Tunable Wettability of a Dual-Faced Covalent Organic Framework Membrane for Enhanced Water Filtration.

Membrane technology plays a central role in advancing separation processes, particularly in water treatment. Covalent organic frameworks (COFs) have transformative potential in this field due to their adjustable structures and robustness. However, conventional COF membrane synthesis methods are often associated with challenges, such as time-consuming processes and limited control over surface properties. Our study demonstrates a rapid, microwave-assisted method to synthesize self-standing COF membranes within minutes. This approach allows control over the wettability of the surface and achieves superhydrophilic and near-hydrophobic properties. A thorough characterization of the membrane allows a detailed analysis of the membrane properties and the difference in wettability between its two faces. Microwave activation accelerates the self-assembly of the COF nanosheets, whereby the thickness of the membrane can be controlled by adjusting the time of the reaction. The superhydrophilic vapor side of the membrane results from -NH2 reactions with acetic acid, while the nearly hydrophobic dioxane side has terminal aldehyde groups. Leveraging the superhydrophilic face, water filtration at high water flux, complete oil removal, increased rejection with anionic dye size, and resistance to organic fouling were achieved. The TTA-DFP-COF membrane opens new avenues for research to address the urgent need for water purification, distinguished by its synthesis speed, simplicity, and superior separation capabilities.

Ionic Covalent Organic Framework as a Dual Functional Sensor for Temperature and Humidity.

Visual sensing of humidity and temperature by solids plays an important role in the everyday life and in industrial processes. Due to their hydrophobic nature, most covalent organic framework (COF) sensors often exhibit poor optical response when exposed to moisture. To overcome this challenge, the optical response is set out to improve, to moisture by incorporating H-bonding ionic functionalities into the COF network. A highly sensitive COF, consisting of guanidinium and diformylpyridine linkers (TG-DFP), capable of detecting changes in temperature and moisture content is fabricated. The hydrophilic nature of the framework enables enhanced water uptake, allowing the trapped water molecules to form a large number of hydrogen bonds. Despite the presence of non-emissive building blocks, the H-bonds restrict internal bond rotation within the COF, leading to reversible fluorescence and solid-state optical hydrochromism in response to relative humidity and temperature.

Insight Study of Trace Elements in PM2.5 During Nine Years in Delhi, India: Seasonal Variation, Source Apportionment, and Health Risks Assessment.

This study investigated the concentrations, seasonal variations, sources, and human health risks associated with exposure to heavy elements (As, Al, Pb, Cr, Mn, Cu, Zn, and Ni) of PM2.5 at an urban location of Delhi (28° 38' N, 77° 10' E; 218 m amsl), India, from January 2013 to December 2021. The average mass concentration of PM2.5 throughout the study period was estimated as 127 ± 77 µg m-3, which is exceeding the National Ambient Air Quality Standards (NAAQS) limit (annual: 40 µg m-3; 24 h: 60 µg m-3). The seasonal mass concentrations of PM2.5 exhibited at the order of post-monsoon (192 ± 110 µgm-3) > winter (158 ± 70 µgm-3) > summer (92 ± 44 µgm-3) and > monsoon (67 ± 32 µgm-3). The heavy elements, Al (1.19 µg m-3), Zn (0.49 µg m-3), Pb (0.43 µg m-3), Cr (0.21 µg m-3), Cu (0.21 µg m-3), Mn (0.07 µg m-3), and Ni (0.14 µg m-3) exhibited varying concentrations in PM2.5, with the highest levels observed in the post-monsoon season, followed by winter, summer, and monsoon seasons. Six primary sources throughout the study period, contributing to PM2.5 were identified by positive matrix factorization (PMF), such as dust (paved/crustal/soil dust: 29.9%), vehicular emissions (17.2%), biomass burning (15.4%), combustion (14%), industrial emissions (14.2%), and Br-rich sources (9.2%). Health risk assessments, including hazard quotient (HQ), hazard index (HI), and carcinogenic risk (CR), were computed based on heavy elements concentrations in PM2.5. Elevated HQ values for Cr and Mn linked with adverse health impacts in both adults and children. High carcinogenic risk values were observed for Cr in both adults and children during the winter and post-monsoon seasons, as well as in adults during the summer and monsoon seasons. The combined HI value exceeding one suggests appreciable non-carcinogenic risks associated with the examined elements. The findings of this study provide valuable insights into the behaviour and risk mitigation of heavy elements in PM2.5, contributing to the understanding of air quality and public health in the urban environment of Delhi.

Chemical characteristics, morphology and source apportionment of PM10 over National Capital Region (NCR) of India.

The present study frames the physico-chemical characteristics and the source apportionment of PM10 over National Capital Region (NCR) of India using the receptor model's Positive Matrix Factorization (PMF) and Principal Momponent Mnalysis/Absolute Principal Component Score-Multilinear Regression (PCA/APCS-MLR). The annual average mass concentration of PM10 over the urban site of Faridabad, IGDTUW-Delhi and CSIR-NPL of NCR-Delhi were observed to be 195 ± 121, 275 ± 141 and 209 ± 81 µg m-3, respectively. Carbonaceous species (organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC)), elemental constituents (Al, Ti, Na, Mg, Cr, Mn, Fe, Cu, Zn, Br, Ba, Mo Pb) and water-soluble ionic components (F-, Cl-, SO42-, NO3-, NH4+, Na+, K+, Mg2+, Ca2+) of PM10 were entrenched to the receptor models to comprehend the possible sources of PM10. The PMF assorted sources over Faridabad were soil dust (SD 15%), industrial emission (IE 14%), vehicular emission (VE 19%), secondary aerosol (SA 23%) and sodium magnesium salt (SMS 17%). For IGDTUW-Delhi, the sources were SD (16%), VE (19%), SMS (18%), IE (11%), SA (27%) and VE + IE (9%). Emission sources like SD (24%), IE (8%), SMS (20%), VE + IE (12%), VE (15%) and SA + BB (21%) were extracted over CSIR-NPL, New Delhi, which are quite obvious towards the sites. PCA/APCS-MLR quantified the similar sources with varied percentage contribution. Additionally, catalogue the Conditional Bivariate Probability Function (CBPF) for directionality of the local source regions and morphology as spherical, flocculent and irregular were imaged using a Field Emission-Scanning Electron Microscope (FE-SEM).

Health risk assessment of aerosol particles (PM2.5 and PM10) during winter crop at the agricultural site of Delhi, India.

For the last few decades, air pollution in developing country like India is increasing, and it is a matter of huge concern due to its associated human health impacts. In this region, the burgeoning population, escalating urbanization and industrialization, has been cited as the major reason for such a high air pollution. The present study was carried out for health risk assessment of aerosol particles (PM10 and PM2.5) and its associated heavy metals of an agriculture farm site at Indian Agricultural Research Institute (IARI) considered to be green urban area in Delhi, India. The concentrations of both PM10 and PM2.5 varied significantly from 136 to 177 µg/m3 and 56 to 162 µg/m3, respectively at the site. In the present case, the highest PM10 and PM2.5 levels were reported in January, followed by December. The levels of ambient PM10 and PM2.5 are influenced by wind prevailing meteorology. These levels of PM10 and PM2.5 are more than the permissible limits of WHO guidelines of 15 and 5 µg/m3, respectively, thereby leading to high aerosol loadings specifically in winters. The PM concentration of the atmosphere was found to be negatively correlated with temperature during the sampling period. The concentrations of surface ozone O3 and NOx in the present study were observed to be high in February and March, respectively. The increasing air pollution in the city of Delhi poses a great risk to the human health, as the particulate matter loaded with heavy metals can enter humans via different pathways, viz., ingestion, inhalation, and absorption through skin. The mean hazard index for metals (Zn, Pb, Cd, As, Cr, and Ni) was observed within the acceptable limit (HI < 1), thereby indicating negligible non-carcinogenic effects to residing population. The carcinogenic risk assessment was conducted for Cd, Pb, and As only, as the concentrations for other metals were found to be quite low. The carcinogenic risk values were also within the limits of USEPA standards, indicating no carcinogenic risks to the health of children and adults residing near the site. This information about the PM pollution at the agricultural site and health risk assessment will serve as a baseline data in assessment of human health impacts due to air pollution at the local scale and can be used for development of mitigation strategies for tackling air pollution.

Association between Acute Exposure to PM2.5 Chemical Species and Mortality in Megacity Delhi, India.

The association between daily all-cause mortality and short-term fine particulate matter (PM2.5) exposure is well established in the literature. However, association between acute exposure to PM2.5 chemical species and mortality is not well known, especially in developing countries like India. Here we examined associations between mortality and acute exposure to PM2.5 mass concentration and their 15 chemical components using data from 2013 to 2016 in megacity Delhi using a semiparametric quasi-Poisson regression model, adjusting for mean temperature, relative humidity, and long-term time trend as the major potential confounders. Mortality estimates were further checked for effect modification by sex, age group, and season. The subspecies of NO3-, NH4NO3, Cr, NH4+, EC, and OC showed a higher mortality impact than the total PM2.5 mass. Males were at higher risk from NO3-, SO42-, and their NH4+ compounds along with carcinogen Cr, whereas female group was at higher risk from EC and OC. Among all age groups, the elderly above 65 years were the most vulnerable group prone to mortality effects from maximum species. The major mortality risk from all hazardous species arose from their winter exposures. Our study provides the first evidence of association between acute exposure to PM2.5 chemical species and mortality anywhere in India and recommends similar studies in other regions so that sectoral mitigation emitting the most toxic species can be prioritized to maximize the health benefits.

Seasonal variations in carbonaceous species of PM2.5 aerosols at an urban location situated in Indo-Gangetic Plain and its relationship with transport pathways, including the potential sources.

The study examines the variation in organic carbon (OC) and elemental carbon (EC) in PM2.5 concentration at an urban location of Indo-Gangetic Plains (IGP) to understand the impact of seasonality and regional crop residue burning activities. Seasonal cluster analysis of backward air masses and concentration-weighted trajectory (CWT) analysis was performed to identify seasonal transport pathways and potential source regions of carbonaceous aerosols. The mean PM2.5 level during the study period was 57 ± 41.6 µgm-3 (5.0-187.3 µgm-3), whereas OC and EC concentration ranges from 2.8 µgm-3 to 28.2 µgm-3 and 1.3 µgm-3 to 15.5 µgm-3 with a mean value of 8.4 ± 5.5 µgm-3 and 5.1 ± 3.3 µgm-3 respectively. The highest mean PM2.5 concentration was found during the winter season (111.3 ± 25.5 µgm-3), which rises 3.6 times compared to the monsoon season. OC and EC also follow a similar trend having the highest levels in winter. Total carbonaceous aerosols contribute ∼38% of PM2.5 composition. The positive linear trend between OC and EC identified the key sources. HYSPLIT cluster analysis of backward air mass trajectories revealed that during the post-monsoon, winters, pre-monsoon, and monsoon, 71%, 81%, 60%, and 43% of air masses originate within the 500 km radius of IGP. CWT analysis and abundance of OC in post-monsoon and winters season establish a linkage between regional solid-biomass fuel use and crop residue burning activities, including meteorology. Moreover, the low annual average OC/EC ratio (1.75) indicates the overall influence of vehicular emissions. The current dataset of carbonaceous aerosols collated with other Indian studies could be used to validate the global aerosol models on a regional scale and aid in evidence-based air pollution reduction strategies.

Taming the Topology of Calix[4]arene-Based 2D-Covalent Organic Frameworks: Interpenetrated vs Noninterpenetrated Frameworks and Their Selective Removal of Cationic Dyes.

A bowl-shaped calix[4]arene with its exciting host-guest chemistry is a versatile supramolecular building block for the synthesis of distinct coordination cages or metal-organic frameworks. However, its utility in the synthesis of crystalline covalent organic frameworks (COFs) remains challenging, presumably due to its conformational flexibility. Here, we report the synthesis of a periodic 2D extended organic network of calix[4]arenes joined by a linear benzidine linker via dynamic imine bonds. By tuning the interaction among neighboring calixarene units through varying the concentration in the reaction mixture, we show the selective formation of interpenetrated (CX4-BD-1) and non-interpenetrated (CX4-BD-2) frameworks. The cone-shaped calixarene moiety in the structural backbone allows for the interweaving of two neighboring layers in CX4-BD-1, making it a unique example of interpenetrated 2D layers. Due to the high negative surface charge from calixarene units, both COFs have shown high performance in charge-selective dye removal and an exceptional selectivity for cationic dyes irrespective of their molecular size. The charge distribution of the COFs and the resulting selectivity for the cationic dyes were further investigated using computational methods.

Covalent Organic Framework Embedded with Magnetic Nanoparticles for MRI and Chemo-Thermotherapy.

Nanoscale imine-linked covalent organic frameworks (nCOFs) were first loaded with the anticancer drug Doxorubicin (Dox), coated with magnetic iron oxide nanoparticles (γ-Fe2O3 NPs), and stabilized with a shell of poly(l-lysine) cationic polymer (PLL) for simultaneous synergistic thermo-chemotherapy treatment and MRI imaging. The pH responsivity of the resulting nanoagents (γ-SD/PLL) allowed the release of the drug selectively within the acidic microenvironment of late endosomes and lysosomes of cancer cells (pH 5.4) and not in physiological conditions (pH 7.4). γ-SD/PLL could efficiently generate high heat (48 °C) upon exposure to an alternating magnetic field due to the nCOF porous structure that facilitates the heat conduction, making γ-SD/PLL excellent heat mediators in an aqueous solution. The drug-loaded magnetic nCOF composites were cytotoxic due to the synergistic toxicity of Dox and the effects of hyperthermia in vitro on glioblastoma U251-MG cells and in vivo on zebrafish embryos, but they were not significantly toxic to noncancerous cells (HEK293). To the best of our knowledge, this is the first report of multimodal MRI probe and chemo-thermotherapeutic magnetic nCOF composites.

Azobenzene-Equipped Covalent Organic Framework: Light-Operated Reservoir.

Light-operated materials have gained significant attention for their potential technological importance. To achieve molecular motion within extended networks, stimuli-responsive units require free space. The majority of the so far reported 2D-extended organic networks with responsive moieties restrict their freedom of motion on account of their connectivity providing constrained free volume for efficient molecular motion. We report here a light-responsive azobenzene-functionalized covalent organic framework (TTA-AzoDFP) designed in a way that the pendent azobenzene groups are pointing toward the pore channels with sufficient free volume necessary for the unencumbered dynamic motion to occur inside the pores of the covalent organic framework (COF) and undergo a reversible trans-cis photoisomerization upon light irradiation. The resulting hydrophobic COF was used for the storage of rhodamine B and its controlled release in solution by the mechanical motion of the azobenzene units triggered by ultraviolet-light irradiation. The TTA-AzoDFP displayed unprecedented photoregulated fluorescence emission behavior upon UV-light irradiation. Size, emission, and degree of hydrophobicity with respect to trans-cis-trans photoisomerization could be reversibly controlled by alternating UV- and visible-light exposure. The results reported here demonstrate once again the importance of the careful design of the linkers not only to allow the incorporation of molecular switches within the chemical structure of COFs but also to provide the required free space for not hindering their motion. The results demonstrate that responsive COFs could be suitable platforms for delivery systems that can be controlled by external stimuli.

Source Apportionment of PM10 Over Three Tropical Urban Atmospheres at Indo-Gangetic Plain of India: An Approach Using Different Receptor Models.

The present work is the ensuing part of the study on spatial and temporal variations in chemical characteristics of PM10 (particulate matter with aerodynamic diameter ≤ 10 µm) over Indo Gangetic Plain (IGP) of India. It focuses on the apportionment of PM10 sources with the application of different receptor models, i.e., principal component analysis with absolute principal component scores (PCA-APCS), UNMIX, and positive matrix factorization (PMF) on the same chemical species of PM10. The main objective of this study is to perform the comparative analysis of the models, obtained mutually validated outputs and more robust results. The average PM10 concentration during January 2011 to December 2011 at Delhi, Varanasi, and Kolkata were 202.3 ± 74.3, 206.2 ± 77.4, and 171.5 ± 38.5 µg m-3, respectively. The results provided by the three models revealed quite similar source profile for all the sampling regions, with some disaccords in number of sources as well as their percent contributions. The PMF analysis resolved seven individual sources in Delhi [soil dust (SD), vehicular emissions (VE), secondary aerosols (SA), biomass burning (BB), sodium and magnesium salt (SMS), fossil fuel combustion, and industrial emissions (IE)], Varanasi [SD, VE, SA, BB, SMS, coal combustion, and IE], and Kolkata [secondary sulfate (Ssulf), secondary nitrate, SD, VE, BB, SMS, IE]. However, PCA-APCS and UNMIX models identified less number of sources (besides mixed type sources) than PMF for all the sampling sites. All models identified that VE, SA, BB, and SD were the dominant contributors of PM10 mass concentration over the IGP region of India.

Redox-Responsive Covalent Organic Nanosheets from Viologens and Calix[4]arene for Iodine and Toxic Dye Capture.

Owing to their chemical and thermal stabilities, high uptake capacities, and easy recyclability, covalent organic polymers (COPs) have shown promise as pollutant sponges. Herein, we describe the use of diazo coupling to synthesize two cationic COPs, COP1++ and COP2++ , that incorporate a viologen-based molecular switch and an organic macrocycle, calix[4]arene. The COPs form nanosheets that have height profiles of 6.00 nm and 8.00 nm, respectively, based on AFM measurements. The sheets remain morphologically intact upon one- or two-electron reductions of their viologen subunits. MD simulations of the COPs containing dicationic viologens indicate that the calix[4]arenes adopt a partial cone conformation and that, in height, the individual 2D polymer layers are 5.48 Šin COP1++ and 5.65 Šin COP2++ , which, together with the AFM measurements, suggests that the nanosheets are composed of 11 and 14 layers, respectively. Whether their viologens are in dicationic, radical cationic, or neutral form, the COPs exhibit high affinity for iodine, reaching up to 200 % mass increase when exposed to iodine vapor at 70 °C, which makes the materials among the best-performing nanosheets for iodine capture reported in the literature. In addition, the COPs effectively remove Congo red from solution in the pH range of 2-10, reaching nearly 100 % removal within 15 minutes at acidic pH.

Viologen-Based Conjugated Covalent Organic Networks via Zincke Reaction.

Morphology influences the functionality of covalent organic networks and determines potential applications. Here, we report for the first time the use of Zincke reaction to fabricate, under either solvothermal or microwave conditions, a viologen-linked covalent organic network in the form of hollow particles or nanosheets. The synthesized materials are stable in acidic, neutral, and basic aqueous solutions. Under basic conditions, the neutral network assumes radical cationic character without decomposing or changing structure. Solvent polarity and heating method determine product morphology. Depending upon solvent polarity, the resulting polymeric network forms either uniform self-templated hollow spheres (HS) or hollow tubes (HT). The spheres develop via an inside-out Ostwald ripening mechanism. Interestingly, microwave conditions and certain solvent polarities result in the formation of a robust covalent organic gel framework (COGF) that is organized in nanosheets stacked several layers thick. In the gel phase, the nanosheets are crystalline and form honeycomb lattices. The use of the Zincke reaction has previously been limited to the synthesis of small viologen molecules and conjugated viologen oligomers. Its application here expands the repertoire of tools for the fabrication of covalent organic networks (which are usually prepared by dynamic covalent chemistry) and for the synthesis of viologen-based materials. All three materials-HT, HS, and COGF-serve as efficient adsorbents of iodine due to the presence of the cationic viologen linker and, in the cases of HT and HS, permanent porosity.

Vehicular pollution as the primary source of oxidative potential of PM2.5 in Bhubaneswar, a non-attainment city in eastern India.

We assessed the oxidative potential (OP) of PM2.5 (n = 230) using dithiothreitol (DTT) assay to identify the major emission sources in Bhubaneswar (20.20°N, 85.80°E), one of the non-attainment cities under the National Clean Air Program, situated on the eastern coast of India. Continuous day and night PM2.5 samples were collected during periods influenced by marine airmass (MAM; April-May 2019) as well as continental airmass (CAM; October 2019-December 2019). Volume normalized DTT (DDTv) activities were approximately two times higher during CAM compared to MAM periods. In contrast, mass normalized DTT activity (DDTm) showed insignificant variations between CAM and MAM periods. This might be due to particulate organic matter, which accounted for more than one-fifth of the PM2.5 mass loading and remained surprisingly invariant during the study periods. Positive matrix factorization (PMF) identified secondary aerosols (MAM: 26% and CAM: 33%) as dominant contributors to PM2.5 mass in both periods. OP, is, however, dominated by vehicular emissions (21%) as identified through multiple linear regression. Conditional Bivariate Probability Function (CBPF) analysis indicated that local sources were the primary drivers for the catalytic activity of PM2.5 in the study region. Additionally, stagnant meteorological conditions, combined with the chemical aging of species during regional transport of pollutants, likely enhanced redox activity of PM2.5 during the CAM period. The study highlights that increasing traffic congestion is primarily responsible for adverse health outcomes in the region. Therefore, it is important to regulate mobility and vehicular movement to mitigate the hazardous impact of PM2.5 in Bhubaneswar.

Emission inventory of inorganic trace gases from solid residential fuels over the National Capital Territory of India.

In developing nations, solid residential fuels are the major sources of primary energy for various domestic activities. To date, the emission inventory of inorganic trace gases over National Capital Territory (NCT) was prepared using either default or country-specific emission factors. In this paper, we report (for the first time) the spatial variation of emission factors (EFs) of inorganic trace gases (SO2, NO, NO2, CO, CO2, and CH4) from the residential fuels used in slums and rural areas of NCT determined using dilution chamber in the laboratory. 147 residential fuel samples, including fuelwood, dung cake, crop residues, coal, etc., were collected at 149 NCT locations out of 675 slum clusters and 146 rural villages. The range of EF(s) of SO2 (0.02 ± 0.01 to 0.04 ± 0.01 g kg-1), CH4 (0.10 to 0.34 g kg-1), NO2 (0.01 to 0.02 g kg-1) is lower than the CO (3.55 ± 1.72 to 6.07 ± 1.53 g kg-1) and CO2 (0 to 129.45 ± 46.94 g kg-1). The north and north west districts of NCT are emission hotspots for CH4, NO, and NO2 emissions, whereas, the southern and northern areas of NCT are for CO2. These citywide emission inventories (0.05° × 0.05°) of inorganic trace gases are prepared using laboratory-determined EFs and available consumption data determined by recent survey information. Among solid residential fuels, fuel wood, and dung cake are two major contributors to inorganic trace gases in NCT.

Identification of sources of coarse mode aerosol particles (PM10) using ATR-FTIR and SEM-EDX spectroscopy over the Himalayan Region of India.

This study attempts to examine the morphological, elemental and physical characteristics of PM10 over the Indian Himalayan Region (IHR) using FTIR and scanning electron microscopy-energy dispersive X-ray (SEM-EDX) analysis. The study aimed at source identification of PM10 by exploring the inorganic ions, organic functional groups, morphology and elemental characteristics. The pollution load of PM10 was estimated as 63 ± 22 µg m-3; 53 ± 16 µg m-3; 67 ± 26 µg m-3 and 55 ± 11 µg m-3 over Mohal-Kullu, Almora, Nainital and Darjeeling, respectively. ATR-FTIR spectrum analysis revealed the existence of inorganic ions (SiO44-, TiO2, SO42-, SO3-, NO3-, NO2-, CO32-, HCO3-, NH4+) and organic functional groups (C-C, C-H, C=C, C≡C, C=O, N-H, C≡N, C=N, O-H, cyclic rings, aromatic compounds and some heterogeneous groups) in PM10 which may arise from geogenic, biogenic and anthropogenic sources. The morphological and elemental characterization was performed by SEM-EDX, inferring for geogenic origin (Al, Na, K, Ca, Mg and Fe) due to the presence of different morphologies (irregular, spherical, cluster, sheet-like solid deposition and columnar). In contrast, particles having biogenic and anthropogenic origins (K, S and Ba) have primarily spherical with few irregular particles at all the study sites. Also, the statistical analysis ANOVA depicts that among all the detected elements, Na, Al, Si, S and K are site-specific in nature as their mean of aw% significantly varied for all the sites. The trajectory analysis revealed that the Uttarakhand, Jammu and Kashmir, the Thar Desert, Himachal Pradesh, Pakistan, Afghanistan, Nepal, Sikkim, the Indo-Gangetic Plain (IGP) and the Bay of Bengal (BoB) contribute to the increased loading of atmospheric pollutants in various locations within the IHR.

Role of South Asian outflow on the oxidative potential of marine aerosols over the Indian Ocean.

Oxidative potential (OP) of fine marine aerosols (PM2.5) over the northern Indian Ocean (N_IO) and equatorial Indian Ocean (E_IO) were studied using shipborne measurements conducted as part of the Integrated Campaign for Aerosols, gases and Radiation Budget (ICARB-2018). During the study, an enhanced concentration of PM2.5 was found over N_IO (27.22 ± 14.29 µg.m-3) compared with E_IO (15.91 ± 2.58 µg.m-3), as N_IO experiences continental outflow from anthropogenically dominated South Asian region. However, E_IO received pristine air masses from the middle of the Arabian Sea, implying a reduced concentration. The OP of PM2.5 was evaluated using a dithiothreitol (DTT) assay. The mass (DTTm or intrinsic OP) and volume (DTTv or extrinsic OP) normalized DTT exhibited a significant spatial variation over the Indian Ocean (IO). Intrinsic OP showed ∼2 times higher values over N_IO than E_IO, indicating aging of aerosols during long-range transport impacts OP of marine aerosol. Similarly, increased concentrations of anthropogenic species such as non-sea sulfate (nssSO42-), nitrate (NO3-), ammonium (NH4+), non-sea potassium ion (nssK+), water-soluble transition metals (Fe, Ti, Zn, Cu, Mn, Cr), elemental carbon (EC), organic carbon (OC), water-soluble organic carbon (WSOC), were also observed over N_IO compared with E_IO. Pearson correlation and multiple linear regression (MLR) analysis revealed that combustion sources, chemical processing and co-transportation of anthropogenic species during long-range transport are the main drivers of intrinsic OP in the outflow region.

Light-driven self-assembly of spiropyran-functionalized covalent organic framework.

Controlling the number of molecular switches and their relative positioning within porous materials is critical to their functionality and properties. The proximity of many molecular switches to one another can hinder or completely suppress their response. Herein, a synthetic strategy involving mixed linkers is used to control the distribution of spiropyran-functionalized linkers in a covalent organic framework (COF). The COF contains a spiropyran in each pore which exhibits excellent reversible photoswitching behavior to its merocyanine form in the solid state in response to UV/Vis light. The spiro-COF possesses an urchin-shaped morphology and exhibits a morphological transition to 2D nanosheets and vesicles in solution upon UV light irradiation. The merocyanine-equipped COFs are extremely stable and possess a more ordered structure with enhanced photoluminescence. This approach to modulating structural isomerization in the solid state is used to develop inkless printing media, while the photomediated polarity change is used for water harvesting applications.

Synthesis of Self-Assembled Single Atomic Layer Gold Crystals-Goldene.

We report, for the first time, a technique to synthesize free-standing, one-atom thick 2D gold crystals (namely, goldene) and self-assembled 2D periodic arrays of goldene. High-resolution transmission electron microscopy (HRTEM) imaging of goldene revealed herringbone and honeycomb lattices, which are primarily gold surface features due to its reconstruction. Imaging of these surface-only features by a nonsurface characterization technique such as HRTEM is an unequivocal proof of the absence of three-dimensionality in goldene. Atomic force microscopy confirmed 1-2 Šthickness of goldene. High-resolution X-ray photoelectron spectroscopy (HR-XPS), selective area electron diffraction, and energy-dispersive X-ray spectroscopy confirmed the chemical identity of goldene. We discovered the phenomenon of electric field-induced self-assembly of goldene supracrystals with a herringbone structure and developed an electric field printing (e-print) technique for goldene arrays. Goldene showed a semiconductor response with a knee voltage of ∼3.2 V, and I/V spectroscopy revealed periodic room temperature Coulomb blockade oscillations. These observations are consistent with the theoretical calculations reported in the literature predicting enhanced Coulombic interactions between gold valence electrons and the nucleus in stable 2D gold. Goldene exhibited multiple, intense, and well-resolved optical absorption peaks and several fine bands across the UV-vis region, and we calculated its optical band gap to be 3.59 eV. Magnetic force microscopy measurements of goldene periodic arrays showed a ∼5 mV peak amplitude confirming its ferromagnetism. Optical and magnetic properties of goldene are consistent with those reported in the literature for 2D planar gold clusters with less than 12 atoms.