Integrating Levels of Hierarchical Organization in Porous Organic Molecular Materials

Porous organic molecular materials(POMMs)are an emergent class of molecular-based materials characterized by the formation of extended porous frameworks,mainly held by non-covalent interactions.POMMs represent a variety of chemical families,such as hydrogen-bonded organic frameworks,porous organic salts,porous organic cages,C-H···πmicroporous crystals,supramolecular organic frameworks,π-organic frameworks,halogen-bonded organic framework,and intrinsically porous molecular materials.In some porous materials such as zeolites and metal organic frameworks,the integration of multiscale has been adopted to build materials with multifunctionality and optimized properties.Therefore,considering the significant role of hierarchy in porous materials and the growing importance of POMMs in the realm of synthetic porous materials,we consider it appropriate to dedicate for the first time a critical review covering both topics.Herein,we will provide a summary of literature examples showcasing hierarchical POMMs,with a focus on their main synthetic approaches,applications,and the advantages brought forth by introducing hierarchy.

An Ultrastable π-π Stacked Porous Organic Molecular Framework as a Crystalline Sponge for Rapid Molecular Structure Determination

The crystalline sponge method is a pragmatic and promising strategy for molecular structure determination.However,the dominant metal-organic framework crystal sponge platforms always face poor chemical stability,especially solvent instability,hampering their application in a vaster domain.Herein,we report an ultrastable π-π stacked porous organic molecular framework which exhibits permanent porosity,high thermal stability,and good chemical resistance.It can efficiently implement an approach to molecular structure determination via a single-crystal-to-single-crystal transformation.This is the first example utilizing π-π stacked porous organic molecular framework as“crystalline sponge”to determine a wide variety of guests,ranging from hydrophilic to hydrophobic,and from aliphatic to aromatic,which complements the crystalline sponges based on the famous metal-organic frameworks.More importantly,it can achieve rapid structure determination of small molecules within 3 h.

Source dynamics of carbonaceous aerosol during the haze bloom-decay process in China based on radiocarbon and organic molecular tracer

With the support by the National Natural Science Foundation of China and the Chinese Academy of Sciences,the research team led by Prof.Li Jun(李军)at the State Key Laboratory of Organic Geochemistry,Guangzhou Institute of Geochemistry,Chinese Academy of Sciences,illustrated the source dynamics of carbonaceous aerosol during the haze bloom-decay process in Beijing and Guangzhou based on

Effect of Dissolved Organic Matter on Titanium Dioxide Nanoparticles in Aquatic Environment:Molecular Weight Fractions

At present,a growing number of consumer products contain engineered nanoparticle TiO2(nano⁃TiO2),which has resulted in the consequences of nano⁃TiO2 entering the aquatic environment directly or indirectly at some stage.The fate of nano⁃TiO2 in the aquatic environment has become the key factor which affects its safety application and nanoecotoxicology.This paper aims to investigate how the dissolved organic matters(DOM),especially the molecular weight fractions in the aquatic environment,affect the aggregation,stability,and fate of nano⁃TiO2,and the interaction mechanism of DOM and nano⁃TiO2.Results of dynamic light scattering(DLS)showed that the molecular weight of DOM molecules caused different aggregation rates of nano⁃TiO2 in aqueous solution.Fourier Transform infrared spectroscopy(FTIR)results indicated the molecular structure is characteristics of DOM fractions and the mechanisms of bonds formation between DOM and nano⁃TiO2.Results of three⁃dimensional excitation⁃emission matrices(3D⁃EEM)confirmed the FTIR results and implied the increase of the stability of theπ-πconjugated system in the presence of DOM.In addition,low molecular weight of DOM fractions appeared to show more affinity with nano⁃TiO2 than high molecular weight fractions.

BiPh-m-BiDPO as a Hole-Blocking Layer for Organic Light-Emitting Diodes： Revealing Molecular Structure-Properties Relationship

We report a simple hole-blocking material （biphenyl-3,3＇-diyl）bis（diphenylphosphine oxide） （BiPh-m-BiDPO） based on our recent advance. The bis（phosphine oxide） compound shows HOMO/LUMO levels of ∽-6.71/- 2.51 eV. Its phosphorescent spectrum in a solid film features two major emission bands peaking at 2.69 and 2.4eV, corresponding to 0-0 and 01 vibronic transitions, respectively. The measurement of the electron-only devices reveals that BiPh-m-BiDPO possesses electron mobility of 2.28 × 10^-9-3.22× 10^-8cm2 V-1s-1 at E = 2- 5 × 10^5 V/cm. The characterization of the sky blue fluorescent and red phosphorescent pin organic light-emitting diodes （OLEDs） utilizing BiPh-m-BiDPO as the hole blocker shows that its shallow LUMO level as well as the low electron mobility affects significantly the power efficiency and hence operational stability, relative to the luminous efficiency, especially at high luminance. In combination with our recent results, the present study provides an indepth insight on the molecular structure-property correlation in the organic phosphinyl-containing hole-blocking materials.

Recent advances in quasi-2D superconductors via organic molecule intercalation

Superconductivity at the 2D limit shows emergent novel quantum phenomena, including anomalously enhanced H_(c2),quantum metallic states and quantum Griffiths singularity, which has attracted much attention in the field of condensed matter physics. In this article, we focus on new advances in quasi-2D superconductors in the bulk phase using an organic molecular electrochemical intercalation method. The enhanced superconductivity and emergent pseudogap behavior in these quasi-2D superconductors are summarized with a further prospect.

Spatial Distribution Characteristics of Organic Acids in Two Late-blooming Rhododendron Species

[Objectives]The spatial distribution characteristics of organic acids in two late-blooming Rhododendron species(Rhododendron decorum and Rhododendron stamineum)in Guizhou Baili Rhododendron National Forest Park were explored,in order to provide reference for exploring the plant-soil relationship of subtropical forest.[Methods]The fresh leaf,stem,root,litter,humus and soil samples of R.decorum and R.stamineum were collected.The contents of eight low molecular weight organic acids including oxalic acid,tartaric acid,malic acid,citric acid,acetic acid,lactic acid,succinic acid and formic acid were determined by high performance liquid chromatography(HPLC).[Results]Oxalic acid is the main organic acid in the two species of Rhododendron.Among different samples,the content of organic acids was in the following order:root>fresh leaf>humus>litter>stem>soil.[Conclusions]The content of organic acids in the root was significantly higher than that in other parts.The types of organic acids in stems were the least.

Building the bridge of small organic molecules to porous carbons via ionic solid principle

Replacing traditional polymer-based precursors with small molecules is a promising pathway toward facile and controllable preparation of porous carbons but remains a prohibitive challenge because of the high volatility of small molecules.Herein,a simple,general,and controllable method is reported to prepare porous carbons by converting small organic molecules into organic molecular salts followed by pyrolysis.The robust electrostatic force holding organic molecular salts together leads to negligible volatility and thus ensures the formation of carbons under high-temperature pyrolysis.Meanwhile,metal moieties in organic molecular salts can be evolved into in-situ templates or activators during pyrolysis to create nanopores.The modular nature of organic molecular salts allows easy control of the porosity and chemical doping of carbons at a molecular level.The sulfur-doped carbon prepared by the ionic solid strategy can serve as robust support to prepare small-sized intermetallic PtCo catalysts,which exhibit a high mass activity of 1.62 A·mgPt^(−1)in catalyzing oxygen reduction reaction for fuel cell applications.

A review of environmental characteristics and effects of low-molecular weight organic acids in the surface ecosystem

Low molecular weight organic acids （LMWOAs） are prevalent on the earth＇s surface. They are vital intermediate products during metabolic pathways of organic matter and participate in the tricarboxylic acid cycle during life activities. Photochemical reactions are pivotal for LMWOAs＇ origination and play a large role in determining their diversity and their ultimate fate. Within the long time that organic matter is preserved in sediments, it can be decomposed and converted to release organic and inorganic pollutants as well as C, N, and P nutrients, which are of potential ecological risk in causing secondary pollution to lake water. The sediment pool is a comprehensive and complex compartment closely associated with overlying water by various biochemical processes, during which LMWOAs play critical roles to transport and transform elements. This article elucidates geochemical behaviors of LMWOAs in the surface environment in details, taking natural water, soil, and aerosol as examples, focusing on reviewing research developments on sources and characteristics, migration and mineralization of LMWOAs and relevant environmental effects. Simultaneously, this review article depicts the categories and contents of LMWOAs or their contribution to DOC in environmental media, and evaluates their importance during organic matter early diagenesis. Through concluding and discussing the conversion mechanisms and influencing factors, the next research orientations on LMWOAs in lake ecosystems are determined, mainly concerning relationships with hydrochemical parameters and microorganisms, and interactions with pollutants. This will enrich the knowledge on organic matter degradation and related environmental effects, and help reconstruct a theoretical framework for organic compound succession and influencing factors, providing basic data for lake eutrophication and ecological risk assessment, conducive to better control over water pollution and proper management of water quality.

Effect of dissolved phosphorus on alkaline phosphatase activity in marine microalgae

Alkaline phosphatase activity (APA) and dissolved phosphorus were monitored during the batch cultures of two bone microalgae. Results indicate that variation of APA was in the shape of 'S' curve. Different specs of dissolved phaphorus had different effects on APA. The concentrations of dis solved inorganic phosphorus (DIP) and and molecular dissolved organic phosphorus (SDOP) had a sig nificant effect on APA, while the concentration of large molecular dissolved organic phosphorus (LDOP) had a little effect on APA., and the increase of APA could accelerate the decomposing of LDOP in the medium. Results also show that algae species and abundance had why a little effect on APA.

Effect of different molecular weight organic components on the increase of microbial growth potential of secondary effluent by ozonation

Ozonation has been widely applied in advanced wastewater treatment. In this study, the effect of ozonation on assimilable organic carbon （AOC） levels in secondary effluents was investigated, and AOC variation of different molecular weight （MW） organic components was analyzed. Although the removal efflciencies were 47%-76% and 94%-100% for UV2s4 and color at ozone dosage of 10 mg/L, dissolved organic carbon （DOC） in secondary effluents was hardly removed by ozonation. The AOC levels increased by 70%-780% at an ozone dosage range of 1-10 mg/L. AOC increased significantly in the instantaneous ozone demand phase, and the increase in AOC was correlated to the decrease in UV254 during ozonation. The results of MW distribution showed that, ozonation led to the transformation of larger molecules into smaller ones, but the increase in low MW （〈1 kDa） fraction did not contribute much to AOC production. The change of high MW （〉100 kDa and 10-100 kDa） fractions itself during ozonation was the main reason for the increase of AOC levels. Furthermore, the oxidation of organic matters with high MWs （〉 100 kDa and 10-100 kDa） resulted in more AOC production than those with low MWs （1-10 kDa and 〈1 kDa）. The results indicated that removing large molecules in secondary effluents could limit the increase of AOC during ozonation.

Effects of low molecular weight organic acids on aggregation behavior of biochar colloids at acid and neutral conditions

Low molecular weight organic acids(LMWOAs),as active components in the rhizosphere carbon cycling,may influence the environmental behaviors of biochar colloids.This study selected the pine-wood and wheat-straw biochars(PB and WB)as two typical biochars.The effects of typical LMWOAs(oxalic acid,citric acid,and malic acid)on aggregation kinetics of PB and WB colloids were investigated under pH 4 and 6 conditions.Critical coagulation concentrations(CCCs)of both PB and WB colloids were decreased with the LMWOAs regardless of the types of biochar and the solution pH,and the most significant effect occurred in pH 4 due to more LMWOAs sorption on the biochar colloids.The different types of LMWOAs caused various CCCs changes.For example,the CCC values of PB colloids decreased from 75 mM to 56,52,and 47 mM in the pH 4 NaCl solutions when 1 mM oxalic acid,citric acid,and malic acid were present in the suspensions,respectively.The chemical structure(functional groups)and molecular weight of LMWOAs,solution pH,and the electrophoretic mobility(EPM)of biochar co-influence the interactions between biochar colloids and LMWOAs,thus affecting the stability of biochar colloids in the presence of LMWOAs.The presence of LMWOAs accelerated the aggregation of colloidal biochar by increasing the interaction of surface bridging bonds(hydrogen bonding)and decreasing the repulsive force between colloidal biochar particles.This study showed that LMWOAs could accelerate the aggregation of biochar colloids in acidic or neutral environments and reduce the mobility of biochar colloids in soil rhizosphere.

Recent advances in photofunctional polymorphs of molecular materials

Recently,molecule-based luminescent materials have been drawing extensive attention due to their desirable properties and promising applications in the fields of sensors,lighting display and cell imaging.Crystalline polymorph is an intriguing phenomenon that the presence of multiple packing and aggregate architectures of the same molecular system.The studies on polymorphs for molecule-based fluorophores provide the opportunities to adjust the mode of molecular packing and photophysical properties,which will help to illustrate the structure-property relationship.In this review,we focus on the recent progress in various feasible methods of molecule-based crystalline polymorphism growth and their adjustable photofunctional properties,which will open up possibilities of variant optical applications.Firstly,several effective ways to prepare and screen polymorphs are sorted out.And then,we discuss the discrepant properties and multifunctional applications(such as sensors,laser and OFET).Finally,the development trends and future prospects of these polymorphs are also briefly introduced.

Microstructure Manipulation of Covalent Organic Frameworks(COFs)-based Membrane for Efficient Separations

Covalent organic framework(COF) membranes have exhibited great potential to become the next-generation membranes for efficient separations due to the diverse structures, ordered framework pores, tunable functionality and excellent stability. This review presents the microstructure manipulation strategies for separation performance enhancement of COF membranes in recent years. Based on the three mechanisms of molecular sieving, surface diffusion, and facilitated transport, the structural modulation methods to enhance the selectivity of COF membranes are analyzed in detail. Next, strategies of realizing ultrashort mass transfer pathways and ultralow mass transfer resistance for the permeability enhancement are elaborated. Furthermore, the framework stability in COFs, interlayer stability between COF nanosheets and interfacial stability between COF layer and substrate are discussed. Finally, we discuss the existing challenges and perspectives on the future development of COF membranes, targeting at identifying the most promising strategies and directions for the engineering of COF membranes.

Effects of ozonation and coagulation on effluent organic matter characteristics and ultrafiltration membrane fouling

Effluent organic matter （EfOM） is the major cause of fouling in the low pressure membranes process for wastewater reuse. Coagulation and oxidation of biological wastewater treatment effluent have been applied for the fouling control of microfiltration membranes. However, the change in EfOM structure by pre-treatments has not been clearly identified. The changes of EfOM characteristics induced by coagulation and ozonation were investigated through size exclusion chromatography, UV/Vis spectrophotometry, fluorescence spectrophotometry and titrimetric analysis to identify the mechanisms in the reduction of ultrafiltration （UF） membrane fouling. The results indicated that reduction of flux decline by coagulation was due to modified characteristics of dissolved organic carbon （DOC） content. Total concentration of DOC was not reduced by ozonation. However, the mass fraction of the molecules with molecular weight larger than 5 kDa, fluorescence intensity, aromaticity, highly condensed chromophores, average molecular weight and soluble microbial byproducts decreased greatly after ozonation. These results indicated that EfOM was partially oxidized by ozonation to low molecular weight, highly charged compounds with abundant electron- withdrawing functional groups, which are favourable for alleviating UF membrane flux decline.

Improving the Performance of TIPS-pentacene Thin Film Transistors via Interface Modification

Understanding the structure-performance relationship is crucial for optimizing the performance of organic thin film transistors. Here, two interface modification methods wereapplied to modulate the thin film morphology of the organic semiconductor, 6,13-bis（triisopropylsilylethynyl）pentacene（TIPS-pentacene）. The resulting different film morphologies and packing structures led to distinct charge transport abilities. A substantial 40-fold increase in charge carrier mobility was observed on the octadecyltrichlorosilane（OTS）-modified sample compared to that of the transistor on the bare substrate. A better charge mobility greater than 1 cm^2· V^-1· s^-1 is realized on the p-sexiphenyl（p-6P）- modified transistors due to the large grain size, good continuity and, importantly, the intimate π-π packing in each domain.

Impact of microbial communities from tropical soils on the mobilization of trace metals during dissolution of cinnabar ore

Biodissolution experiments on cinnabar ore （mercury sulphide and other sulphide minerals, such as pyrite） were performed with microorganisms extracted directly from soil. These experiments were carried out in closed systems under aerobic and anaerobic conditions with 2 different soils sampled in French Guyana. The two main objectives of this study were （1） to quantify the ability of microorganisms to mobilize metals （Fe, A1, Hg） during the dissolution of cinnabar ore, and （2） to identify the links between the type and chemical properties of soils, environmental parameters such as season and the strategies developed by indigenous microorganisms extracted from tropical natural soils to mobilize metals, Results indicate that microbial communities extracted directly from various soils are able to （1） survive in the presence of cinnabar ore, as indicated by consumption of carbon sources and, （2） leach Hg from cinnabar in oxic and anoxic dissolution experiments via the acidification of the medium and the production of low molecular mass organic acids （LMMOAs）. The dissolution rate of cinnabar in aerobic conditions with microbial communities ranged from 4.8 x 10-4 to 2.6 x 10-3 μmol/m2/day and was independent of the metabolites released by the microorganisms. In addition, these results suggest an indirect action by the microorganisms in the cinnabar dissolution. Additionally, because iron is a key element in the dynamics of Hg, microbes were stimulated by the presence of this metal, and microbes released LMMOAs that leached iron from iron-bearing minerals, such as pyrite and oxy-hydroxide of iron, in the mixed cinnabar ore.