Non-centrosymmetric molecular crystals have a plethora of applications, such as piezoelectric transducers, energy storage and nonlinear optical materials owing to their unique structural order which is absent in other synthetic materials. As most crystals are brittle, their efficiency declines upon prolonged usage due to fatigue or catastrophic failure, limiting their utilities. Some natural substances, like bone, enamel, leaf and skin, function efficiently, last a life-time, thanks to their inherent self-healing nature. Therefore, incorporating self-healing ability in crystalline materials will greatly broaden their scope. Here, we report single crystals of a dibenzoate derivative, capable of self-healing within milliseconds via autonomous actuation. Systematic quantitative experiments reveal the limit of mechanical forces that the self-healing crystals can withstand. As a proof-of-concept, we also demonstrate that our self-healed crystals can retain their second harmonic generation (SHG) with high efficiency. Kinematic analysis of the actuation in our system also revealed its impressive performance parameters, and shows actuation response times in the millisecond range.
Installing proton-coupled electron transfer (PCET) in Ir-complexes is indeed a newly explored phenomenon, offering high quantum efficiency and tunable photophysics; however, the prospects for its application in various fields, including interrogating biological systems, are quite open and exciting. Herein, we developed various organelle-targeted Ir(iii)-complexes by leveraging the photoinduced PCET process to see the opportunities in phototherapeutic application and investigate the underlying mechanisms of action (MOAs). We diversified the ligands' nature and also incorporated a H-bonded benzimidazole-phenol (BIP) moiety with π-conjugated ancillary ligands in Ir(iii) to study the excited-state intramolecular proton transfer (ESIPT) process for tuning dual emission bands and to tempt excited-state PCET. These visible or two-photon-NIR light activatable Ir-catalysts generate reactive hydroxyl radicals (ËOH) and simultaneously oxidize electron donating biomolecules (1,4-dihydronicotinamide adenine dinucleotide or glutathione) to disrupt redox homeostasis, downregulate the GPX4 enzyme, and amplify oxidative stress and lipid peroxide (LPO) accumulation. Our homogeneous photocatalytic platform efficiently triggers organelle dysfunction mediated by a Fenton-like pathway with spatiotemporal control upon illumination to evoke ferroptosis poised with the synergistic action of apoptosis in a hypoxic environment leading to cell death. Ir2 is the most efficient photochemotherapy agent among others, which provided profound cytophototoxicity to 4T1 and MCF-7 cancerous cells and inhibited solid hypoxic tumor growth in vitro and in vivo.
A series of chiral peptide luminophores containing the coumarin moiety was synthesized via a simple and efficient solution-based procedure. The peptides, containing either L-Phe, or L-Ala, or L-Leu (designated, respectively, as p1, p2, and p3), self-aggregate to form anti-parallel sheet-like structures. The self-assembly of the peptide luminophores leads to non-centrosymmetric crystals which display significant second harmonic generation (SHG). The dependence of the SHG intensity on the input laser polarization revealed a strong correlation between the SHG and the crystal packing. In the polar plots, the SHG intensity as a function of the linear polarization orientation of the input laser beam gave a four-petal pattern for p1, a predominantly two-petal pattern for p2, and a dumbbell-shaped pattern for p3. This reflects the dependence of the second order optical susceptibility tensor on the crystal symmetry. The polar plots can be fitted very well with the theoretical expressions derived from the second order polarization equation after incorporating crystal symmetry in the second order optical susceptibility tensor. The strong polarization-dependent SHG from organic crystals may be interesting for polarization controlled nonlinear optical switches, sensors, and actuators.
Semiconductor nanostructures with near-unity photoluminescence quantum yields (PLQYs) are imperative for light-emitting diodes and display devices. A PLQY of 99.7 ± 0.3% has been obtained by stabilizing 91% Sn2+ in the Dion-Jacobson (8N8)SnBr4 (8N8-DJ) perovskite with 1,8-diaminooctane (8N8) spacer. The PLQY is favored by a longer spacer molecule and out-of-plane octahedral tilting. The PLQY shows one-month ambient stability under high relative humidity (RH) and temperature. With n-octylamine (8N) spacer, Ruddlesden-Popper (8N)2SnBr4 (8N-RP) also shows PLQY of 91.7 ± 0.6%, but it has poor ambient stability. The 5-300 K PL experiments decipher the self-trapped excitons (STEs) where the self-trapping depth is 25.6 ± 0.4 meV below the conduction band because of strong carrier-phonon coupling. The microsecond long-lived STE dominates over the band edge (BE) peaks at lower excitation wavelengths and higher temperatures. The higher PLQY and stability of 8N8-DJ are due to the stronger interaction between SnBr64- octahedra and 8N8 spacer, leading to a rigid structure.
Optical control of helicity-dependent photocurrent in topological insulator (TI) Sb2Te2Se has been studied at room temperature on epitaxial thin-films grown by pulsed laser deposition (PLD). Comparison with a theoretical model, which fits the data very well, reveals different contributions to the measured photocurrent. Study of the dependence of photocurrent on the angle of incidence (wave-vector) of the excitation light with respect to the sample normal helps to identify the origin of different components of the photocurrent. Enhancement and inversion of the photocurrent in the presence of the photothermal gradient for light incident on two opposite edges of the sample occur due to selective spin-state excitation with two opposite circularly polarized lights in the presence of the unique spin-momentum locked surface states. These observations render the PLD-grown epitaxial TI thin-films promising for optoelectronic devices such as sensors, switches, and actuators whose response can be controlled by polarization as well as the angle of incidence of light under ambient conditions. The polarization response can also be tuned by the photothermal effect by suitably positioning the incident light beam on the device.
In recent times, organelle-targeted drug delivery systems have gained tremendous attention due to the site-specific delivery of active drug molecules, resulting in enhanced bioefficacy. In this context, a phototriggered drug delivery system (DDS) for releasing an active molecule is superior, as it provides spatial and temporal control over the release. So far, a near-infrared (NIR) light-responsive organelle-targeted DDS has not yet been developed. Hence, we introduced a two-photon NIR light-responsive lysosome-targeted "AIE + ESIPT" active single-component DDS based on the naphthalene chromophore. The two-photon absorption cross section of our DDS is 142 GM at 850 nm. The DDS was converted into pure organic nanoparticles for biological applications. Our nano-DDS is capable of selective targeting, AIE luminogenic imaging, and drug release within the lysosome. In vitro studies using cancerous cell lines showed that our single-component photoresponsive nanocarrier exhibited enhanced cytotoxicity and real-time monitoring ability of drug release.
Biocompatible Materials/chemistry , Nanoparticles/chemistry , Naphthalenes/chemistry , Photons , Biocompatible Materials/chemical synthesis , Biocompatible Materials/pharmacology , Cell Line, Tumor , Cell Survival/drug effects , Drug Carriers/chemistry , Drug Delivery Systems , Humans , Infrared Rays , Materials Testing , Molecular Structure , Naphthalenes/pharmacology , Particle Size , Surface Properties , Time Factors
We demonstrated for the first time without any chemical modification the two-photon absorption (TPA) cross-section can be enhanced and red-shifted to the near-infrared (NIR) region by the ground-state proton-transfer (GSPT) process. Using GSPT, we developed a simple binol-based aggregation-induced emission (AIE)-fluorogenic phototrigger having a large two-photon uncaging cross-section in the "phototherapeutic window". As a proof of concept, we showed our phototrigger for the release of two different anticancer drugs in the NIR region.
We report a two-photon responsive drug delivery system (DDS), namely, p-hydroxyphenacyl-naphthalene-chlorambucil (pHP-Naph-Cbl), having a two-photon absorption (TPA) cross-section of ≥20 GM in the phototherapeutic window (700 nm). Our DDS exhibited both AIE and ESIPT phenomena, which were utilized for the real-time monitoring of anti-cancer drug release.
Antineoplastic Agents, Alkylating/chemistry , Chlorambucil/chemistry , Drug Carriers/chemistry , Naphthalenes/chemistry , Antineoplastic Agents, Alkylating/metabolism , Antineoplastic Agents, Alkylating/pharmacology , Cell Survival/drug effects , Chlorambucil/metabolism , Chlorambucil/pharmacology , Drug Liberation , Humans , Light , MCF-7 Cells , Microscopy, Confocal , Photons
We present a simple but mathematically complete first-principles theory for the pump-probe differential reflectivity experiment at negative delay (probe preceding the pump) to show how it gives information about the perturbed-free-induction-decay of coherent polarization. The calculation, involving the optical Bloch equations to describe the induced polarization and the Ewald-Oseen idea to calculate the reflected signal as a consequence of the free oscillations of perturbed dipoles, also explicitly includes the process of lock-in detection of a double-chopped signal after it has passed through a monochromator. The theory giving a closed form expression for the measured signal in both time and spectal domains is compared with experiments on high quality GaAs quantum well sample. The dephasing time inferred experimentally at 4 K compares remarkably well with the inverse of the absorption linewidth of the continuous-wave photoluminescence excitation spectrum. Spectrally-resolved signal at negative delay calculated from our theoretical expression nicely reproduces the coherent spectral oscillations observed in our experiments, although exact fitting of the experimental spectra with the theoretical expression is difficult on account of multiple resonances.
We have closely examined the emission spectrum at the heavy-hole exciton resonance in a high-quality GaAs multi-quantum well sample using picosecond excitation-correlation photoluminescence (ECPL) spectroscopy. Dynamics of the ECPL signal at low and high energy sides of the excitonic photoluminescence (PL) peak show complementary behavior. The ECPL signal is positive (negative) below (above) the PL peak and it changes sign within a narrow band of energy lying between the excitonic absorption and emission peaks. The energy at which this sign change takes place is interpreted as the excitonic mobility edge as it separates localized excitons in quantum dot-like states from mobile excitons in quantum well-like states.
The molecular self-assembly, growth and nonlinear thermo-optical properties of three synthetic aromaticaliphatic hybrid nitropeptides have been investigated. The X-ray crystallography of nitropeptide 2 containing a glutamic acid moiety shows that the peptide adopts a dimeric structure using intermolecular hydrogen bonding as well as face to face ππ stacking interactions. Moreover, nitropeptide 2 exhibits nonlocal nonlinear optical properties. When a Gaussian laser beam passes through nitropeptide 2, the peptide shows several concentric rings due to spatial self-phase modulation (SSPM). However, the homologous peptide 1 containing an aspartic acid moiety and peptide 3 containing an achiral α-aminoisobutyric acid (Aib) moiety adopt sheet-like structures and have no self-phase modulation effect. The report describes the thermo-optical properties consistent with assumption and calculation and is promising for their applications in nonlinear optical modulation devices.
Peptides/chemistry , Temperature , Crystallography, X-Ray , Hydrogen Bonding , Models, Molecular , Molecular Conformation , Particle Size , Peptides/chemical synthesis , Surface Properties
We study a specific type of lifetime broadening resulting in the well-known exponential "Urbach tail" density of states within the energy gap of an insulator. After establishing the frequency and temperature dependence of the Urbach edge in GaAs quantum wells, we show that the broadening due to the zero-point optical phonons is the fundamental limit to the Urbach slope in high-quality samples. In rough analogy with Welton's heuristic interpretation of the Lamb shift, the zero-temperature contribution to the Urbach slope can be thought of as arising from the electric field of the zero-point longitudinal-optical phonons. The value of this electric field is experimentally measured to be 3 kV cm-1, in excellent agreement with the theoretical estimate.
