Cyanide Research Articles

Simple Air-Stable [3]Radialene Anion Radicals as Environmentally Switchable Catholytes in Water.

The hexacyano[3]radialene radical anion (1) is an attractive catholyte material for use in redox flow battery (RFB) applications. The substitution of cyano groups with ester moieties enhances solubility while maintaining redox reversibility and favorable redox potentials. Here we show that these ester-functionalized, hexasubstituted [3]radialene radical anions dimerize reversibly in water. The dimerization mode is dependent on the substitution pattern and can be switched in solution. Stimuli-responsive behavior is achieved by exploiting an unprecedented tristate switching mechanism, wherein the radical can be toggled between the free radical, a π-dimer, and a σ-dimer-each with dramatically different optical, magnetic, and redox properties-by changing the solvent environment, temperature, or salinity. The symmetric, triester-tricyano[3]radialene (3) forms a solvent-responsive, σ-dimer in water that converts to the radical anion with the addition of organic solvents or to a π-dimer in brine solutions. Diester-tetracyano[3]radialene (2) exists primarily as a π-dimer in aqueous solutions and a radical anion in organic solvents. The dimerization behavior of both 2 and 3 is temperature dependent in methanol solutions. Dimerization equilibrium has a direct impact on catholyte stability during galvanostatic charge-discharge cycling in static H-cells. Specifically, conditions that favor the free radical anion or π-dimer exhibit significantly enhanced cycling profiles.

Chemistry and Biology of Cyanides: A Literature Review

The term cyanide is used to describe compounds that contain the cyano, -C≡N, group. The cyanides exist in nature as inorganic as well as organic compounds in the forms of gas or liquid such as HCN, CNCl and acetonitrile, or solids such as NaCN, KCN, and Ca(CN)2. Cyanide compounds are also found in addible plants as cyanogenic glycosides. Compounds that can release cyanide are known as cyanogenic compounds. HCN has a low boiling point (25.63 oC) and is as weakly acidic with a pKa 9.2. It partially ionizes in water to give the cyanide anion, -CN. Cyanide ion from salt reacts with acid to give HCN, but at high pH (8-10), it remains as cyanide ion even if the temperature of the water is 80.0-100.0 °C. Cyanide is one of the deadliest poisons, LC50 is 1.1 and 5.0 mg/kg for HCN and NaCN, which can cause death to those who come into contact within a few minutes or hours of exposure, depending on the level and route of exposure. It is a rapidly acting, potentially deadly chemical that interferes with the body’s ability to use oxygen. Due to its toxicity, cyanide has many roles in industry such as pesticides and medicines as nitrile-containing pharmaceuticals. Organic compounds that have a −C≡N functional group are called nitriles. Over 30 nitrile-containing pharmaceuticals are currently marketed for a diverse variety of medicinal indications with more than 20 additional nitrile-containing leads in clinical development. In addition, over 120 naturally occurring nitriles have been isolated from terrestrial and marine sources. In plants, cyanides are usually bound to sugar molecules in the form of cyanogenic glycosides. Hydrogen cyanide can be released from hydrolysis of cyanogenic glycosides which are commonly present in edible plants. Because it is a relatively common toxin in the environment, the body can detoxify a small amount of cyanide. The major route of metabolism for cyanides is detoxification in the liver by the mitochondrial enzyme rhodanese, which catalyzes the transfer of the sulfane sulfur of thiosulfate to the cyanide ion to form thiocyanate. Ingested cyanide may be countered by administering antidotes, such as natural vitamin B12 and sodium thiosulfate, that detoxify cyanide or bind to it.

Tailoring thermosetting benzoxazoles for optimal performance: Balancing thermal stability, dielectric properties, and processability

Polybenzoxazole (PBO) has excellent heat resistance and dielectric properties. However, it lacks a distinct melting point and is only soluble in sulfuric and methyl sulfonic acids. This limited solubility significantly hinders its practical application due to poor processability. In order to improve the processability of PBO while preserving its thermal stability and dielectric properties, this paper investigates the impact of introducing bridging structures between benzoxazole groups and employing cross-linking groups at the chain ends. The study primarily focuses on assessing the effects of these modifications on the thermosetting PBO properties, including heat resistance, dielectric properties, and processability. The results indicate that the cured polymer exhibits high thermal stability when a biphenyl group is used as bridging structure and a cyano group as the end group. Among these thermosetting monomers, p-LARBCN has the best overall performance. The 5 % thermal decomposition temperature (Td5) of cured p-LARBCN is 612 °C, which is very similar to PBO. The dielectric constant of the cured p-LARBCN is below 2.7, and the dielectric loss is below 0.02. The dielectric performance is close to that of PBO. In addition, p-LARBCN shows good solubility in solvents like DMSO, DMF, and DMAc, which greatly improves its processability compared to PBO. This study presents a modified thermosetting PBO resin that combines high thermal stability with improved processability. This resin holds promise for applications in the aviation and aerospace fields, particularly as a high-temperature-resistant material.

Distinctive interphasial properties and high structural reversibility endowed by B-/CN– electrolyte additive and its superior electrochemical performance for graphite/LiCoO2 pouch cells

The exploration of high energy density batteries requires cathodes with a high specific capacity and high voltage. LiCoO2 (LCO), a prospective cathode material for lithium-ion batteries (LIBs), displays a decent capacity but without a compatible electrolyte to withstand its high voltage. To create an enduring cathode electrolyte interphase (CEI), a novel electrolyte additive, 2-cyanophenylboronic acid (CBB), which possesses both cyano (CN–) and boronic acid (B-) functional group, is firstly put forward to be applied in LCO/Li cells as well as graphite/LCO pouch cell. Data from experimental and theoretical research both reveal that CBB preferentially decomposes on LCO surface, constructing a thin, robust and homogeneous CEI film rich in B-F/B-O species with fast kinetics and low impedance, suppressing the LCO surface transformation upon cycling due to the alleviated Co dissolution. CBB additive can enhance the structural reversibility (in-situ X-ray diffraction), decrease the electrolyte decomposition and eliminate the HF formation, constructing a much smoother surface than base electrolyte. LCO/Li cells with 1% CBB deliver more excellent capacity retention (96%) and a much superior rate capability (145 mAh/g, 5C) than that of base electrolyte (67%, 115 mAh/g). Intriguingly, graphite/LCO pouch batteries containing 1% CBB for 300 cycles deliver more outstanding capacity retention of 80% than that of base electrolyte (2%). This work reveals that CBB can function as an efficient electrolyte additive for high voltage LCO cathode, of which its distinctive CEI modification on the LCO surface provides valuable perspectives for its commercial application towards high energy density LIBs.

Constructing Cooperative Interface via Bi-Functional COF for Facilitating the Sulfur Conversion and Li+ Dynamics.

Lithium-sulfur (Li-S) batteries stand out for their high theoretical specific capacity and cost-effectiveness. However, the practical implementation of Li-S batteries is hindered by issues such as the shuttle effect, tardy redox kinetics, and dendrite growth. Herein, an appealingly designed covalent organic framework (COF) with bi-functional active sites of cyanide groups and polysulfide chains (COF-CN-S) is developed as cooperative functional promoters to simultaneously address dendrites and shuttle effect issues. Combining in situ techniques and theoretical calculations, it can be demonstrated that the unique chemical architecture of COF-CN-S is capable of performing the following functions: 1) The COF-CN-S delivers significantly enhanced Li+ transport capability due to abundant ion-hopping sites (cyano-groups); 2) it functions as a selective ion sieve by regulating the dynamic behavior of polysulfide anions and Li+ , thus inhibiting shuttle effect and dendrite growth; 3) by acting as a redox mediator, the COF-CN-S can effectively control the electrochemical behavior of polysulfides and enhance their conversion kinetics. Based on the above advantages, the COF-CN-S endows Li-S batteries with excellent performance. This study highlights the significance of interface modification and offers novel insights into the rational design of organic materials in the Li-S realm.

A Facile and General Oxidative Hydroxylation of Organoboron Compounds: Citric Acid as an Efficient Catalyst in Water to Access Phenolic and Alcoholic Motifs

An efficient and convenient method for the synthesis of phenols and aliphatic alcohols is described in this paper. The oxidative hydroxylation reaction of various organoboron compounds proceeded smoothly by employing H2O2 as the oxidant and citric acid as the catalyst in water at room temperature to produce phenols and aliphatic alcohols in satisfactory to excellent yields (up to 99% yield). Various synthetically useful functional groups, such as halogen atom, cyano, and nitro groups, remain intact during the oxidative hydroxylation. The developed catalytic system also could accommodate phenylboronic pinacol ester and potassium phenyltrifluoroborate to give the target product good yields.

Boronyl-Based Polycyclic Superhalogens.

Superhalogenity refers to the tendency of radicals to have higher electron affinity (EA) than halogens or anions to possess higher vertical detachment energy (VDE) than do halides (3.64 eV). In Srivastava, A. K. J. Phys. Chem. A 2023, 127, 4867-4872, we demonstrated a simple strategy in which some polycyclic hydrocarbons (PHs) can be turned into polycyclic superhalogens (PSs) by substituting CN groups in the place of hydrogens. We also notice that the superhalogenity of cyanide-based PSs is related to their aromaticity. Boronyl (BO) is an isoelectronic and inorganic analog of the cyano (CN) group. Therefore, we consider the substitution of BO in PHs and compare them with CN-based PSs using the density functional theory. In the case of C5H5-, we notice that the B3LYP and CCSD(T) calculated VDEs of resulting C5H5-n(BO)n- anions increase with the increase in the number of BO substituents (n) such that they become superhalogens for n ≥ 3 like C5H5-n(CN)n- anions. However, their aromaticity does not correspond to the superhalogenity, unlike C5H5-n(CN)n-. Similarly, all BO-substituted PHs possess structures similar to their CN analogs. Although their aromaticity is reduced compared to CN-based anions, the VDE of all these BO-based polycyclic anions and the EA of their radicals exceed 5 eV than those of the corresponding CN-based PSs. Therefore, this study proposes a new class of boronyl-based polycyclic superhalogens. These superhalogen anions might attract synthetic chemists and experimentalists for further explorations.

Re-evaluation of solution enthalpies of aliphatic hydrocarbons functional derivatives and terpenes in n-heptane and their validation by thermochemical consistency

The aim of this study was to investigate the influence of the position of the functional group and the choice of solvent on the relationships between the enthalpies of solution and the alkyl chain length of aliphatic hydrocarbons functional derivatives. The results show that the selection of an appropriate solvent for functional derivatives, such as methanol for alcohols and acetonitrile for alkyl nitriles, is not a viable option because the enthalpies of solution increase non-linearly with increasing alkyl chain length, leading to significant errors in the prediction of enthalpies of solution.On the other hand, the enthalpies of solution of aliphatic hydrocarbons functional derivatives in n-heptane decrease non-linearly with increasing number of methylene fragments in the chain. In this work, complementary measurements of the enthalpies of solution of homologous series of dialkyl ethers, alkyl-amines and nitroalkanes in n-heptane were carried out. These new data were used to develop an approach to estimate the enthalpies of solution of dialkyl ethers, alkyl-nitriles and alkyl-amines in n-heptane. The absolute deviations between predicted and experimental solution enthalpies for most of the investigated compounds do not exceed 0.5 kJ mol−1. The proposed approach to predict the solution enthalpies of aliphatic hydrocarbon derivatives in n-heptane was applied to estimate the enthalpies of fusion of 11 aliphatic hydrocarbon derivatives, which agreed well with the values obtained by differential scanning calorimetry. Complementary vapour pressure measurements were carried out on cyclic aliphatic hydrocarbons from the terpene family using a transpiration method to derive their enthalpies of vaporisation. The latter were used for independent validation of the re-evaluated solution enthalpies.

Synthesis, recovery, and application of environmentally friendly disperse dyes with high light fastness

Dye wastewater has attracted great attention due to high pollution and toxicity which can cause harm to the living environment. It is common for azo-disperse dyes to be used to dye hydrophobic fibers. A reduction clearing method is used to eliminate the dye particles on the fabric after dyeing. However, when azo disperse dyes on the fiber surface are eliminated by the reduction clearing process, this can give rise to an effluent discharge due to the presence of sodium hydrosulfite. The introduction of carboxylic ester groups into dye molecules can effectively avoid this issue. Six novel environmentally friendly alkali-clearable disperse dyes, containing cyano and carboxylic ester groups, were readily synthesized by a diazo coupling reaction with various diazo components. Their dyeing properties on polyethylene terephthalate fabrics were respectively measured and compared with those of commercial reference dyes. It was indicated that some fastness properties of the synthesized dyes on polyethylene terephthalate fabrics after the alkali clearing were improved compared with those of the reference dyes due to the existence of the carboxylic ester group. Moreover, the chromaticity of dye wastewater can be further reduced by recovering hydrolyzed dyes.

Synthesis of a Pinacol Boronate Precursor for [18F]Rucaparib Radiosynthesis

AbstractA novel synthetic approach toward pinacol boronate used as a precursor in the recent radiosynthesis of [18F]rucaparib is described in this study. The Heck reaction of an ortho‐iodoaniline derivative bearing a chloride group at the meta‐position with acrylonitrile produced the desired (E)‐2‐aminocinnamonitrile derivative. The subsequent cyanide‐catalyzed imino‐Stetter reaction of aldimine derived from the obtained 2‐aminocinnamonitrile and aldehyde afforded the required trisubstituted indole‐3‐acetonitrile. The reduction of the nitrile group with cobalt boride followed by the construction of an azepinone scaffold generated indoloazepinone bearing a chloride substituent at the C6‐position of the indole scaffold. The Suzuki–Miyaura borylation of the chloride substituent produced pinacol boronate previously used in the synthesis of [18F]rucaparib. Detailed outcomes of different approaches using different 2‐aminocinnamonitriles were discussed as well.

Effect of Complexation with Closo-Decaborate Anion on Photophysical Properties of Copolyfluorenes Containing Dicyanophenanthrene Units in the Main Chain

The functionalization of copolyfluorenes containing dicyanophenanthrene units by closo-decaborate anion is described. Target copolyfluorenes were analyzed using SEM, UV-vis, luminescence, NMR, and Fourier-transform infrared (FTIR) spectroscopy. The effect of complexation with the closo-decaborate anion on the photophysical properties was studied both experimentally and theoretically. The PL data indicate an efficient charge transfer from fluorene to the dicyanophenanthrene units coordinated to the closo-decaborate. The coordination of closo-decaborate clusters to the nitrile groups of copolyfluorenes provides an important route to new materials for sensors and light-emitting devices while, at the same time, serving as a platform for further study of the nature of boron clusters.

Surface Functionalized Mesoporous Silica Nanoparticles for Enhanced Removal of Heavy Metals: A Review

Human health and environmental sustainability are strongly influenced by the contamination of water resources with hazardous heavy metal ions due to the accumulation in human body via food chains. Thereby, researchers’ attention has been paid on effective methods for heavy metal ion scavenging to prevent them releasing to environment. Notably, Mesoporous Silica Nanoparticles (MSNPs) with high surface area, massive surface area to volume ratio, large pore volume and uniform pore distribution play a crucial role in addressing this challenge. Additionally, researchers focus on novel surface functionalization methods of MSNPs with suitable organic and inorganic moieties to amplify the adsorption efficiency of heavy metals. MSNPs possess easily functionalizable surface which facilitates the modifications and enhanced removal of heavy metals. The review article summarizes the different moieties used for functionalization of MSNPs such as amino, thio, carboxyl, phenyl, cyano groups, different types of polymers, inorganic functional groups. Further, a comparison has been made between functional and unmodified MSNPs to elaborate how these modifications have enhanced the removal performance of heavy metals in water. Further, this review provides an overview on different synthesis routes and structure directing agent used in synthesis of MSNPs. Moreover, pH effect on adsorption andreusability of modified NPs, while illustrating the mechanism of adsorption on to modified MSNPs surface has also been elaborated. Maximum adsorption capacity of each functional moiety has been taken into consideration with the aim of supporting future advancements.
 Keywords: Adsorption, Mesoporous silica nanoparticles, Heavy metals, Functionalization, Maximum adsorption capacity

Interaction Mechanisms Between Nitrogen‐Containing Groups and Alkali Metals with Molecular Model System of HATCN**

AbstractTo enable the practical implementation of alkali metal batteries (AMBs), significant endeavors have been focused on enhancing the stability of alkali metal anodes (AMAs) using a range of strategies, such as optimizing electrolyte compositions, constructing anode deposition hosts, and establishing artificial protective layers. Despite significant progress in enhancing battery performance, limited attention has been given to comprehending the interaction mechanisms between alkali metals and protective materials, which is pivotal for the informed development of novel protective materials. Thus, aiming to enhance the comprehension of interaction processes between AMAs and organic protective materials containing various nitrogen groups, we conducted a mechanism study utilizing 1,4,5,8,9,11‐hexaazatriphenylenehexacarbonitrile (HATCN) as the model material, based on in‐situ x‐ray and ultraviolet photoelectron spectroscopy (XPS/UPS), and near edge x‐ray absorption fine structure (NEXAFS), as well as density functional theory (DFT) calculations. Through the investigation of interaction processes between HATCN and Li/Na, we find that Li or Na interacts with the two different nitrogen‐containing groups of HATCN in the same order: preferentially interacts with the inner imine groups of HATCN before interacting with the outer nitrile groups. Interestingly, our findings also reveal that the two distinct nitrogen‐containing groups exhibit a smaller difference in their sodiophilicity compared to their difference in lithiophilicity. These valuable insights shed light on the intricate interactions between nitrogen‐containing protective materials and AMAs, paving the way for the development of more effective protective materials in the future.

Boosting photocatalytic antibiotic degradation with simultaneous H2O2 production of g-C3N4 by building dual-dragging force for efficient charge separation

Graphitic carbon nitride (g-C3N4) is a promising candidate for photocatalytic antibiotic degradation with simultaneous H2O2 production. However, g-C3N4 suffers from a high charge recombination and insufficient visible-light absorption. Herein, the benzene-ring and cyano groups were successfully grafted onto the surface of g-C3N4 (BCN-ND) by a simple coupling route involving copolymerization and secondary calcination, which provided a dual-dragging force was generated for the directional separation of photogenerated electrons and holes. The benzene-ring establishes a mid-state slightly above the valence band, which results in a dragging force for holes and extends the response of g-C3N4 to visible light. Moreover, the cyano group exhibits a powerful electron-withdrawing capacity, acting as an electron-dragging force and narrowing the intrinsic bandgap. Therefore, BCN-ND exhibits remarkable photocatalytic activity with a sulfamethoxazole degradation percentage of 99.5 % and simultaneous H2O2 production of 62 μmol/L after 80 min of visible light irradiation. This work provides new perspectives for enhancing photocatalytic activity by constructing of a dual-dragging center for oppositely directional charge separation.

Investigation of Mechanochromic Luminescence of Pyrene-based Aggregation-Induced Emission Luminogens: Correlation between Molecular Packing and Luminescence Behavior.

To better understand the correlation between molecular structure and optical properties such as aggregation-induced emission (AIE) and mechanochromic luminescence (MCL) emission, two new pyrene-based derivatives with substitutions at the 4- and 5-positions (1HH) and at the 4-, 5-, 9-, and 10-positions (2HH) were designed and synthesized. Cyano groups were introduced at the periphery of the synthesized compounds (1HCN, 1OCN, 1BCN, 2HCN, 2OCN, and 2BCN) to investigate the influence of these groups on the emission properties of the pyrene derivatives both in solution and in the solid state. The fluorescence emission performance of these compounds in water/acetone mixtures was simultaneously studied, revealing outstanding aggregation-induced emission properties. The typical shift in emission maxima to higher values was attributed to J-aggregate formation in the aggregate state. Careful investigation of the crystal structures demonstrated abundant and intense intermolecular interactions, such as C-H…π and C-H…N hydrogen bonds, contributing to the remarkable mechanochromic luminescence performance of these compounds. The MCL properties of all the compounds were investigated using powder X-ray diffraction, and the remarkable mechanochromic properties were attributed to J-aggregate phenomena in the solid state. These results provide valuable insights into the structure-property relationship of organic MCL materials, guiding the design of efficient organic MCL materials.

Ongoing Phase III Randomized Trial of Salvage DFP-10917 Vs. Non-Intensive Reinduction or Intensive Reinduction for Acute Myelogenous Leukemia (AML)

Background: DFP-10917 is a deoxycytidine analogue with a novel structure. It contains a side chain cyanide (CN) group at the 2 carbon of deoxyribose that induces DNA damage in a manner unique from structurally related nucleoside analogues (eg, cytarabine, decitabine, or gemcitabine). When administered at high doses, DFP-10917 inactivates deoxyribonucleic acid (DNA) polymerase leading to S-phase arrest similar to cytarabine. When administered at low concentrations by continuous infusion, it displays an alternative, potentially advantageous, mechanism of action - DNA strand breakage leading to G2/M phase arrest and ultimately cell apoptosis. The strand breakage occurs via a spontaneous beta elimination reaction that requires no additional enzymatic activity. There is no current standard treatment for patients with relapsed/refractory (R/R) AML. Results of a completed Phase I/II study in R/R AML (D11-11002; NCT01702155) demonstrated preliminary efficacy of DFP-10917 in this indication, with a ~50% complete response (CR) rate in Phase II. Five of 14 patients who achieved CR proceeded to stem cell transplantation. Based on completed studies, risks associated with DFP-10917 are predominantly hematological (eg, neutropenia, anemia, febrile neutropenia, leukopenia, lymphopenia, thrombocytopenia). Study Design and Methods: Based on promising Phase II results, the Sponsor initiated Study D18-11141 (NCT03926624), a Phase III, randomized, controlled study to compare the rate and duration of CR in patients with AML R/R to 2-4 prior induction regimens. Patients receive either DFP-10917 or non-intensive reinduction (low-dose cytarabine [LoDAC], azacitidine, decitabine, venetoclax + LoDAC or azacitidine or decitabine) or intensive reinduction (high and intermediate dose cytarabine regimens). Patients assigned to DFP-10917 receive 6 mg/m 2/day by continuous infusion for 14 days followed by a 14-day rest period. Control treatment is administered per physician's decision. Adults aged ≥18 years with histologically or pathologically confirmed diagnosis of AML based on World Health Organization classification and adequate performance status (≤2) and organ function are eligible. Study Status: The study is ongoing at 34 study centers in the United States. As of July 2023, 162 patients were enrolled, with 82 assigned to DFP-10917. A majority of the patients are male (57.4%) and aged <75 years (83.3%). Overall, 44% have AML with myelodysplasia-related changes; 36% have AML not otherwise specified; and <20% have AML with recurrent genetic abnormalities or therapy-related myeloid neoplasms. Enrollment and management of patients were affected from 2020 to 2021 by COVID-19 restrictions. A prospectively-planned interim analysis will occur after the 150 th patient randomized is followed for >2 months. Based on recruitment projections, this analysis is scheduled for 09/2023. At that time, the Data Safety Monitoring Board will review an unblinded estimate of the treatment effect for the primary endpoint of CR, with the study either stopped for superiority or futility or continuing to a final analysis. If continued, the number of patients required for the final analysis will range from 300 to 450, in increments of 50, with the number determined based on the size of the interim treatment effect for the primary endpoint of CR or the secondary endpoint of overall survival.

Precisely designed NIR based conjugated framework as a solid state emitter for selective recognition of cyanide ion in solid state and cancer cells

Cyanide is undoubtedly dangerous and fast acting chemical employed in various industrial applications with toxic side effects, which raises urgent need for its monitoring. In this context, oxazolonaphthoimidazo[1,2-a]pyridine-malononitrile (ONIM) conjugate linked by vinyl linkage was designed, synthesized and characterised by FT-IR, NMR and mass spectrometry. The developed probe has been evaluated for the colorimetric and fluorometric detection of cyanide ion. An obvious color change with unique rapid “turn-off” fluorometric response was observed within 5 s upon addition of CN– thus reflecting its better acuteness and sensitivity over other competing anions. The developed probe exhibits a detection limit of 9.54 nM which is very low in comparison to maximum permitable amount of cyanide in drinking water (1.9 µM). The probe is stable within the pH range of 2–9 and suitable for the recognition of CN– in the pH range of 7 to 10, specially at neutral pH conditions. The chemodosimetric approach based detection mechanism was authenticated by 1H NMR titration and DFT calculations. The solid state applications were established by utilising ONIM impregnated TLC plates and filter paper in cyanide recognition. The solid state emissive behaviour of ONIM offers on-spot detection of the cyanide anion. Additionally, the practicability of ONIM has been extended in live cell imaging of CN– in human breast cancer cell (MDA-MB-231), which revealed a “turn-off” fluorescence response for the probe in the presence of CN– ion.

Modelling CN Zeeman effect observations of the envelopes of a low-mass protostellar disc and a massive protostar

ABSTRACT We use the polaris radiative transfer code to produce simulated circular polarization Zeeman emission maps of the cyanide (CN) J = 1–0 molecular line transition for two types of protostellar envelope magnetohydrodynamic simulations. Our first model is a low-mass disc envelope system (box length L = 200 au), and our second model is the envelope of a massive protostar (L = 104 au) with a protostellar wind and a CN-enhanced outflow shell. We compute the velocity-integrated Stokes I and V, as well as the implied V/I polarization percentage, for each detector pixel location in our simulated emission maps. Our results show that both types of protostellar environments are in principle accessible with current circular polarization instruments, with each containing swaths of envelope area that yield percentage polarizations that exceed the 1.8 per cent nominal sensitivity limit for circular polarization experiments with the Atacama Large Millimeter/submillimeter Array. In both systems, high-polarization (≳1.8 per cent) pixels tend to lie at an intermediate distance away from the central star and where the line-centre opacity of the CN emission is moderately optically thin (τLC ∼ 0.1–1). Furthermore, our computed V/I values scale roughly with the density-weighted mean line-of-sight magnetic field strength, indicating that Zeeman observations can effectively diagnose the strength of envelope-scale magnetic fields. We also find that pixels with large V/I are preferentially co-located where the absolute value of the velocity-integrated V is also large, suggesting that locations with favourable percentage polarization are also favourable in terms of raw signal.

Spectroscopic and Theoretical Studies on the Selective Detection of Cyanide Ions by a Turn-On Fluorescent Chemo-Dosimeter and its Application in Living Cell Imaging.

A new chemo-dosimeter AK4 containing quinoline fluorophore has rationally been designed, synthesised and characterized using 1H and 13C NMR and mass spectral techniques. The probe senses explicitly CN- ion through a dramatic enhancement in fluorescence over other commonly coexistent anions in H2O:DMSO (9:1 v/v) medium over a broad pH range (4-10). 1H NMR titration revealed the deprotonation followed by nucleophilic addition reaction of CN-, which was supported by 13C NMR and mass spectral examinations. The Job's continuous variation method indicated the formation of a 1:1 adduct between AK4 and CN- with a binding constant of 1.62 × 104M-1. A limit of detection (LOD) towards CN- of 0.69 µM has been determined, which is much lower than the World Health Organization (WHO) recommended limit of CN- in drinking water (1.9 µM). The changes in the optical properties of AK4 upon reaction with CN- were delineated using Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) calculations. Moreover, fluorescence microscopic studies established that AK4 could be an effective probe for imaging intracellular CN- in HeLa cells.

Structure elucidation, DFT and IRI computational investigations of a novel 4-(3-(4-chlorophenyl)-1-phenyl-1H-pyrazol-4-yl)2,6-dimethyl-1,4-dihydropyridine-3,5-dicarbonitrile

A novel symmetric dihydropyridine possessing cyano group at C11 and C14 has been synthesized using a modified Hantzsch method. The compound (▪) was characterized spectroscopically by Mass, IR and 1H NMR methods and finally confirmed by X-ray diffraction study. The compound crystallizes in a monoclinic crystal class with P21/c space group. In the title molecule, the dihydropyridine ring is puckered and displayed an envelope conformation of the type E1. The solid state of the title compound is governed by an intermolecular C–H…N, C–H…Cl and C–H…π interactions in the building of a crystal. It is investigated by three dimensional Hirshfeld surfaces mapped on different properties, also the relevant fingerprint graphs are obtained to recognize the percentage contribution from various inter atomic contacts. The topology of three dimensional interaction energy frameworks were constructed using the energy density wave function of DFT/B3LYP/6-311++G(d,p) and the energy corresponding to intermolecular interactions were assessed. The density functional theory analysis has been carried out and hence an energy gap and global index parameters are evaluated, also the geometric parameters are computed by optimizing the molecular structure of the title compound. The natural bonding orbitals (NBO) analysis is carried out to know the intermolecular charge transfer in the molecule. Reduced density gradients (RDG) and interaction region indicators (IRI) analysis reveals the chemical bonding and weak interactions regions. The molecular docking has been performed on 1B38, 2OHM, 3VNT and 4URO receptors shows good binding affinities and their results reveal that it serves as potential anti-cancer agent.