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Rule of proportionality strikes a bargain in launching attacks. It demands that military commanders suspend or cancel operations if collateral damage anticipated from an attack exceeds the potential military advantage offered. The definitional phrase military advantage has been the subject of a rich debate, varyingly interpreted to expand or limit the scope of attacks. This paper participates in the debate, advocating that military advantage must be limited to exclude attacks on objects that indirectly contribute to military potential, such as, economic, social, psychological or political advantage, which invariably target civilians or civilian enterprises. It critically engages with the principles and precedents invoked to legitimise a broader understanding of military advantage. It posits that such attacks disregard belligerents’ privileges, and render unbound categories of civilian objects susceptible to destruction. Pursuantly, the rule of proportionality, originally articulated to nuance and improve the rule of distinction, is usurped to violate the latter. [ABSTRACT FROM AUTHOR]

The interactions of diglycine with sulphathiazole drug as a function of temperatures have been studied using volumetric and acoustic parameters. Densities and speeds of sound of diglycine in (0.001, 0.002, 0.005 and 0.010) mol·kg-1 aqueous solutions of sulphathiazole drug have been measured at five different temperatures of (288.15, 293.15, 298.15, 303.15 and 308.15) K under 0.1 MPa pressure. From density data, the apparent molar volume, the partial molar volume and the standard partial molar volume of transfer for glycine from water to aqueous sulphathiazole solutions have been calculated. Partial molar isentropic compression and partial molar isentropic compression of transfer have been calculated from the speed of sound data. Transfer parameters by using cosphere overlap model have been explained on the basis of ionic-hydrophilic, hydrophilic-hydrophilic, hydrophilic-hydrophobic and hydrophobic-hydrophobic group interactions. To draw the conclusion from the volumetric and acoustic data, limiting apparent molar expansion as well as the hydration numbers have been studied. The calculated values of thermal expansion coefficient have small and positive values. All of these derived or calculated parameters are explained to understand the solvation behaviour and various types of interactions born in the ternary solutions of (dipeptide + drug + water) due to change in structure. We have also attempted to examine the temperature and concentration dependence of such interactions. [ABSTRACT FROM AUTHOR]

The densities (ρ) and speeds of sound (u) for glycine in aqueous solutions of (0.01, 0.02, 0.03, and 0.04) mol·kg-1 sulphathiazole drug have been measured at T = (288.15, 293.15, 298.15, 303.15 and 308.15) K, using vibrating tube digital densimeter and sound analyser Anton-Paar Model DSA - 5000. The apparent molar properties like apparent molar volume (vφ), apparent molar adiabatic compressibility (Kφ, s) and the apparent molar volume (Vφ 0) and adiabatic compressibility at infinite dilution (Kφ, s 0) of glycine have been determined in water as well as in ternary mixtures containing sulphathiazole drug at different concentrations and at different temperatures from experimental data of densities and speeds of sound under atmospheric pressure. These data were also used to calculate the transfer parameters. Transfer parameters have been explained from the point of view of concentration dependence of solute-solute and solute-solvent interactions. The limiting apparent molar expansibility (Eφ°) values for glycine in aqueous solutions of drug have been calculated. The calculated values of thermal expansion coefficient (α2) have small and positive values. These results are explained on the basis of drug-amino acid - water interactions and hydrophobic-hydrophilic interactions. [ABSTRACT FROM AUTHOR]

Polyaniline nanofibers were synthesized by the oxidative polymerization of aniline. Surfactant treated lipase from Burkholdaria cepacia was immobilized on these polyaniline nanofibers by adsorption. The activity of immobilized preparation was six times higher than that of free lipase with an enhanced dispersion in organic solvents. Five-level-four-factor central composite design was applied for the optimization of immobilization parameters (viz. reaction time, pH, stirring rate and enzyme-support ratio) which were evaluated on the basis of lipase loading and activity. The thermal stability of the lipase in the nanobioconjugate, demonstrated in terms of the half-life at 80 °C was almost sixteen-fold higher than in the free form. The reusability data revealed the utility of the nanoconjugate for seven consecutive cycles with a slow and gradual decline in the activity. However, the nanoconjugate retained almost 30% of their initial activity after seven cycles of reuse revealing its utility of in industrial applications. The nanoconjugate was used in the kinetic resolution of (RS)-1-(7-(3-chloro-2-hydroxypropoxy)benzofuran-2-yl) ethanone, racemic intermediate of an important β-blocker (Befunolol), with a high conversion rate of 48.2%, 98% ee -value and enantioselectivity (E) of 188, which signify its importance as a nanobiocatalyst. Unlabelled Image • Facile immobilization of surfactant activated biocatalyst on polyaniline nanofibers. • Six folds increase in the enzyme activity. • Excellent increase in thermal stability (16-folds) and reusability (upto 7 cycles). • Five-level-four-factor central composite design applied for optimization of immobilization parameters. • Immobilized lipase applied in the synthesis of enantiopure β-blocker (Befunolol). [ABSTRACT FROM AUTHOR]

Pseudomonas fluorescens lipase (PFL) was covalently immobilized on carbon nanofiber (CNF) using 1‑ethyl‑3‑[3‑dimethylaminopropyl] carbodiimide (EDC)/ N ‑hydroxysuccinimide (NHS). Surface functionalization of carbon nanofiber augments dispersibility as well as efficiency of covalent immobilization. Crucial parameters for immobilization such as pH, enzyme-support ratio, reaction time and mixing rate were optimized using one factor at a time (OFAT) approach. The nanobiocatalyst prepared under optimized conditions demonstrated a ten-fold increase in enzyme activity and the advantage of high thermal stability (up to 85 °C) along with 10 cycles of reusability. Subsequently practical application of the nanobiocatalyst was explored in the kinetic resolution of racemic 1‑phenylethanol into (S)‑1‑phenylethanol [C = 49.1%, ee p = 99.5%, ee s = 98.5% and E value = 151.4] followed by Mitsunobu reaction with a substituted pyrrole, giving an enantiopure (R)-carboetomidate analogue (yield = 83%). Tailoring a robust and recyclable nanobiocatalyst by immobilization of Pseudomonas fluorescens lipase on carbon nanofiber and its application in synthesis of enantiopure carboetomidate analogue. Unlabelled Image • Fabrication of a robust and recyclable nanobiocatalyst • Ten folds increase in the enzyme activity • High thermal and storage stability • Application in the synthesis of enantiopure carboetomidate analogue [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Proposed two process intensified designs viz., symmetrical and asymmetrical CCFI. • Evaluated RTD and pressure drop experimentally and numerically over 10 ⩽ N R e ⩽ 145. • An evolution of narrower RTD with increasing tube length is computed numerically. • Revealed superiority of symmetrical CCFI over asymmetrical CCFI and CFI. Abstract The present study focuses on the intensification of flow and mixing in coiled flow inverter (CFI) geometries in order to achieve higher mixing efficiency with a lower base footprint. For this, two designs of "compact coiled flow inverter (CCFI)", namely, symmetrical compact coiled flow inverter and asymmetrical compact coiled flow inverter, are proposed within the same floor area as covered by a standard design of a conventional CFI. The design of the symmetrical CCFI is based on incorporating as many as possible 90° bends, whereas the asymmetrical CCFI is based on incorporating as much as possible mixing volume. In order to quantify the improvements caused by proposed designs, all three geometries (two CCFIs and one standard CFI) are compared (experimentally and numerically) with each other in terms of dimensionless dispersion number (D / UL) and mixing efficiency (that measures induced radial mixing by incorporating pressure drop penalty), over laminar flow regime (10 ⩽ N R e ⩽ 145). After validation of the numerical model (CFD) with experimental data, the RTD at different cross-sectional planes along the length of coiled tube is investigated. Such a study provides the relative contribution of helical turns and 90° bends in reducing axial dispersion, and also provides an insight of the required length of coiled tube that is sufficient to achieve a desired reduction in the axial dispersion. The present study reveals that the symmetrical compact coiled flow inverter has the highest mixing efficiency per unit occupied floor area, and requires the least length of coiled tube in order to reduce the axial dispersion at same extent. Thus, the symmetrical CCFI has potential to save significant material and operational energy cost in the Industry. [ABSTRACT FROM AUTHOR]

Abstract Herein, we demonstrate the immobilization of Pseudomonas fluorescens lipase (PFL) on polyaniline nanofibers (PANFs) via physical adsorption. Polyaniline nanofibers (PANFs) were synthesized by the oxidative polymerization of aniline. The developed robust nanobiocatalyst (PANFs-PFL) exhibited eight times higher activity than free PFL. In addition, immobilization of lipase on PANFs imparted operational stability of the nanobioconjugate. The various reaction parameters for immobilization (viz. reaction time, pH, stirring rate and enzyme-support ratio) were optimized using statistical design in terms of lipase activity and loading. Furthermore, facile separation, enhanced reusability (upto 6 cycles) and thermostability (upto 75 °C) were additional advantages of the nanobioconjugate. The catalytic prowess of nanobioconjugate was examined in the kinetic resolution of (RS)- N -(4-(3-chloro-2-hydroxypropoxy)phenyl)acetamide and (RS)-1-(1-naphthyl) ethanol in comparison to free PFL. PANFs-PFL demonstrated 49.9% and 48.1% conversion for (RS)- N -(4-(3-chloro-2-hydroxypropoxy)phenyl)acetamide and (RS)-1-(1-naphthyl) ethanol, respectively which signified its importance as a nanobiocatalyst. Graphical abstract Unlabelled Image [ABSTRACT FROM AUTHOR]

A profoundly time-efficient chemoenzymatic method for the synthesis of ( S) -3-(4-chlorophenoxy)propan-1,2-diol and ( S) -1-chloro-3-(2,5-dichlorophenoxy)propan-2-ol, two important pharmaceutical intermediates, was successfully developed using Pseudomonas fluorescens lipase (PFL). Kinetic resolution was successfully achieved using vinyl acetate as acylating agent, toluene/hexane as solvent, and reaction temperature of 30°C giving high enantioselectivity and conversion. Under optimized condition, PFL demonstrated 50.2% conversion, enantiomeric excess of 95.0%, enantioselectivity (E = 153) in an optimum time of 1 hour and 50.3% conversion, enantiomeric excess of 95.2%, enantioselectivity (E = 161) in an optimum time of 3 hours, for the two racemic alcohols, respectively. Docking of the R- and S-enantiomers of the intermediates demonstrated stronger H-bond interaction between the hydroxyl group of the R-enantiomer and the key binding residues of the catalytic site of the lipase, while the S-enantiomer demonstrated lesser interaction. Thus, docking study complemented the experimental outcome that PFL preferentially acylated the R form of the intermediates. The present study demonstrates a cost-effective and expeditious biocatalytic process that can be applied in the enantiopure synthesis of pharmaceutical intermediates and drugs. [ABSTRACT FROM AUTHOR]

Lidocaine HCl and procaine HCl are local anesthetics widely used in minor chirurgic procedures; nevertheless, spectral information about their behavior is not complete at present. In this context, in this paper, absorbance and fluorescence studies of both the drugs with α- and β-cyclodextrins (CDs) have been measured at 298.15 K. The thermodynamic parameters: binding constant ( K) and standard state Gibbs energy (∆ G°) were calculated for the systems in which complex formation was observed. The α- and β-CD study indicates that the lidocaine HCl and procaine HCl drugs form 1:1 inclusion complex with α- and β-CD. Both experimental and theoretical studies revealed that the phenyl ring with the amide group of the drug is encapsulated in the hydrophobic CD cavity. van der Waals interactions are mainly responsible for complex formation of lidocaine hydrochloride and procaine hydrochloride with CDs. [ABSTRACT FROM AUTHOR]

The apparent molar volumes, V ϕ , apparent molar adiabatic compressibilities, K ϕ , s , apparent molar volumes at infinite dilution, V ϕ 0 , and apparent molar adiabatic compressibilities at infinite dilution, K ϕ , s 0 are evaluated from the measured densities, ρ , and speeds of sound, u , values, for α-cyclodextrin and β-cyclodextrin in aqueous sulfamethoxazole solutions at T = (288.15, 293.15, 298.15, 303.15, 308.15) K. Further, transfer partial molar volume, ΔV ϕ 0 at infinite dilution, transfer partial molar adiabatic compressibilities, ΔK ϕ , s 0 at infinite dilution and pairwise and triplet interaction coefficients, are discussed in terms of solute–solute and solute–solvent occurring in the ternary solution of present study. [ABSTRACT FROM AUTHOR]

In this work, densities have been measured for glycinein aqueoussolutions of (0.01, 0.02, 0.03, and 0.04) mol·kg–1sulfanilamide, sulfanilic acid, and sulfosalicylic acid dihydrateat temperatures from (288.15 to 308.15) K, using vibrating tube digitaldensimeter. These solution densities were used to calculate the partialmolar volume values at infinite dilution, Vϕ∞,for the glycine. The calculated parameters are used to interpret thesolute–solute and solute–solvent interactions and structuremaking/breaking ability of the amino acid in the given aqueous sulfadrug solution. [ABSTRACT FROM AUTHOR]

CoS@MorphcdtH NPs and CoS@4‐MPipzcdtH NPs were synthesized by precipitation method involving three mechanisms: inclusion, occlusion, and adsorption. The synthesized NPs were characterized with the help of UV‐Vis spectroscopy, FESEM‐EDAX, powder x‐ray diffraction, TEM, ESIMS, TG/DSC analysis. The morphology of the CoS@MorphcdtH NPs and CoS@4‐MPipzcdtH NPs were hexagonal and rectangular, and the particles were in the range 7–12 nm. UV–visible spectral measurements showed surface plasmon resonance at 320 nm–340 nm with band gap of 3.65 eV–3.86 eV. The catalytically active CoSNPs called were investigated for the reduction of 4‐nitrophenol (4‐NP) via hydrogenation using sodium borohydride (NaBH4) as a reducing agent. Both the CoS NPs successfully reduced 4‐NP to 4‐ aminophenol (4‐AP) in a short time, catalytic performances are almost unchanged for the first five cycles. Herein, we report the preparation and characterizations of efficient active CoS NPs consisting carbodithioic acid framework as a support/capping material, along with catalytic property. [ABSTRACT FROM AUTHOR]

Abstract: Densities, ρ, were measured for ternary mixture of diglycine in aqueous of (0.01, 0.02, 0.03, and 0.04)molkg−1 sulphanilamide (SAM), sulphanilic acid (SAN), and sulphosalicylic (SSAD) acid dihydrate at T =288.15–308.15K, using vibrating tube digital densimeter. Apparent molar volume, , has been determined from the experimental densities and the least-square fitting was carried out for the calculation of limiting apparent molar volumes values , and the increase in the values has the following order in the investigated system: SAN

The spectral characteristics of different drugs i.e. sulfanilamide, sulfanilic acid, sulfosalicylic acid dihydrate (SSAD) and sulfamethoxazole in aqueous α-cyclodextrin (CD) have been investigated at neutral pH. The formation of inclusion complexes of sulfa drugs with α-CD leads to the changes in fluorescence and absorption spectra which further enable the calculation of association constant of the bind processes by implementing the non-linear regression on the experimental data. The standard Gibbs energy ΔG was also calculated for the systems in which complex formation was observed. The α-CD study indicates that the sulpha drugs form 1:1 inclusion complex with α-CD. [ABSTRACT FROM AUTHOR]

Thermodynamic and spectroscopic properties of α-cyclodextrin and β-cyclodextrin in aqueous solution sulfathiazole have been investigated by volumetric, ultrasonic measurements at T  = (288.15–308.15 K) along with absorption spectra and fluorescence studies. The apparent molar volumes at infinite dilution, V ϕ 0 and the apparent molar isentropic compression at infinite dilution K ϕ , S 0 , have been calculated from density and speed of sound data. Furthermore, partial molar volumes of transfer, Δ tr V ϕ 0 , partial molar isentropic compression of transfer, Δ tr K ϕ , S 0 , apparent molar expansivity, E ϕ 0 , Hepler’s constant values, ∂ E ϕ 0 ∂ T P and thermal expansion coefficient, α have also been evaluated to support the conclusions obtained from the volumetric and acoustic studies. These parameters are helpful to study the solvation behavior and various interactions present in the ternary solutions of (α-cyclodextrin/β-cyclodextrin + sulfathiazole + water). Further, absorption and emission spectra has been recorded for aqueous sulfathiazole solution in α-cyclodextrin to analyze the host-guest interactions. The inclusion complex of sulfathiazole with α-cyclodextrin is investigated by UV–visible spectroscopy and fluorescence. The study indicates that sulpha drug forms 1:1 inclusion complexes with α-cyclodextrin. [ABSTRACT FROM AUTHOR]