the vitality of bacteria. This article provides a novel strategy for the development of ultrasound-active metal-based antibiotics.

Sonodynamic cancer therapy by novel iridium-gold nanoassemblies

Metal-based compounds with excellent photo-physical properties show good photochemotherapeutic performance.But,low in-depth tissue penetration of light limits their effectivity for deeply buried tumors.Encouraged by the sonosensitizing ability of the traditional organic photosensitizers,here,we developed AuNPs@Ir1 as a sonosensitizer by hybridizing an organometallic Ir(Ⅲ) complex(Ir1) with ultrasmall gold nanoparticles(AuNPs) for efficient tumor sonodynamic therapy(SDT) for the first time.AuNPs@Ir1 rapidly entered the cancer cells,produced ^(1)O_(2),and catalytically oxidized NADH to NAD;under ultrasound(US)irradiation,thus resulted in cancer cells oncosis.Because of efficient passive retention in tumors post intravenous injection,AuNPs@Ir1 further efficiently inhibited the growth of tumors in-vivo under US stimulation without long-term toxicity to other organs.Overall,this work presents the excellent US triggered in-vitro and in-vivo anticancer profile of the novel AuNPs@Ir1.It is expected to increase the scope of SDT for metal-based anticancer drugs.