Cell Engineering with Functional Poly(oxanorbornene) Block Copolymers

Cell‐based therapies are gaining prominence in treating a wide variety of diseases and using synthetic polymers to manipulate these cells provides an opportunity to impart function that could not be achieved using solely genetic means. Herein, we describe the utility of functional block copolymers synthesized by ring‐opening metathesis polymerization (ROMP) that can insert directly into the cell membrane via the incorporation of long alkyl chains into a short polymer block leading to non‐covalent, hydrophobic interactions with the lipid bilayer. Furthermore, we demonstrate that these polymers can be imbued with advanced functionalities. A photosensitizer was incorporated into these polymers to enable spatially controlled cell death by the localized generation of ¹O₂ at the cell surface in response to red‐light irradiation. In a broader context, we believe our polymer insertion strategy could be used as a general methodology to impart functionality onto cell‐surfaces.     

Stealth Luminescent Organic Nanoparticles Made from Quadrupolar Dyes for Two-Photon Bioimaging: Effect of End-Groups and Core

Molecular-based Fluorescent Organic Nanoparticles (FONs) are versatile light-emitting nano-tools whose properties can be rationally addressed by bottom-up molecular engineering. A challenging property to gain control over is the interaction of the FONs’ surface with biological systems. Indeed, most types of nanoparticles tend to interact with biological membranes. To address this limitation, we recently reported on two-photon (2P) absorbing, red to near infrared (NIR) emitting quadrupolar extended dyes built from a benzothiadiazole core and diphenylamino endgroups that yield spontaneously stealth FONs. In this paper, we expand our understanding of the structure-property relationship between the dye structure and the FONs 2P absorption response, fluorescence and stealthiness by characterizing a dye-related series of FONs. We observe that increasing the strength of the donor end-groups or of the core acceptor in the quadrupolar (D-π-A-π-D) dye structure allows for the tuning of optical properties, notably red-shifting both the emission (from red to NIR) and 2P absorption spectra while inducing a decrease in their fluorescence quantum yield. Thanks to their strong 1P and 2P absorption, all FONs whose median size varies between 11 and 28 nm exhibit giant 1P (10⁶ M⁻¹.cm⁻¹) and 2P (10⁴ GM) brightness values. Interestingly, all FONs were found to be non-toxic, exhibit stealth behaviour, and show vanishing non-specific interactions with cell membranes. We postulate that the strong hydrophobic character and the rigidity of the FONs building blocks are crucial to controlling the stealth nano-bio interface.     

Anion-Responsive Fluorescent Supramolecular Gels

Three novel bis-urea fluorescent low-molecular-weight gelators (LMWGs) based on the tetraethyl diphenylmethane spacer—namely, L1, L2, and L3, bearing indole, dansyl, and quinoline units as fluorogenic fragments, respectively, are able to form gel in different solvents. L2 and L3 gel in apolar solvents such as chlorobenzene and nitrobenzene. Gelator L1 is able to gel in the polar solvent mixture DMSO/H₂O (H₂O 15% v/v). This allowed the study of gel formation in the presence of anions as a third component. An interesting anion-dependent gel formation was observed with fluoride and benzoate inhibiting the gelation process and H₂PO₄⁻, thus causing a delay of 24 h in the gel formation. The interaction of L1 with the anions in solution was clarified by ¹H-NMR titrations and the differences in the cooperativity of the two types of NH H-bond donor groups (one indole NH and two urea NHs) on L1 when binding BzO⁻ or H₂PO₄⁻ were taken into account to explain the inhibition of the gelation in the presence of BzO⁻. DFT calculations corroborate this hypothesis and, more importantly, demonstrate considering a trimeric model of the L1 gel that BzO⁻ favours its disruption into monomers inhibiting the gel formation.     

Antiviral Activities of Algal-Based Sulfated Polysaccharides

An antiviral agent is urgently needed based on the high probability of the emergence and re-emergence of future viral disease, highlighted by the recent global COVID-19 pandemic. The emergence may be seen in the discovery of the Alpha, Beta, Gamma, Delta, and recently discovered Omicron variants of SARS-CoV-2. The need for strategies besides testing and isolation, social distancing, and vaccine development is clear. One of the strategies includes searching for an antiviral agent that provides effective results without toxicity, which is well-presented by significant results for carrageenan nasal spray in providing efficacy against human coronavirus-infected patients. As the primary producer of sulfated polysaccharides, marine plants, including macro- and microalgae, offer versatility in culture, production, and post-isolation development in obtaining the needed antiviral agent. Therefore, this review will describe an attempt to highlight the search for practical and safe antiviral agents from algal-based sulfated polysaccharides and to unveil their features for future development.     

Control of resonant peak depths of tunable long-period fiber gratings using overcoupling

We present a method to reduce changes in the resonant peak depth of a long-period fiber grating (LPFG) as the resonant band is tuned by varying the external refractive index. We theoretically analyze the effects of the initial coupling strength on the peak depth change as external refractive index is varied. By controlling the initial coupling strength, it is experimentally demonstrated that an optimum peak depth can be obtained over a range of operating wavelengths that will maximize the sensitivity and stability of LPFG based sensors and tunable filters.     

Analysis of KrF excimer laser beam modification resulting from ablation under closed thick film flowing filtered water

The application of a closed thick film flowing filtered water to immerse the ablation etching mechanism of an excimer laser poses interesting possibilities concerning debris control, modification of machined feature topography and modification of the ablation rate. Furthermore, these parameters have been shown to be dependent on flow velocity; hence, offering further user control of machining characteristics. However, the impact of this technique requires investigation. This contribution offers comparison of the calculated ablation pressure and the effect on feature surface characteristics given for laser ablation of bisphenol A polycarbonate using KrF excimer laser radiation in ambient air against laser ablation of the same substrate under closed thick film flowing filtered water immersion. Also, an impact of such immersion equipment on the optical performance of the micromachining centre used is quantified and reviewed. The pressure is calculated to have risen by a magnitude of 48, when using the liquid immersed ablation technique. This increase in pressure is proposed to have an increased surface roughness, promoting the number of asperities with a surface area lower than 16 μm²; resulting in a diffuse reflection of light and an apparent darkening of features. The focal length of the optical system was accurately predicted to increase by 2.958 mm, when using the closed flowing liquid immersion equipment. This equipment is predicted to have increased the optical depth of focus via reduction in the angle of convergence of the two defining image rays; yet the perceived focus, measured discretely by mean feature wall angle, was found to be 25% smaller when using the closed thick film flowing filtered water immersion technique instead of similar laser ablation in ambient air. A compressed plume interaction is proposed as a contributing factor in this change.     

Noise robustness of the nonlocality of entangled quantum states

We study the nonlocal properties of states resulting from the mixture of an arbitrary entangled state rho of two d-dimensional systems and completely depolarized noise, with respective weights p and 1-p. We first construct a local model for the case in which rho is maximally entangled and p at or below a certain bound. We then extend the model to arbitrary rho. Our results provide bounds on the resistance to noise of the nonlocal correlations of entangled states. For projective measurements, the critical value of the noise parameter p for which the state becomes local is at least asymptotically log(d) larger than the critical value for separability.     

Low dose 60Co gamma-irradiation effects on electronic carrier transport and DC characteristics of AlGaN/GaN high-electron-mobility transistors

The impact of internal irradiation with secondary Compton electrons, generated by gamma-photons, on the characteristics of III-N/GaN-based devices was explored. N-channel AlGaN/GaN high-electron-mobility transistors (HEMTs) were exposed to gamma-radiation from a ⁶⁰Co source for doses up to 600?Gy. Temperature-dependent electron beam-induced current (EBIC) was employed to measure minority carrier transport properties. For low doses below ～250?Gy, the minority carrier diffusion length in AlGaN/GaN HEMTs is shown to increase by about 40%. This increase is likely due to longer minority carrier lifetime induced by internal Compton electron irradiation. An associated decrease in activation energy, extracted from temperature-dependent EBIC, was also found. The obtained increase in transconductance and decrease in gate leakage current indicate an improvement in performance of the devices after low doses of irradiation. For high doses of gamma-irradiation, above ～300?Gy, the performance of HEMTs showed a deterioration. The deterioration results from the onset of increased carrier scattering due to additional radiation-induced defects, as is translated in a decrease of minority carrier diffusion length.     

Periodic magnetic geodesics on Heisenberg manifolds

Annals of Global Analysis and Geometry - We study the dynamics of magnetic flows on Heisenberg groups, investigating the extent to which properties of the underlying Riemannian geometry are...     

Objectively discerning Autler-Townes splitting from electromagnetically induced transparency

Autler-Townes splitting (ATS) and electromagnetically induced transparency (EIT) both yield transparency in an absorption profile, but only EIT yields strong transparency for a weak pump field due to Fano interference. Empirically discriminating EIT from ATS is important but so far has been subjective. We introduce an objective method, based on Akaike's information criterion, to test ATS vs EIT from experimental data for three-level atomic systems and determine which pertains. We apply our method to a recently reported induced-transparency experiment in superconducting-circuit quantum electrodynamics.