Oxygen and relative humidity monitoring with films tailored for enhanced photoluminescence

Approaches to generate porous or doped sensing films, which significantly enhance the photoluminescence (PL) of oxygen optical sensors, and thus improve the signal-to-noise (S/N) ratio, are presented. Tailored films, which enable monitoring the relative humidity (RH) as well, are also presented. Effective porous structures, in which the O₂-sensitive dye Pt octaethylporphyrin (PtOEP) or the Pd analog PdOEP was embedded, were realized by first generating blend films of polyethylene glycol (PEG) with polystyrene (PS) or with ethyl cellulose (EC), and then immersing the dried films in water to remove the water-soluble PEG. This approach creates pores (voids) in the sensing films. The dielectric contrast between the films’ constituents and the voids increases photon scattering, which in turn increases the optical path of the excitation light within the film, and hence light absorption by the dye, and its PL. Optimized sensing films with a PEG:PS ratio of 1:4 (PEG’s molecular weight M_w ∼8000) led to ∼4.4× enhancement in the PL (in comparison to PS films). Lower M_w ∼200 PEG with a PEG:EC ratio of 1:1 led to a PL enhancement of ∼4.7×. Film-dependent PL enhancements were observed at all oxygen concentrations. The strong PL enhancement enables (i) using lower dye (luminophore) concentrations, (ii) reducing power consumption and enhancing the sensor’s operational lifetime when using organic light emitting diodes (OLEDs) as excitation sources, (iii) improving performance when using compact photodetectors with no internal gain, and (iv) reliably extending the dynamic range.     

Computational Exploration of Mechanistic Avenues in Metal-Free CO2 Reduction to CO by Disilyne Bisphosphine Adduct and Phosphonium Silaylide

Recent years have seen a growing interest in metal-free CO₂ activation by silylenes, silylones, and silanones. However, compared to mononuclear silicon species, CO₂ reduction mediated by dinuclear silicon compounds, especially disilynes, has been less explored. We have carried out extensive computational investigations to explore the mechanistic avenues in CO₂ reduction to CO by donor-stabilized disilyne bisphosphine adduct ( R1^M ) and phosphonium silaylide ( R2 ) using density functional theory calculations. Theoretical calculations suggest that R1^M exhibits donor-stabilized bis(silylene) bonding features with unusual Si−Si multiple bonding. Various modes of CO₂ coordination to R1^M have been investigated and the coordination of CO₂ by the carbon center to R1^M is found to be kinetically more facile than that by oxygen involving only one or both the silicon centers. Both the theoretically predicted reaction mechanisms of R1^M and R2 -mediated CO₂ reduction reveal the crucial role of silicon-centered lone pairs in CO₂ activations and generation of key intermediates possessing enormous strain in the Si−C−O ring, which plays the pivotal role in CO extrusion.     

Modular-type relations associated to the Rankin–Selberg <Emphasis Type="Italic">L</Emphasis>-function

Hafner and Stopple proved a conjecture of Zagier relating to the asymptotic behaviour of the inverse Mellin transform of the symmetric square L-function associated with the Ramanujan tau function. In this paper, we prove a similar result for any cusp form over the full modular group.     

Pairs of integers which are mutually squares

We derived an asymptotic formula for the number of pairs of integers which are mutually squares. Earlier results dealt with pairs of integers subject to the restriction that they are both odd, co-prime and squrefree. Here we remove all these restrictions and prove (similar to the best known one with restrictions) that the number of such pair of integers upto a large real X is asymptotic to \(\frac{{c{X^2}}}{{\log X}}\) with an absolute constant c which we give explicitly. Our error term is also compatible to the best known one.     

Design and development of bioactive α-hydroxy carboxylate group modified MnFe2O4 nanoparticle: Comparative fluorescence study,magnetism and DNA nuclease activity

Three new α-hydroxy carboxylate group functionalized MnFe₂O₄ nanoparticles (NPs) have been developed to explore the microscopic origin of ligand modified fluorescence and magnetic properties of nearly monodispersed MnFe₂O₄ NPs. The surface functionalization has been carried out with three small organic ligands (tartrate, malate, and citrate) having different number of α-hydroxy carboxylate functional group along with steric effect. Detailed study unveils that α-hydroxy carboxylate moiety of the ligands plays key role to generate intrinsic fluorescence in functionalized MnFe₂O₄ NPs through the activation of ligand to metal charge transfer transitions, associated with ligand–Mn²⁺/Fe³⁺ interactions along with d–d transition corresponding to d–orbital energy level splitting of Fe³⁺ ions on NP surface. Further, MnFe₂O₄ NPs show a maximum 140.88% increase in coercivity and 97.95% decrease in magnetization compared to its bare one upon functionalization. The ligands that induce smallest crystal field splitting of d–orbital energy level of transition metal ions are found to result in strongest ferrimagnetic activation of the NPs. Finally, our developed tartrate functionalized MnFe₂O₄ (T-MnFe₂O₄) NPs have been utilized for studying DNA binding interaction and nuclease activity for stimulating their beneficial activities toward diverse biomedical applications. The spectroscopic measurements indicate that T-MnFe₂O₄ NPs bind calf thymus DNA by intercalative mode. The ability of T-MnFe₂O₄ NPs to induce DNA cleavage was studied by gel electrophoresis technique where the complex is found to promote the cleavage of pBR322 plasmid DNA from the super coiled form I to linear coiled form II and nicked coiled form III with good efficiency.     

A review on adsorption mediated phosphate removal and recovery by biomatrices

Low cost biosorbents have gained considerable importance in the past decade for their removal efficiency of contaminants from wastewaters. Both removal and recycle of the phosphate anion through benign methods are relevant to sustain a steady balance. An attempt has been made to give a comprehensive insight into several physico-chemical factors leading to the adsorption process by various natural biosorbents. Few important facts regarding phosphate biosorption have emerged out as key points viz., pH < pHpzc, high uptake capacity; correlation with Langmuir isotherm model and pseudo second order kinetics; decrease of uptake capacity with longer contact time; enhancement of adsorption process in presence of counter ions, etc. Also, it was noted that the adsorbate: adsorbent ratio is crucial for the removal efficiency of the phosphate ions. A few biosorbents exhibit removal efficiency to a large extent (>95%) although even higher adsorption capacity can be obtained by the modification of the adsorbents. Commercial biomatrices like biochars have shown wide applications for removal of phosphates. Magnetic biochars have shown special performance owing to the presence of iron and a porous nature of their structure. Desorption studies revealed that almost complete recovery of the phosphate ion is possible through simple ion exchange mechanism.     

Copper‐Catalyzed (2+1) Annulation of Acetophenones with Maleimides: Direct Synthesis of Cyclopropanes

A practical copper‐catalyzed direct oxidative cyclopropanation of electron‐deficient alkenes with acetophenone derivatives is reported. The dehydrogenative annulation involves a double C? H bond functionalization at the α‐position of the ketone using di‐tert‐butyl peroxide as oxidant. The broad scope of the reaction and excellent functional‐group tolerance is demonstrated for the stereoselective synthesis of fused cyclopropanes. The developed transformation revealed an unprecedented reactivity for copper‐catalyzed processes.     

Kinetics and mechanism of oxidation of aliphatic aldehydes by quinolinium fluorochromate

Oxidation of aliphatic aldehydes by quinolinium fluorochromate (QFC) proceeds by a mechanism involving transfer of a hydride ion from the aldehyde to the oxidantvia an intermediate complex.