Optical Property Control by the Interligand Charge Transfer Excited State in Brominated Homoleptic and Heteroleptic Aluminum Dinuclear Triple-Stranded Helicates.

The utilization of aluminum, an abundant and inexpensive element, for the synthesis of novel functional complexes is extremely important, but the design and control of photofunctionality are still unexplored. In this study, we focused on our previously developed dinuclear triple-stranded helicates incorporating two aluminum ions (ALPHY) to synthesize both homoleptic and heteroleptic complexes with bromine atoms at the 3-position of the pyrrole moiety in the Schiff base ligands. The brominated Schiff base ligands were reacted with AlCl3 to synthesize homoleptic complexes, while different ligands were mixed to prepare heteroleptic complexes. Single-crystal X-ray structural analysis revealed the structures of these novel complexes. We found that increasing the degree of bromination resulted in a tunable emission color, shifting progressively from 550 (yellow) to 566 nm (orange). Optical resolution of the complexes facilitated the observation of mirror-image circular dichroism and circularly polarized luminescence. Furthermore, employing ultrafast spectroscopy techniques, we have elucidated that the optical properties are governed by the interligand charge transfer (ILCT) among the three ligands. The formation of heteroleptic complexes induces the ILCT state even in nonpolar environments, thereby accelerating nonradiative decay and intersystem crossing. These findings mark significant advancements in photofunctional materials based on multinuclear complexes.

Unraveling the Remarkable Influence of Substituents on the Emission Variation and Circularly Polarized Luminescence of Dinuclear Aluminum Triple-Stranded Helicates.

This study explored the development of functional dyes using aluminum, focusing on aluminum-based dinuclear triple-stranded helicates, and examined the effects of substituent variations on their structural and optical properties. Key findings revealed that the modification of methyl groups to the pyrrole positions significantly extended the conjugation system, resulting in a red shift in the absorption and emission spectra. Conversely, the modification of methyl groups at the methine positions due to steric hindrances increased the torsion angle of the ligands, leading to a blue shift in the absorption and emission spectra. A common feature across all complexes was that in the excited state, one of the three ligands underwent significant structural relaxation. This led to a pronounced Stokes shift and minimal spectra overlap with high photoluminescence behaviors. Moreover, our research extended to the optical resolution of the newly synthesized complexes by analyzing the chiroptical properties of the resulting enantiomers, including their circular dichroism and circularly polarized luminescence. These insights offer valuable contributions to the design and application of novel aluminum-based functional dyes, potentially influencing a range of fields, from materials science to optoelectronics.

Solid lipid nanoparticles of lutein with improved dissolution behavior and oral absorption.

The present study aimed to develop solid lipid nanoparticles of lutein (SLN/LT) with improved dissolution behavior and oral absorption. SLN/LT were prepared by a flash nanoprecipitation method using a multi-inlet vortex mixer, and their physicochemical, photochemical, and pharmacokinetic properties were evaluated. The mean particle size of SLN/LT re-dispersed in water was 237 nm, and small spherical particles with no significant aggregation were observed. LT significantly generated singlet oxygen upon exposure to pseudo-sunlight (250 W/m2, 1 h), suggesting its high photoreactivity. The remaining LT in LT solution, crystalline LT, and SLN/LT after irradiation with pseudo-sunlight (250 W/m2, 2 h) were 56.3, 86.7, and 101%, respectively. SLN/LT showed improved dissolution behavior of LT in simulated intestinal fluid, and the dissolved amounts of LT at 2 h were at least 50 times higher than that of crystalline LT. Orally administered SLN/LT (100 mg-LT/kg) exhibited enhanced oral absorption of LT, as evidenced by a relative bioavailability of 3.7 to crystalline LT in rats. SLN/LT may be a promising dosage form for orally available LT supplements, possibly leading to enhanced nutritional functions of LT.

Thoracic esophageal injury due to a neck stab wound: a case report.

BACKGROUND: Traumatic esophageal injury leads to severe complications such as mediastinitis, pyothorax, and tracheoesophageal fistula. Although prompt diagnosis and treatment are required, there are no established protocols to guide diagnosis or treatment. In particular, thoracic esophageal injury tends to be diagnosed later than cervical esophageal injury because it has few specific symptoms. We report a case of thoracic esophageal injury caused by a cervical stab wound; the patient was stabbed with a sharp blade. CASE PRESENTATION: A 74-year-old woman was attacked with a knife while sleeping at home. The patient was taken to the emergency room with an injury localized to the left section of her neck. She was suspected of a left jugular vein and recurrent laryngeal nerve injury from cervical hematoma and hoarseness. On the day following the injury, computed tomography revealed a thoracic esophageal injury. Emergency surgery was performed for an esophageal perforation and mediastinal abscesses. Although delayed diagnosis resulted in suture failure, the patient was able to resume oral intake of food a month later following enteral feeding with a gastrostomy. Esophageal injuries due to sharp trauma are rare, and most are cervical esophageal injuries. There are very few reports on thoracic esophageal injuries. CONCLUSIONS: The possibility of thoracic esophageal injury should always be considered when dealing with neck stab wounds, particularly those caused by an attack.

Laparoscopic appendectomy during the second trimester of a twin pregnancy.

Acute appendicitis during pregnancy may lead to increased maternal and fetal risks. Laparoscopic appendectomy is commonly performed during pregnancy. Compared with open appendectomy in pregnant women, laparoscopic appendectomy has shown non-inferior safety for pregnancy outcomes and superior safety for surgical outcomes. Over the last few decades, the occurrence of twin pregnancy has been increasing. Performing an operation on a patient with a twin pregnancy is more difficult than with a singleton pregnancy. Only a few operations of this kind have been reported. Here, we present a case of a 20-week twin pregnant woman who presented with acute appendicitis. Laparoscopic appendectomy was performed, and no maternal complications occurred. This report contributes to discussions on the safety of the laparoscopic approach for appendicitis during twin pregnancies.

Supersaturable Self-Emulsifying Drug Delivery System of Krill Oil with Improved Oral Absorption and Hypotriglyceridemic Function.

This study aimed to develop a supersaturable self-emulsifying drug delivery system (S-SEDDS) of krill oil (KO), a rich source of docosahexaenoic acid and eicosapentaenoic acid (EPA), to improve its hypotriglyceridemic function. S-SEDDS of KO (KO/S-SEDDS) was prepared by the addition of lysolecithin, glycerin, and hydroxypropyl methylcellulose (HPMC). Self-emulsifying drug delivery system of KO (KO/SEDDS) and KO with HPMC (KO/HPMC) were also prepared for comparison purposes. The physicochemical and pharmacokinetic properties of KO samples were characterized, and the hypotriglyceridemic function of KO/S-SEDDS was evaluated. Micronized droplets in KO/SEDDS and KO/S-SEDDS with a mean diameter of ca. 270 nm could be observed in comparison to KO and KO/HPMC. Both KO/HPMC and KO/S-SEDDS tended to enhance the dissolution behavior of KO, and the S-SEDDS formulation improved the dissolution behavior of KO as a result of micronized droplets and the addition of HPMC. KO/S-SEDDS (60 mg of EPA/kg) improved the oral absorption of KO based on the pharmacokinetic profiling of EPA, and repeated oral administration of KO/S-SEDDS (250 mg of KO kg-1 day-1) for 7 days had a potent hypotriglyceridemic effect on rats with corn-oil-induced hypertriglyceridemia compared to orally administered KO. On the basis of these findings, the S-SEDDS approach might be an efficacious dosage option to enhance the nutraceutical properties of KO.

Self-micellizing solid dispersion of cyclosporine A for pulmonary delivery: Physicochemical, pharmacokinetic and safety assessments.

The present study aimed to develop an inhalable self-micellizing solid dispersion of cyclosporine A (SMSD/CsA) for the direct delivery to the respiratory system with improved therapeutic efficacy and minimized systemic exposure. SMSD/CsA was obtained by wet-milling, and then jet-milled SMSD/CsA was blended with lactose carrier, producing a respirable powder of SMSD/CsA (SMSD/CsA-RP). The physicochemical, pharmacological, and pharmacokinetic properties of SMSD/CsA-RP were characterized, and the hepatotoxic and nephrotoxic potentials were investigated by biomarker analysis. Cascade impactor analysis demonstrated that SMSD/CsA-RP had high in vitro inhalation performance, with a fine particle fraction of 36%. In simulated lung fluid, the SMSD/CsA exhibited better dissolution behavior than amorphous CsA. Pretreatment with SMSD/CsA-RP resulted in significant suppression of antigen-evoked inflammatory events in rats. After intratracheal administration of SMSD/CsA-RP at a pharmacologically effective dose (100µg-CsA/rat), the AUC0-24 value was <1% of that after oral administration of Neoral® at a toxic dose (10mg-CsA/kg). Compared with oral Neoral®, insufflated SMSD/CsA-RP showed 99% reductions of CsA concentrations in both liver and kidney. No significant increases of biomarker levels in plasma were observed even after repeated intratracheal administration of SMSD/CsA-RP for 7days. From these findings, SMSD/CsA-RP might be a favorable dosage form for effective and safe inhalation therapy of CsA.