Surface topography of ultrashort laser-irradiated CaF2

A single-crystal CaF₂ (111) was irradiated with single and multiple laser (Ti:sapphire, 800 nm, 25 fs) shots at fluences ranging from 0.25 to 1.5 J cm^?2. In this fluence regime, a single laser pulse usually leads to typical bump-like features ranging from 200 nm to 1.5 μm in diameter and 10–50 nm in height. These bumps are related to compressive stresses due to a pressure build-up induced by fast laser heating and their subsequent relaxation. When CaF₂ is irradiated with successive (in our case 20) shots at a laser fluence of 1.5 J cm^?2, nanocavities at the top of the microbumps are observed. The formation of these nanocavities is regarded as an explosion and is attributed to the explosive expansion generated by shock waves due to laser-induced plasma after the nonlinear absorption of the laser energy by the material. Such kinds of surface structures at the nanometre scale could be attractive for nanolithography.     

Laser irradiation effects on the surface,structural and mechanical properties of Al–Cu alloy 2024

Laser irradiation effects on surface, structural and mechanical properties of Al–Cu–Mg alloy (Al–Cu alloy 2024) have been investigated. The specimens were irradiated for various fluences ranging from 3.8 to 5.5 J/cm² using an Excimer (KrF) laser (248 nm, 18 ns, 30 Hz) under vacuum environment. The surface and structural modifications of the irradiated targets have been investigated by scanning electron microscope (SEM) and X-ray diffractometer (XRD), respectively. SEM analysis reveals the formation of micro-sized craters along the growth of periodic surface structures (ripples) at their peripheries. The size of the craters initially increases and then decreases by increasing the laser fluence. XRD analysis shows an anomalous trend in the peak intensity and crystallite size of the specimen irradiated for various fluences. A universal tensile testing machine and Vickers microhardness tester were employed in order to investigate the mechanical properties of the irradiated targets. The changes in yield strength, ultimate tensile strength and microhardness were found to be anomalous with increasing laser fluences. The changes in the surface and structural properties of Al–Cu alloy 2024 after laser irradiation have been associated with the changes in mechanical properties.     

Characterization of polyoxyethylenes according to the number of hydroxy end groups by hydrophilic interaction chromatography at critical conditions for polyethylene glycol

Polyoxyethylenes with different functionality and architecture can be separated according to the number of terminal hydroxy groups on polar stationary phases in acetone water mobile phases containing 90–97% acetone. The best results were obtained on a HILIC column. Typical samples, which can be analyzed by this technique, are polyethylene glycols, their mono- and dialkyl ethers, macromonomers, the fatty esters of PEG, and ethoxylated glycerol.     

Arbutin derivatives from the seeds of Madhuca latifolia

A new arbutin derivative, madhuglucoside (1), along with three known arbutin derivatives were isolated from the seeds of Madhuca latifolia in addition to seven other known constituents. Their structures were established on the basis of spectral analysis. Compounds 1a, 2a and 3a were obtained in a pure state after acetylation of the mother fraction and characterized as their acetyl derivatives.     

Eremophilenolide‐Type Sesquiterpenes from Hertia intermedia

Hertidins A–E ( 1 – 5 , resp.), new eremophilenolide‐type sesquiterpenes, have been isolated from the AcOEt‐soluble fraction of Hertia intermedia. Structures of 1 – 5 were elucidated on the basis of extensive spectroscopic studies.     

In vitro binding studies of organotin(IV) complexes of 1,2-bis(1H-benzimidazol-2-yl)ethane-1,2-diol with CT-DNA and nucleotides (5′-GMP and 5′-TMP): Effect of the ancillary ligand on the binding propensity

The chiral benzimidazole ligand, 1,2-Bis(1H-benzimidazol-2-yl)ethane-1,2-diol, L, exhibiting coordination mode with an oxygen atom of alcohol group directed towards the metal ion and another -OH group with different molecular axis directed away from the metal center was utilized as a building block for organotin complexes [C₁₈H₁₉N₄O₂SnCl], [C₂₈H₂₃N₄O₂SnCl] and [C₅₂H₄₂N₄O₂Sn₂] (1-3). Complexes 1 and 3 exhibit a pentacoordinate geometry while the complex 2 reveals hexacoordinated environment around the Sn(IV) metal ions as evidenced by ¹¹⁹Sn NMR studies. The DNA binding ability of benzimidazole ligand and their organotin(IV) complexes 1-3 were examined by employing different biophysical methods. The absorption titration of the complexes with CT-DNA reveal significant hyperchromic effect together with strong bathochromic shift of 4-5 nm which infer substantial binding of the complexes with CT-DNA. The intrinsic binding constant K_b values of the complexes 1-3 were found to be 2.16 ± 0.04 × 10⁴, 3.47 ± 0.04 × 10⁴ and 4.60 ± 0.04 × 10³ M⁻¹, respectively, suggesting pronounced binding of complex 2 with DNA double helix. The mechanism of binding of the complexes was further ascertained by the interaction studies of these complexes with nucleotides (5′-GMP and 5′-TMP) using absorption spectroscopy suggesting a clear preference for 5′-GMP binding which was further authenticated by NMR (¹H and ³¹P NMR) studies.     

Influence of ambient gas and its pressure on the laser-induced breakdown spectroscopy and the surface morphology of laser-ablated Cd

The ablation of Cd has been performed by employing Q-switched Nd: YAG 10 ns laser pulses with a central wavelength of 1064 nm for a pulsed energy of 200 mJ under various ambient environments of argon, air and helium. The optical emission spectroscopy of Cd plasma has been studied under different filling pressures of shield gases ranging from 5 torr to 760 torr using LIBS spectrometer system. The effect of different gases and their pressures on the intensity of spectral emission, electron temperature and density of the laser-produced plasma has been investigated. SEM analysis has been performed to investigate the dependence of surface morphological changes of an irradiated target on the nature and pressure of an ambient gas. A strong correlation has revealed the vital role of electron temperature and density of laser-induced plasma for the surface modification of Cd. These results strongly indicate that the nature and pressure of the ambient atmosphere is one of the controlling factors of the plasma characteristics, as well as the factors related to the laser energy absorption for surface modification.     

Identification of ultra-fast electronic and thermal processes during femtosecond laser ablation of Si

Ultra-fast electronic and thermal processes for the energy deposition mechanism during femtosecond laser ablation of Si have been identified by means of atomic force microscopy and Raman scattering techniques. For this purpose, Si targets were exposed with 800-nm, 25-fs Ti:sapphire laser pulses for different laser fluencies in air and under UHV (ultra high vacuum) conditions. Various nano- and microstructures on the surface of the irradiated samples are revealed by a detailed surface topography analysis. Ultra-fast electronic processes are dominant in the lower-fluence regime. Therefore, by starting from the ablation threshold three different fluence regimes have been chosen: a lower-fluence regime (0.06–0.5 J?cm^?2 single-shot irradiation under UHV condition and 0.25–2.5 J?cm^?2 single-shot irradiation in ambient condition), a moderate-fluence regime (0.25–1.5 J?cm^?2 multiple-shot irradiation), and a higher-fluence regime (2.5–3.5 J?cm^?2 multiple-shot irradiation). Around the ablation threshold fluence, most significant features identified at the Si surface are nanohillock-like structures. The appearance of these nanohillocks is regarded as typical features for fast electronic processes (correlated with existence of hot electrons) and is explained on the basis of Coulomb explosion. The growth of these typical features (nanohillocks) by femtosecond laser irradiation is an element of novelty. At moderate irradiation fluence, a ring-shaped ablation with larger bumps and periodic surface structures is observed and is considered as a footprint of ultra-fast melting. Further increase in the laser fluence, i.e. a higher-fluence regime, resulted in strong enhancement of the thermal process with the appearance of larger islands. The change in surface topography provides an innovative clue to differentiate between ultra-fast electronic processes, i.e. Coulomb explosion (sub-100 fs) at a lower-fluence regime and ultra-fast melting (hundreds of fs) at a moderate-fluence regime, and slow thermal processes (ps time scale) at a higher-fluence regime. These fast electronic and thermal processes are well correlated to structural and crystallographic alterations, inferred from Raman spectroscopy.     

Meliloester, a new melilotic ester from Melilotus alba

A new melilotic ester, meliloester [2-ethyl-hexyl-3-(2-hydroxyphenyl) propionate], was isolated from the whole plant of Melilotus alba. Its structure was elucidated on the basis of spectroscopic and mass spectrometric analyses, including EI-MS, HR-MS, and UV, IR, 1D and 2D-NMR spectroscopic studies.     

A Combination of Visudyne and a Lipid‐anchored Liposomal Formulation of Benzoporphyrin Derivative Enhances Photodynamic Therapy Efficacy in a 3D Model for Ovarian Cancer

A major objective in developing new treatment approaches for lethal tumors is to reduce toxicity to normal tissues while maintaining therapeutic efficacy. Photodynamic therapy (PDT) provides a mechanistically distinct approach to treat tumors without the systemic toxicity of chemotherapy drugs. PDT involves the light‐based activation of a small molecule, a photosensitizer (PS), to generate reactive molecular species (RMS) that are toxic to target tissue. Depending on the PS localization, various cellular and subcellular components can be targeted, causing selective photodamage. It has been shown that targeted lysosomal photodamage followed by, or simultaneous with, mitochondrial photodamage using two different PS results in a considerable enhancement in PDT efficacy. Here, two liposomal formulations of benzoporphyrin derivative (BPD): (1) Visudyne (clinically approved) and (2) an in‐house formulation entrapping a lipid conjugate of BPD are used in combination with direct PS localization to mitochondria, endoplasmic reticulum and lysosomes, enabling simultaneous photodamage to all three organelles using a single wavelength of light. Building on findings by our group, and others, this study demonstrates, for the first time in a 3D model for ovarian cancer, that BPD‐mediated photodestruction of lysosomes and mitochondria/ER significantly enhances PDT efficacy at lower light doses than treatment with either PS formulation alone.