A high-precision ratiometric fluorosensor for pH: implementing time-dependent non-linear calibration protocols for drift compensation

We present a versatile time-dependent non-linear calibration protocol for optical sensors, implemented on the pH sensitive ratiometric fluorophore 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS) immobilized in ethyl-cellulose. The calibration protocol individually compensated for the progressive drift of calibration parameters, whereby sensor precision and accuracy, as well as applicable lifetime were improved. A severely reduced photoacidity was observed for the immobilized fluorophore, for which excited state dynamics was characterized and benefited from during measurements. Due to the significantly reduced photoacidity of HPTS immobilized in the ethyl-cellulose sensing membrane, a dual excitation/dual emission (F₁, ex/em: 405/440 nm and F₂, ex/em: 465/510 nm) ratiometric (RF₁,F₂ = F₁/F₂) sensing scheme could be used to amplify sensor response. The signal to noise (S/N) ratio was enhanced by ∼400% utilizing the dual excitation/dual emission ratiometric sensing scheme, rather than the more commonly used protocol of dual excitation/single emission for HPTS fluorescence. Apparent pK_a of the fluorophore ranged from 6.74 to 8.50, mainly determined by the immobilization procedure. The repeatability (IUPAC, pooled standard deviation) over three pH values (6.986, 7.702 and 7.828) was 0.0044 pH units for the optical sensor, compared to 0.0046 for the electrode used for standardization. Sensor analytical characteristics were thereby in principle limited by the performance of the standardization procedure.     

Recovery decisions of a producer in a legislative disposal fee environment

The main objectives of the environmental legislation originating from extended producer responsibility (EPR) principle are to lead producers to undertake recovery initiatives for their end-of-use products and to promote environmentally desirable product design. It is still controversial whether current implementations of EPR principle are effective in attaining these objectives. This study seeks to answer the following questions: (1) What is the impact of EPR legislation on the product recovery decisions of producers? (2) How do the redesign opportunities (i.e., design for disassembly) affect the willingness of producers for product recovery? (3) How do the investment needs to start recovery practices and the reluctance of producers to allocate sufficient funds for this purpose affect the optimal recovery decisions? We use stylized economic models to represent the implementation in practice and solving our models we obtain closed form and numerical solutions that help us to see the impact of various parameters on the optimal decisions of a producer. Our findings indicate that redesign opportunities encourage producers for more recovery, however the reluctance of producers to cover the initial investments may substantially reduce the effectiveness of the legislation and the recovery amounts.     

pH Controlled Intersystem Crossing and Singlet Oxygen Generation of 8-Azaadenine in Aqueous Solution

Azabases are intriguing DNA and RNA analogues and have been used as effective antiviral and anticancer medicines. However, photosensitivity of these drugs has also been reported. Here, pH-controlled intersystem crossing (ISC) process of 9H 8-azaadenine (8-AA) in aqueous solution is reported. Broadband transient absorption measurements reveal that the hydrogen atom at N9 position can greatly affect ISC of 8-AA and ISC is more favorable when 8-AA is in its neutral form in aqueous solution. The initial excited ππ* (S₂) state evolves through ultrafast internal conversion (IC) (4.2 ps) to the lower-lying nπ* state (S₁), which further stands as a door way state for ISC with a time constant of 160 ps. The triplet state has a lifetime of 6.1 μs. On the other hand, deprotonation at N9 position promotes the IC from the ππ* (S₂) state to the ground state (S₀) and the lifetime of the S₂ state is determined to be 10 ps. The experimental results are further supported by time-dependent density functional theory (TDDFT) calculations. Singlet oxygen generation yield is measured to be 13.8 % for the neutral 8-AA while the deprotonated one exhibit much lower yield (<2 %), implying that this compound could be a potential pH-sensitized photodynamic therapy agent.     

pH and temperature-responsive wormlike micelles formed by single amine oxide surfactant

In this paper, a novel type of pH- and temperature-responsive smart wormlike micelles based on (Z)-N,N-dimethyl-3-(octadec-9-enamido) propan-1-amine oxide (OAPAO) synthesized was studied. The structure of OAPAO was characterized by ¹H NMR and FTIR. The micellization and aggregation properties of the OAPAO surfactant in aqueous solution at different pH values were studied using equilibrium surface tension. The OAPAO solution exhibited pH-regulated surface activity at the air–water interface by assessing relevant parameters such as cmc, γ_cmc, Г_max, and A_min at pH?=?2.10, 6.80, and 11.90. The viscosity and rheological measurements demonstrated the pH-sensitive flowing behavior and property, which was attributed to the interactions transition between the OAPAO head groups. Moreover, the system could be promptly switched between low viscous fluid and highly viscoelastic fluid by alternatively adjusting the pH between 2.05 and 6.82. Combining the distribution state of OAPAO, a mechanism for the different intermolecular forces at different pH regions was proposed. Furthermore, the OAPAO solution exhibited an evident temperature-responsiveness at pH?=?6.82 and 11.88 in a certain temperature range (25–65°C) resulting from the effect of temperature on the hydrophobic effect and the intermicellar branching junctions.     

Stability studies of potent opioid analgesic,morphine‐6‐O‐sulfate in various buffers and biological matrices by HPLC‐DAD analysis

The 6‐O‐ sulfate ester of morphine (M6S) has previously been shown to be an analgesic with greater potency and fewer side effects than morphine. However, being a sulfate ester derivative of morphine, the question exists as to whether this compound is stable in biological fluids and tissues with regard to pH‐ and esterase‐mediated degradation. To date, no studies have focused on the stability profile of M6S across the physiologically relevant pH range of 1.2–7.4. In addition, the stability of M6S is not known in rat plasma and rat brain homogenate, or in simulated rat gastric and intestinal fluids. This study determines the stability profile of M6S (utilized as the sodium salt) and demonstrates that M6S is highly stable and resilient to either enzymatic‐ or pH‐dependent hydrolysis in vitro .     

Biocompatible and pH-Responsive Colloidal Surfactants with Tunable Shape for Controlled Interfacial Curvature

Molecular-surfactant-stabilized emulsions are susceptible to coalescence and Ostwald ripening. Amphiphilic particles, which have a much stronger anchoring strength at the interface, could effectively alleviate these problems to form stable Pickering emulsions. Herein, we describe a versatile method to fabricate biocompatible amphiphilic dimer particles through controlled coprecipitation and phase separation. The dimer particles consist of a hydrophobic PLA bulb and a hydrophilic shellac–PEG bulb, thus resembling nonionic molecular surfactants. The size and diameter ratio of the dimer particles are readily tunable, providing flexible control over the water/oil interfacial curvature and thus the type of emulsion. The particle-stabilized emulsions were stable for a long period of time and could be destabilized through a pH-triggered response. The biocompatible amphiphilic dimer particles with tunable morphology and functionality are thus ideal colloidal surfactants for various applications.     

Effect of pH on the Final Connectivity Distribution of the Silicon Atoms in the Stöber Particles

Using ²⁹Si MAS-NMR we investigate the effect of pH on the final connectivity distribution of the silicon atoms in the Stöber particles. Our data suggest that the fraction of the silicon atoms that are ully-connected decreases as the ammonia concentration is increased. This suggests a more negative first shell substitution effect in the precipitated phase (liquid droplet) if condensation reactions are irreversible. A simple model is developed to describe the condensation kinetics in the precipitated phase, and the results support the negative first shell substitution effect. These findings challenge the notion of a positive first shell substitution effect in alkaline conditions.     

ESR and NMR studies of poly (amidoamine) dendrimers with ionic surfactants in different media

The electron paramagnetic resonance (EPR) study has been carried out for the micellar solutions of various ionic surfactant solutions as well as various generations of aqueous dendrimer both in their respective presence as well as their absence at 25°C and in different media. From these measurements, the rotation correlation time (τ_B) have been calculated for all the ionic surfactant + PAMAM + water system. A variation in the τ_Bvalue remains mostly constant for the dodecyltrimethyammonium bromide (DTAB) and tetradecyltrimethylammonium bromide (TTAB) + PAMAM + water ternary mixtures. The τ_Bvalue shows an increase with the increase in the amount of PAMAM for SDS in basic medium and for 12-2-12 in acidic medium. It has been concluded from these results that SDS undergo complexation with all generations of PAMAM in basic medium and 12-2-12 in acidic medium and produce stronger hydrophobic environment. The nuclear magnetic resonance study (NMR) allowed us to evaluate the spin–spin relaxation (T₁) times of SDS in the presence of all generations of PAMAM. The T₁ values for all the tail protons of SDS showed a slight decrease with the increase in the constant amount of PAMAM suggesting the adsorption of PAMAM molecules on the micelle surface.