Inflammatory-stimuli-responsive turn-on NIR fluorogenic theranostic prodrug: adjuvant delivery of diclofenac and hydrogen sulfide attenuates acute inflammatory disorders.

Prolonged use of very commonly prescribed non-steroidal anti-inflammatory drugs (NSAIDs) is often associated with undesired side effects, including gastrointestinal ulcers due to the non-selective inhibition of cyclooxygenases. We describe the development of an inflammatory-stimuli-responsive turn-on fluorogenic theranostic prodrug DCF-HS for adjuvant drug delivery. Upon activation by reactive oxygen species (ROS), the prodrug releases diclofenac DCF (active drug) and the NIR fluorophore DCI-NH2 along with carbonyl sulfide (COS). The second activation of COS by the enzyme carbonic anhydrase (CA) generates hydrogen sulfide (H2S). The prodrug was conveniently synthesized using multi-step organic synthesis. The UV-Vis and fluorescence studies revealed the selective reactivity of DCF-HS towards ROS such as H2O2 in the aqueous phase and the desired uncaging of the drug DCF with turn-on NIR fluorescent reporter under physiological conditions. Furthermore, the release of fluorophore DCI-NH2 and drug DCF was confirmed using the reverse phase HPLC method. Compatibility of prodrug activation was studied next in the cellular medium. The prodrug DCF-HS was non-toxic in a representative cancer cell line (HeLa) and a macrophage cell line (RAW 264.7) up to 100 µM concentration, indicating its biocompatibility. The intracellular ROS-mediated activation of the prodrug with the release of NIR dye DCI-NH2 and H2S was investigated in HeLa cells using the H2S-selective probe WSP2. The anti-inflammatory activity of the active drug DCF from the prodrug DCF-HS was studied in the lipopolysaccharide (LPS)-induced macrophage cell line and compared to that of the parent drug DCF using western blot analysis and it was found that the active drug resulted in pronounced inhibition of COX-2 in a dose-dependent manner. Finally, the anti-inflammatory potential of the prodrug and the turn-on fluorescence were validated in the inflammation-induced Wister rat models.

Stimuli-responsive biotin-anchored prodrug for the targeted delivery of anti-cancer agent NBDHEX with turn-on NIR fluorescence.

Biothiol-activatable prodrug RK-296 was designed for the delivery of potent anti-cancer agent NBDHEX with concomitant turn-on near infrared (NIR) fluorescence. NBDHEX exhibits anti-cancer activity by selectively inhibiting glutathione-S-transferase pi (GSTP1), which is overexpressed in cancer cells and responsible for the inactivation of chemotherapeutic drugs. The sustained release of NBDHEX from the prodrug would be useful for ameliorating the off-target side-effects of NBDHEX.

Control of trion-to-exciton conversion in monolayer WS2 by orbital angular momentum of light.

Controlling the density of exciton and trion quasiparticles in monolayer two-dimensional (2D) materials at room temperature by nondestructive techniques is highly desired for the development of future optoelectronic devices. Here, the effects of different orbital angular momentum (OAM) lights on monolayer tungsten disulfide at both room temperature and low temperatures are investigated, which reveal simultaneously enhanced exciton intensity and suppressed trion intensity in the photoluminescence spectra with increasing topological charge of the OAM light. In addition, the trion-to-exciton conversion efficiency is found to increase rapidly with the OAM light at low laser power and decrease with increasing power. Moreover, the trion binding energy and the concentration of unbound electrons are estimated, which shed light on how these quantities depend on OAM. A phenomenological model is proposed to account for the experimental data. These findings pave a way toward manipulating the exciton emission in 2D materials with OAM light for optoelectronic applications.

Experimental demonstration of in situ surface and thickness profile measurements of thin film during deposition using a grating array based wavefront sensor.

Here we introduce an in situ and non-intrusive surface and thickness profile monitoring scheme of thin-film growth during deposition. The scheme is implemented using a programmable grating array based zonal wavefront sensor integrated with a thin-film deposition unit. It provides both 2D surface and thickness profiles of any reflecting thin film during deposition without requiring the properties of the thin-film material. The proposed scheme comprises a mechanism to nullify the effect of vibrations which is normally built in with the vacuum pumps of thin-film deposition systems and is largely immune to the fluctuations in the probe beam intensity. The final thickness profile obtained is compared with independent off-line measurement and the two results are observed to be in agreement.

Correlation between surface scaling behavior and surface plasmon resonance properties of semitransparent nanostructured Cu thin films deposited via PLD.

The surface scaling behavior of nanostructured Cu thin films, grown on glass substrates by the pulsed laser deposition technique, as a function of the deposition time has been studied using height-height correlation function analysis from atomic force microscopy (AFM) images. The scaling exponents α, ß, 1/z and γ of the films were determined from AFM images. The local roughness exponent, α, was found to be ∼0.86 in the early stage of growth of Cu films deposited for 10 minutes while it increased to 0.95 with a longer time of deposition of 20 minutes and beyond this, it was nearly constant. Interface width w (rms roughness) scales with depositing time (t) as ∼ t ß , with the value of the growth exponent, ß, of 1.07 ± 0.11 and lateral correlation length ξ following ξ = t 1/z and the value of 1/z = 0.70 ± 0.10. These exponent values convey that the growth dynamics of PLD Cu films can be best described by a combination of local and non-local models under a shadowing mechanism and under highly sticking substrate conditions. From the scaling exponents and power spectral density function, it is concluded that the films follow a mound like growth mechanism which becomes prominent at longer deposition times. All the Cu films exhibited SPR properties where the SPR peak shifts towards red with increasing correlation length (ξ) whereas bandwidth increases initially with ξ and thereafter decreases gradually with ξ.