Decoupling excitons from high-frequency vibrations in organic molecules.

The coupling of excitons in π-conjugated molecules to high-frequency vibrational modes, particularly carbon-carbon stretch modes (1,000-1,600 cm-1) has been thought to be unavoidable1,2. These high-frequency modes accelerate non-radiative losses and limit the performance of light-emitting diodes, fluorescent biomarkers and photovoltaic devices. Here, by combining broadband impulsive vibrational spectroscopy, first-principles modelling and synthetic chemistry, we explore exciton-vibration coupling in a range of π-conjugated molecules. We uncover two design rules that decouple excitons from high-frequency vibrations. First, when the exciton wavefunction has a substantial charge-transfer character with spatially disjoint electron and hole densities, we find that high-frequency modes can be localized to either the donor or acceptor moiety, so that they do not significantly perturb the exciton energy or its spatial distribution. Second, it is possible to select materials such that the participating molecular orbitals have a symmetry-imposed non-bonding character and are, thus, decoupled from the high-frequency vibrational modes that modulate the π-bond order. We exemplify both these design rules by creating a series of spin radical systems that have very efficient near-infrared emission (680-800 nm) from charge-transfer excitons. We show that these systems have substantial coupling to vibrational modes only below 250 cm-1, frequencies that are too low to allow fast non-radiative decay. This enables non-radiative decay rates to be suppressed by nearly two orders of magnitude in comparison to π-conjugated molecules with similar bandgaps. Our results show that losses due to coupling to high-frequency modes need not be a fundamental property of these systems.

Assessment of water quality and source apportionment of pollution in a tropical river in eastern India: A study utilizing multivariate statistical tools and the APCS-MLR receptor model.

The Mundeswari River, an ecologically distressed river in eastern India, has been subjected to water quality deterioration largely due to anthropogenic activities in its vicinity. This study aimed to comprehensively evaluate the current state of pollution in the river and assess the appropriateness of river water for irrigation, given its extensive use for agricultural purposes. Monthly water quality monitoring was undertaken at four distinct sampling sites (SP1-SP4) over a two-year period (2020-2022), considering seventeen water quality parameters. This research employed principal component analysis/factor analysis (PCA/FA) and absolute principal component score-multiple linear regression (APCS-MLR) receptor modelling. These methodologies were used to discern and quantify potential sources of pollution influencing the water quality of the Mundeswari River. The study revealed that the water quality of the Mundeswari River was most degraded during the pre-monsoon season. Among the four sampling sites, SP3 exhibited the highest level of pollution with mean biochemical oxygen demand (BOD) and chemical oxygen demand (COD) values of 5.36 mg/L and 44.72 mg/L, respectively. According to the one-way analysis of variance (ANOVA), there was considerable spatial and seasonal disparities (P < 0.05) in most water quality parameters. The PCA/FA extracted four latent pollution sources, accounting for 81.5% of the total variance. The primary factors influencing the quality of river water are natural weathering processes, discharge of domestic effluent and waste, and agricultural runoff. The APCS-MLR receptor model further revealed that agricultural drainage factors and the discharge of domestic effluent and waste had a greater impact on the Mundeswari River. The investigation concluded that the mean values of all indicators for irrigation suitability were below the defined threshold limits, indicating that the water of the studied river appears suitable for irrigation. The outcomes of this study may significantly contribute to the formulation of sustainable strategies for the ecological rejuvenation of the Mundeswari River.

Tailoring Interlayer Charge Transfer Dynamics in 2D Perovskites with Electroactive Spacer Molecules.

The family of hybrid organic-inorganic lead-halide perovskites are the subject of intense interest for optoelectronic applications, from light-emitting diodes to photovoltaics to X-ray detectors. Due to the inert nature of most organic molecules, the inorganic sublattice generally dominates the electronic structure and therefore the optoelectronic properties of perovskites. Here, we use optically and electronically active carbazole-based Cz-Ci molecules, where Ci indicates an alkylammonium chain and i indicates the number of CH2 units in the chain, varying from 3 to 5, as cations in the two-dimensional (2D) perovskite structure. By investigating the photophysics and charge transport characteristics of (Cz-Ci)2PbI4, we demonstrate a tunable electronic coupling between the inorganic lead-halide and organic layers. The strongest interlayer electronic coupling was found for (Cz-C3)2PbI4, where photothermal deflection spectroscopy results remarkably reveal an organic-inorganic charge transfer state. Ultrafast transient absorption spectroscopy measurements demonstrate ultrafast hole transfer from the photoexcited lead-halide layer to the Cz-Ci molecules, the efficiency of which increases by varying the chain length from i = 5 to i = 3. The charge transfer results in long-lived carriers (10-100 ns) and quenched emission, in stark contrast to the fast (sub-ns) and efficient radiative decay of bound excitons in the more conventional 2D perovskite (PEA)2PbI4, in which phenylethylammonium (PEA) acts as an inert spacer. Electrical charge transport measurements further support enhanced interlayer coupling, showing increased out-of-plane carrier mobility from i = 5 to i = 3. This study paves the way for the rational design of 2D perovskites with combined inorganic-organic electronic properties through the wide range of functionalities available in the world of organics.

Chemical Tuning of Zwitterionic Ionic Liquids for Variable Thermophysical Behaviours, Nanostructured Aggregates and Dual-Stimuli Responsiveness.

The design and synthesis of a series of zwitterionic ionic liquids (ZILs) to understand the structure-property relationship towards an increase of the thermal stability, a variation of the glass transition temperature, the shape-tuning of nanostructured aggregates and the tuning of the stimuli responsiveness are demonstrated. The substitution reaction of imidazole with various aliphatic and aromatic bromides followed by the reaction of the corresponding substituted imidazoles with bromoalkyl carboxylic acids of varying spacer length produces the ZILs. In aqueous solution, a ZIL molecule either exist in its ionic liquid (substituted imidazolium bromide) form or its zwitterionic (substituted imidazolium alkyl carboxylate) form with an isoelectric point (pI) depending on the pH value of the solution. Upon changing the pH to near or above the pI, the aqueous ZIL solution undergoes transition from a transparent to a turbid phase due to the formation of insoluble hierarchical nanostructured aggregates of various morphologies, such as spheres, tripods, tetrapods, fern-like, flower-like, dendrites etc. depending on the pH of the solution and the nature of the alkyl/vinyl/aryl substituents. Upon heating the solution a phase transition occurs from turbid to transparent, exhibiting a distinct reversible upper critical solution temperature (UCST)-type cloud point (Tcp ). It is observed that the cloud point varies with the nature of the substituent, an increase of the concentration of the ZIL as well as with changes of the pH of the solution.

Untying arsenite tolerance mechanisms in contrasting maize genotypes attributed to NIPs-mediated controlled influx and root-to-shoot translocation, redox homeostasis and phytochelatin-mediated detoxification pathway.

Contamination of ground water and soil with toxic metalloids like arsenic (As) poses a serious hazard to the global agricultural food production. One of the best ways to restrict entry of As into the food chain is selection of germplasms which accrue extremely low level of As in grains. Here, we screened diverse maize genotypes under high arsenite (100 µM AsIII) stress and identified PMI-PV-9 and PMI-PV-3 as AsIII-tolerant and -sensitive maize genotype respectively. Expression of genes associated with As uptake, vacuolar sequestration, biosynthesis of phytochelatins, root-to-shoot translocation, in vivo ROS generation, fine tuning of antioxidant defense system, DNA and membrane damage, H2O2 and superoxide anion (O2•-) levels were compared among the selected genotypes. PMI-PV-9 plants performed much better than PMI-PV-3 in terms of plant growth with no visible symptom of As toxicity. Susceptibility of PMI-PV-3 to AsIII stress may be attributed to comparatively low expression of genes involved in phytochelatins (PCs) biosynthesis. Concomitant decrease in ABCC1 expression might be another key factor for futile sequestration of AsIII into root vacuoles. Moreover, up-regulation of ZmNIP3;1 might contribute in high root-to-leaf As translocation. Substantial spike in H2O2, O2•- and MDA levels indicates that PMI-PV-3 plants have experienced more oxidative stress than PMI-PV-9 plants. Appearance of prominent deep brown and dark blue spots/stripes on leaves as revealed after DAB and NBT staining respectively suggest severe oxidative burst in PMI-PV-3 plants. Marked reduction in DHAR and MDAR activity rendered PMI-PV-3 cells to recycle ascorbate pool ineffectively, which might have exacerbated their susceptibility to AsIII stress. In a nutshell, incompetent PCs mediated detoxification system and disruption of cellular redox homeostasis owing to feeble antioxidant defence system resulting oxidative burst might be the prime reasons behind reduced performance of PMI-PV-3 plants under AsIII stress.

Efficient near-infrared organic light-emitting diodes with emission from spin doublet excitons.

The development of luminescent organic radicals has resulted in materials with excellent optical properties for near-infrared emission. Applications of light generation in this range span from bioimaging to surveillance. Although the unpaired electron arrangements of radicals enable efficient radiative transitions within the doublet-spin manifold in organic light-emitting diodes, their performance is limited by non-radiative pathways introduced in electroluminescence. Here we present a host-guest design for organic light-emitting diodes that exploits energy transfer with up to 9.6% external quantum efficiency for 800 nm emission. The tris(2,4,6-trichlorophenyl)methyl-triphenyl-amine radical guest is energy-matched to the triplet state in a charge-transporting anthracene-derivative host. We show from optical spectroscopy and quantum-chemical modelling that reversible host-guest triplet-doublet energy transfer allows efficient harvesting of host triplet excitons.

Synthesis of model heterojunction interfaces reveals molecular-configuration-dependent photoinduced charge transfer.

Control of the molecular configuration at the interface of an organic heterojunction is key to the development of efficient optoelectronic devices. Due to the difficulty in characterizing these buried and (probably) disordered heterointerfaces, the interfacial structure in most systems remains a mystery. Here we demonstrate a synthetic strategy to design and control model interfaces, enabling their detailed study in isolation from the bulk material. This is achieved by the synthesis of a polymer in which a non-fullerene acceptor moiety is covalently bonded to a donor polymer backbone using dual alkyl chain links, constraining the acceptor and donor units in a through space co-facial arrangement. The constrained geometry of the acceptor relative to the electron-rich and -poor moieties in the polymer backbone can be tuned to control the kinetics of charge separation and the energy of the resultant charge-transfer state giving insight into factors that govern charge generation at organic heterojunctions.

Extending the defect tolerance of halide perovskite nanocrystals to hot carrier cooling dynamics.

Defect tolerance is a critical enabling factor for efficient lead-halide perovskite materials, but the current understanding is primarily on band-edge (cold) carriers, with significant debate over whether hot carriers can also exhibit defect tolerance. Here, this important gap in the field is addressed by investigating how intentionally-introduced traps affect hot carrier relaxation in CsPbX3 nanocrystals (X = Br, I, or mixture). Using femtosecond interband and intraband spectroscopy, along with energy-dependent photoluminescence measurements and kinetic modelling, it is found that hot carriers are not universally defect tolerant in CsPbX3, but are strongly correlated to the defect tolerance of cold carriers, requiring shallow traps to be present (as in CsPbI3). It is found that hot carriers are directly captured by traps, instead of going through an intermediate cold carrier, and deeper traps cause faster hot carrier cooling, reducing the effects of the hot phonon bottleneck and Auger reheating. This work provides important insights into how defects influence hot carriers, which will be important for designing materials for hot carrier solar cells, multiexciton generation, and optical gain media.

Near-infrared luminescent open-shell π-conjugated systems with a bright lowest-energy zwitterionic singlet excited state.

Open-shell systems with extensive π-conjugation have fascinating properties due to their narrow bandgaps and spin interactions. In this work, we report neutral open-shell di- and polyradical conjugated materials exhibiting intriguing optical and magnetic properties. Our key design advance is the planarized geometry allowing for greater interaction between adjacent spins. This results in absorption and emission in the near infrared at 803 and 1050 nanometers, respectively, and we demonstrate a unique electronic structure where a bright zwitterionic excited state is the lowest-accessible electronic transition. Electron paramagnetic resonance spectroscopy and superconducting quantum interference device measurements reveal that our materials are open-shell singlets with different degrees of spin interactions, dynamics, and antiferromagnetic properties, which likely contributed to the formation of their emissive zwitterionic singlet excited state and near-infrared emission. In addition, our materials show reversible and stable electrochromic switching with more than 500 cycles, indicating their potential for optoelectronic and electrochemical energy storage applications.

microRNAomic profiling of maize root reveals multifaceted mechanisms to cope with Cr (VI) stress.

Chromium (Cr) contamination of soil and water poses serious threats to agricultural crop production. MicroRNAs (miRNAs) are conserved, non-coding small RNAs that play pivotal roles in plant growth, development and stress responses through fine-tuning of post-transcriptional gene expression. To better understand the molecular circuit of Cr-responsive miRNAs, two sRNA libraries were prepared from control and Cr (VI) [100 ppm] exposed maize roots. Using deep sequencing, we identified 80 known (1 up and 79 down) and 18 downregulated novel miRNAs from Cr (VI) challenged roots. Gene ontology (GO) analysis reveals that predicted target genes of Cr (VI) responsive miRNAs are potentially involved in diverse cellular and biological processes including plant growth and development (miR159c, miR164d, miR319b-3p and zma_25.145), redox homeostasis (miR528-5p, miR396a-5p and zma_9.132), heavy metal uptake and detoxification (miR159f-5p, 164e-5p, miR408a, miR444f and zma_2.127), signal transduction (miR159f, miR160a-5p, miR393a-5p, miR408-5p and zma_43.158), cell signalling (miR156j, 159c-5p, miR166c-5p and miR398b). Higher accumulation of Cr in maize roots might be due to upregulation of ABC transporter G family member 29 targeted by miR444f. Instead of isolated increase in SOD expression, significant decline in GSH:GSSH ratio and histochemical staining strongly suggest Cr (VI) stress mediated disruption of ROS scavenging machinery thus unbalancing normal cellular homeostasis. Moreover, miR159c-mediated enhanced expression of GAMYB might be a reason for impaired root growth under Cr (VI) stress. In a nutshell, the present microRNAomic study sheds light on the miRNA-target gene regulatory network involved in adaptive responses of maize seedlings to Cr (VI) stress.