Au₂₀ Nanocluster Protected by Hemilabile Phosphines

A novel phosphine-protected Au₂₀ nanocluster was isolated through the reduction of Au­(PPhpy₂)Cl by NaBH₄ (PPhpy₂ = bis­(2-pyridyl)-phenylphosphine). Its composition was determined to be [Au₂₀(PPhpy₂)₁₀Cl₄]­Cl₂, and single crystal X-ray structural analysis revealed that the Au₂₀ core can be viewed as being generated from the fusion of two Au₁₁ clusters via sharing two vertices. Optical absorption spectroscopy indicated this Au₂₀ has a large HOMO–LUMO gap (<i>E</i>_g ≈ 2.24 eV). This is the first example of a ligand-protected gold nanocluster with a core generated from incomplete icosahedral Au₁₁ building units

Near-Infrared Light-Activatable Microneedle System for Treating Superficial Tumors by Combination of Chemotherapy and Photothermal Therapy

Because of the aggressive and recurrent nature of cancers, repeated and multimodal treatments are often necessary. Traditional cancer therapies have a risk of serious toxicity and side effects. Hence, it is crucial to develop an alternative treatment modality that is minimally invasive, effectively treats cancers with low toxicity, and can be repeated as required. We developed a light-activatable microneedle (MN) system that can repeatedly and simultaneously provide photothermal therapy and chemotherapy to superficial tumors and exert synergistic anticancer effects. This system consists of embeddable polycaprolactone MNs containing a photosensitive nanomaterial (lanthanum hexaboride) and an anticancer drug (doxorubicin; DOX), and a dissolvable poly­(vinyl alcohol)/polyvinylpyrrolidone supporting array patch. Because of this supporting array, the MNs can be completely inserted into the skin and embedded within the target tissue for locoregional cancer treatment. When exposed to near-infrared light, the embedded MN array uniformly heats the target tissue to induce a large thermal ablation area and then melts at 50 °C to release DOX in a broad area, thus destroying tumors. This light-activated heating and releasing behavior can be precisely controlled and switched on and off on demand for several cycles. We demonstrated that the MN-mediated synergistic therapy completely eradicated 4T1 tumors within 1 week after a single application of the MN and three cycles of laser treatment. No tumor recurrence and no significant body weight loss of mice were observed. Thus, the developed light-activatable MN with a unique embeddable feature offers an effective, user-friendly, and low-toxicity option for patients requiring long-term and multiple cancer treatments

Au₂₀ Nanocluster Protected by Hemilabile Phosphines

A novel phosphine-protected Au₂₀ nanocluster was isolated through the reduction of Au­(PPhpy₂)Cl by NaBH₄ (PPhpy₂ = bis­(2-pyridyl)-phenylphosphine). Its composition was determined to be [Au₂₀(PPhpy₂)₁₀Cl₄]­Cl₂, and single crystal X-ray structural analysis revealed that the Au₂₀ core can be viewed as being generated from the fusion of two Au₁₁ clusters via sharing two vertices. Optical absorption spectroscopy indicated this Au₂₀ has a large HOMO–LUMO gap (<i>E</i>_g ≈ 2.24 eV). This is the first example of a ligand-protected gold nanocluster with a core generated from incomplete icosahedral Au₁₁ building units

Near-Infrared Light-Responsive Composite Microneedles for On-Demand Transdermal Drug Delivery

This study presents near-infrared (NIR) light-responsive polymer–nanostructure composite microneedles used for on-demand transdermal drug delivery. Silica-coated lanthanum hexaboride (LaB₆@SiO₂) nanostructures were incorporated into polycaprolactone microneedles, serving as an NIR absorber. When the microneedles were irradiated with NIR light, light-to-heat transduction mediated by the LaB₆@SiO₂ nanostructures caused the microneedle melting at 50 °C. This increased the mobility of the polymer chains, enabling drug release from the matrix. Drug release from the microneedles was evaluated for four laser on/off cycles. In each cycle, the samples were irradiated until the temperature reached 50 °C for 3 min (laser on); the laser was then turned off for 30 min (laser off). The results showed that light-induced phase transition in the polymer triggered drug release from the melted microneedles. A stepwise drug-release behavior was observed after multiple cycles of NIR light exposure. No notable drug leakage was found in the off state. This NIR-light-triggerable device exhibits excellent reproducibility, low off-state leakage, and noninvasive triggerability and, thus, represents an advance in transdermal delivery technology

DataSheet_1_Adjuvant therapy provides no additional recurrence-free benefit for esophageal squamous cell carcinoma patients after neoadjuvant chemoimmunotherapy and surgery: a multi-center propensity score match study.docx

PurposeThe need for adjuvant therapy (AT) following neoadjuvant chemoimmunotherapy (nICT) and surgery in esophageal squamous cell cancer (ESCC) remains uncertain. This study aims to investigate whether AT offers additional benefits in terms of recurrence-free survival (RFS) for ESCC patients after nICT and surgery.MethodsRetrospective analysis was conducted between January 2019 and December 2022 from three centers. Eligible patients were divided into two groups: the AT group and the non-AT group. Survival analyses comparing different modalities of AT (including adjuvant chemotherapy and adjuvant chemoimmunotherapy) with non-AT were performed. The primary endpoint was RFS. Propensity score matching(PSM) was used to mitigate inter-group patient heterogeneity. Kaplan-Meier survival curves and Cox regression analysis were employed for recurrence-free survival analysis.ResultsA total of 155 nICT patients were included, with 26 patients experiencing recurrence. According to Cox analysis, receipt of adjuvant therapy emerged as an independent risk factor(HR:2.621, 95%CI:[1.089,6.310], P=0.032), and there was statistically significant difference in the Kaplan-Meier survival curves between non-AT and receipt of AT in matched pairs (p=0.026). Stratified analysis revealed AT bring no survival benefit to patients with pathological complete response(p= 0.149) and residual tumor cell(p=0.062). Subgroup analysis showed no significant difference in recurrence-free survival between non-AT and adjuvant chemoimmunotherapy patients(P=0.108). However, patients receiving adjuvant chemotherapy exhibited poorer recurrence survival compared to non-AT patients (p= 0.016).ConclusionIn terms of recurrence-free survival for ESCC patients after nICT and surgery, the necessity of adjuvant therapy especially the adjuvant chemotherapy, can be mitigated.</p