Mycobacterial biofilms: Understanding the genetic factors playing significant role in pathogenesis, resistance and diagnosis.

Even though the genus Mycobacterium is a diverse group consisting of a majority of environmental bacteria known as non-tuberculous mycobacteria (NTM), it also contains some of the deadliest pathogens (Mycobacterium tuberculosis) in history associated with chronic disease called tuberculosis (TB). Formation of biofilm is one of the unique strategies employed by mycobacteria to enhance their ability to survive in hostile conditions. Biofilm formation by Mycobacterium species is an emerging area of research with significant implications for understanding its pathogenesis and treatment of related infections, specifically TB. This review provides an overview of the biofilm-forming abilities of different species of Mycobacterium and the genetic factors influencing biofilm formation with a detailed focus on M. tuberculosis. Biofilm-mediated resistance is a significant challenge as it can limit antibiotic penetration and promote the survival of dormant mycobacterial cells. Key genetic factors promoting biofilm formation have been explored such as the mmpL genes involved in lipid transport and cell wall integrity as well as the groEL gene essential for mature biofilm formation. Additionally, biofilm-mediated antibiotic resistance and pathogenesis highlighting the specific niches, sites of infection along with the possible mechanisms of biofilm dissemination have been discussed. Furthermore, drug targets within mycobacterial biofilm and their role as potential biomarkers in the development of rapid diagnostic tools have been highlighted. The review summarises the current understanding of the complex nature of Mycobacterium biofilm and its clinical implications, paving the way for advancements in the field of disease diagnosis, management and treatment against its multi-drug resistant species.

Hourglass-Shaped Homo- and Heteronuclear Nonanuclear Lanthanide Clusters: Structures, Magnetism, Photoluminescence, and Theoretical Analysis.

Synthesis of nonameric cationic clusters [Dy9(acac)16(µ3-OH)8(µ4-OH)2]OH·6H2O (1), [Dy8Tb (acac)16(µ3-OH)8(µ4-OH)2]OH·2H2O (2), and [Gd9(acac)16(µ3-OH)8(µ4-OH)2]OH·6H2O (3) (acac = acetylacetonate) is reported. The emission spectrum of 1 shows Dy(III) ion characteristic bands assignable to the 4F9/2 → 6HJ (J = 15/2 to 9/2) transitions. Emission due to both Dy(III) and Tb(III) ions is observed for 2 in the visible range, with Tb(III) specific bands appearing due to the 5D4 → 7FJ (J = 6, 4, and 3) transitions. Cluster 3 exhibits a significant magnetocaloric effect (MCE), with -ΔSm values increasing with decrease in temperature and increase in field, reaching -ΔSmmax = 20.98 J kg-1 K-1 at 2 K and 9 T. Isotropic magnetic coupling constants (Js) in 3 derived from density functional theory (DFT) calculations reveal that the exchange interactions are antiferromagnetic and weak. Compound 3 possesses S = 7/2 ground state arising from the central Gd(III) ion along with several nested excited states due to competing antiferromagnetic interactions that yield reasonably large MCE values. Utilizing computed exchange coupling interactions, we have performed ab initio CASSCF/RASSI-SO/POL_ANISO calculations on antiferromagnetic 1 and 2 to estimate the exchange interactions using the Lines model. For 2, Dy(III)···Tb(III) exchange interactions were extracted for the first time and were found to be weakly antiferromagnetically coupled.

Memory Effect by Melt Crystallization Observed in Polymorphs of a Benzothieno-Benzothiophene Derivative.

This work provides a comprehensive illustration of a crystalline melt memory effect recorded for three solvates of the 2,7-bis(2-(2-methoxyethoxy)ethoxy)benzo[b]benzo[4,5] thieno[2,3-d]thiophene (OEG-BTBT) molecule with dichloromethane (DCM) molecules. Combined optical microscopy and X-ray diffraction measurements at different temperatures are used to get an overview of the structural and morphological properties like melting points, isotropic transition temperatures, induction times, and crystallization kinetics of the three forms. An outstanding observation is made upon annealing the three polymorphs at temperatures well above their respective melting points as well as above the optical clearance temperature. After cooling back to room temperature, recrystallization results in the formation of the initial phase present before the annealing process. This melt memory effect is observed for all three solvates. These observations can be correlated to the strong interaction between the DCM molecules and the oligoethylene glycol side chains, even in the molten state. This conclusion rationalizes the experimental observation made upon solvent vapor annealing of the crystalline sample with DCM, which unambiguously transformed the system into a disordered state.

Polymorph screening at surfaces of a benzothienobenzothiophene derivative: discovering new solvate forms.

The discovery of new polymorphs opens up unique applications for molecular materials since their physical properties are predominantly influenced by the crystal structure type. The deposition of molecules at surfaces offers great potential in the variation of the crystallization conditions, thereby allowing access to unknown polymorphs. With our surface crystallization approach, four new phases are found for an oligoethylene glycol-benzothienobenzothiophene molecule, and none of these phases could be identified via classical polymorph screening. The corresponding crystal lattices of three of the new phases were obtained via X-ray diffraction (XRD). Based on the volumetric considerations together with X-ray fluorescence and Raman spectroscopy data, the phases are identified as solvates containing one, two or three solvent molecules per molecule. The strong interaction of dichloromethane with the oligoethylene glycol side chains of the molecules may be responsible for the formation of the solvates. Temperature-dependent XRD reveals the low thermal stability of the new phases, contrary to the thermodynamically stable bulk form. Nevertheless, the four solvates are stable under ambient conditions for at least two years. This work illustrates that defined crystallization at surfaces enables access to multiple solvates of a given material through precise and controlled variations in the crystallization kinetics.

Capacity analysis of underwater visible light communication systems over a lossy channel in the presence of noises.

Absorption and scattering losses due to impurities and turbidity in the water affect the transmission quality of underwater visible light communication links, restricting the channel capacity. For the first time to our knowledge, this paper analytically studies the channel capacity of a point-to-point underwater visible light communication link in the presence of input-independent and -dependent noises along with absorption and scattering losses. This way, novel lower and upper bound expressions on channel capacity are derived when average and peak-intensity constraints are imposed on the channel input. Our proposed upper and lower bounds are tight at high optical signal-to-noise ratio. The derived analytic expression of capacity also helps to evaluate the available data rate in the presence of different types of noise and water. From the results, we can say that input-dependent noise causes more system capacity degradation than input-independent noise. The results show that good water quality is crucial for high-capacity communication links. Furthermore, it is shown that the attenuation of the optical signal is more in water when compared to air as a medium, and channel capacity decreases as the link range increases. The results reported in this paper provide valuable insight into the design of underwater visible light communication systems.

The Redox Journey of Iconic Ferrocene: Ferrocenium Dications and Ferrocenate Anions.

The recent discoveries of both dicationic and monoanionic ferrocene derivatives throw light on the effect of the substituents on the C5 ring as well as the choice of redox agents and solvent system in the preparation of previously believed to be difficult synthetic targets. These oxidized and reduced forms of ferrocene are of interest to spectroscopists, magnetochemists, and theoreticians.

A novel approach to improve the oil miscibility and incorporate multifunctionality in ionic liquids as lubricant additives.

Recently ionic liquids (ILs) have shown promising tribological properties as additives in base oils; however their lack of miscibility is a problem, with very few ILs being compatible with lubricant oil formulation (non-polar base oils). This work shows the use of a surfactant which can increase the range of available ILs that are stable when added to these base oils. In this study a range of tetraalkylphosphonium based ILs were successfully blended with a PIBSA surfactant and these blends were all shown to be miscible in a non-polar base oil. Without the PIBSA a number of the ILs were immiscible in the base oil. The tribological properties of IL additives that are miscible in the non-polar base oils were compared with and without the surfactant present and showed that the presence of the PIBSA did not affect the IL additives performance. Additionally, two ILs that are immiscible without the surfactant showed the greatest reduction in friction and wear. SEM analysis showed an increase in the amount of phosphorus on the wear surface when the surfactant was present, suggesting that the PIBSA enhances tribo-film formation. NMR, FTIR, DLS and TEM investigations into the interactions between the PIBSA and the ILs showed that the improved stability in the base oil may be due to intermolecular interactions such as hydrophobic, van der Waals, dipole-dipole or ion-dipole that reduce the size distribution of the previously immiscible ILs. The presence of the ILs was also shown to improve the resistance to corrosion. Prior to this study the ILs available for use as lubricant additives was severely limited and compromised, mostly based upon their miscibility. Here the use of PIBSA to increase the range of ILs available as lubricant additives has vastly improved the promise that they represent in this area.

Development, validation of QuEChERS-based method for simultaneous determination of multiclass pesticide residue in milk, and evaluation of the matrix effect.

Extraction and quantification of pesticide residue from the milk matrix at or below the established maximum residue limit (MRL) is a challenging task for both analytical chemists and the regulatory institutions to take corrective actions for the human health and safety. The main aim of the study is to develop a simple rapid and less expensive QuEChERS extraction and cleanup method for simultaneous analysis of 41 multiclass pesticide residue in milk by gas chromatography-electron capture detector (GC-ECD), followed by confirmation of the residues with gas chromatography-mass spectrometer (GC-MS). Effect of sorbent type, temperature, spiking concentration, matrix effect (ME), measurement uncertainty (MU), inter- and intra-assay repeatability, reproducibility of recovery, and trueness of the results were investigated to validate the effectiveness of the method. Limit of determination (LOD) and limit of quantitation (LOQ) for all the analytes ranged within 0.001-0.02 and 0.002-0.05 µg mL-1, respectively. The % recovery of all the pesticides ranged between 91.38 and 117.56% with relative standard deviation (RSD) below 2.79%. The MU for all the analytes was ≤29% of respective LOQs, and except for few pesticides, the ME was largely negative. The method fulfilled all the SANTE guidelines and thus can be extended for routine analysis of multiclass pesticide residue in milk.

Persistence, dissipation and consumer risk assessment of a combination formulation of flubendiamide and deltamethrin on cucumber.

Multi-location supervised field trials were conducted in India at four locations of the All India Network Project (AINP) on Pesticide Residues to study the persistence, dissipation and risk assessment of flubendiamide and deltamethrin on cucumber (Cucumis sativus). Residues of flubendiamide and deltamethrin on cucumber resulting from three spray applications of a combination formulation (flubendiamide 90% + deltamethrin 60%, 150 SC) at recommended (22.5 + 15 g a.i./ha) and double the recommended (45 + 30 g a.i./ha) dose were analysed. On the basis of persistence and dissipation studies, the half- life (T1/2) of flubendiamide on cucumber varied from 1.40 to 2.98 (recommended dose) and 1.55 to 2.76 days (double the recommended dose), while that of deltamethrin ranged from 2.5 to 4.9 (recommended dose) and 2.7 to 3.9 days (double the recommended dose) at the four locations. On the basis of supervised field trial data and using OECD calculator, MRLs in the combination product of 3 mg kg-1 for flubendiamide and 1.5 mg kg-1 for deltamethrin has been proposed for consideration by the Food Safety and Standards Authority of India (FSSAI). Codex, EU and EPA have fixed MRL of 0.2 mg kg-1 for flubendiamide and deltamethrin.