A Free Phosphaborene Stable at Room Temperature

Free phosphaborenes (R–PB–R) are PB analogues of alkynes, and their isolation is a long-sought-after goal. Herein, we demonstrate that the combination of a π-donating and a π-accepting substituent with bulky flanking arene rings enables the isolation of a crystalline free phosphaborene 5 at room temperature. This electron push–pull cooperation, combined with the kinetic protection, hinders its inherent tendency to oligomerize. This species features a PB double bond consisting of a conventional σ bond and a delocalized π bond. The lone pair of electrons at P slightly contributes to the PB bonding. Preliminary reactivity studies show that 5 undergoes facile (cyclo)addition reactions with p-methyl benzaldehyde, p-fluoroacetophenone, and carbon disulfide, the last of which results in facile PB double bond cleavage. Our strategy has a significant impact on the future synthesis of ambiphilic heterodiatomic multiply bonded main group species

Synthesis and Characterization of Coinage Metal Aluminum Sulfur Species

The synthesis of heterobimetallic cluster with the Al–S–M (M = Cu and Ag) structural unit has been realized for the first time by the reaction of aluminum-dithiol LAl­(SH)₂ (L = HC­[C­(Me)­N­(Ar)]₂, Ar = 2,6-<i>i</i>Pr₂C₆H₃) with (MesCu)₄ and (MesAg)₄ (Mes = 2,4,6-Me₃C₆H₂), respectively. The isolated clusters exhibit core structures of Al₂Cu₄S₄ and Al₄Ag₈S₈, respectively. During the formation of the [LAl­(SAg)₂]₄, a side product of LAlS₆ is formed. However, the reaction of LAl­(SH)₂ with excess of sulfur and (MesAg)₄ resulted in the formation of LAlS₄ as the only product soluble in organic solvents. Both of them represent rare examples of aluminum polysulfides. All compounds were characterized by spectroscopic methods and single crystal X-ray diffraction studies

DataSheet_1_Treatment- and immune-related adverse events of immune checkpoint inhibitors in esophageal or gastroesophageal junction cancer: A network meta-analysis of randomized controlled trials.zip

ObjectiveTo systematically evaluate the safety and adverse event profiles of immune checkpoint inhibitors (ICIs) in patients with esophageal cancer (EPC) or gastroesophageal junction cancer (GEJC).MethodsPubMed, Web of Science, Cochrane Library, and major conference proceedings were systematically searched for all phase II or phase III randomized controlled trials (RCTs) in EPC or GEJC using ICIs. Safety outcomes including treatment-related adverse events (trAEs), immune-related adverse events (irAEs), and serious trAEs were evaluated by network meta-analysis or dichotomous meta-analysis based on the random-effects model.ResultsEleven RCTs involving EPC (five RCTs) and GEJC (six RCTs) were included in the final meta-analysis. NMA showed that placebo was associated with the best safety ranking for grade 3–5 trAEs (SUCRA = 96.0%), followed by avelumab (78.6%), nivolumab (73.9%), ipilimumab (57.0%), and pembrolizumab (56.6%). Conventional pairwise meta-analysis (CPM) showed that ICIs have similar grade 3–5 trAE risk compared with chemotherapy (RR = 0.764, 95% CI: 0.574 to 1.016, I2 = 95.7%, Z = 1.85, P = 0.065). NMA showed that the general safety of grade 3–5 irAEs ranked from high to low is as follows: ChT (85.1%), placebo (76.5%), ipilimumab (56.0%), nivolumab (48.5%), avelumab (48.4%), camrelizumab (41.8%), pembrolizumab (36.4%), and nivolumab + ipilimumab (21.6%). CPM showed that the rates of grade 3–5 irAEs in the ICI group and the chemotherapy group were 7.35% (154/2,095, 95% CI: [6.23%, 8.47%]) versus 2.25% (42/1,869, 95% CI: [1.58%, 2.92%]), with statistical significance (RR = 3.151, 95% CI = 2.175 to 4.563, Z = 6.07, P = 0.000). The most common irAEs in the ICI group were skin reaction (15.76%, 95% CI: [13.67%, 17.84%]), followed by hypothyroidism (9.73%, 95% CI: [8.07%, 11.39%]), infusion-related reactions (5.93%, 95% CI: [4.29%, 7.58%]), hepatitis (5.25%, 95% CI: [4.28%, 6.22%]), and pneumonitis (4.45%, 95% CI: [3.5%, 5.4%]).ConclusionDifferent ICIs had different toxicity manifestations and should not be considered as an entity. Compared with chemotherapy, ICIs were more prone to irAEs, but the overall rates remained low and acceptable. For clinicians, it is important to recognize and monitor the adverse events caused by ICIs for patients with EPC or GEJC.</p

Schematic diagram of homologous recombination events between pBsLPNCB and CC-2654 mtDNA.

<p>The dotted line represents the deletion part of mtDNA in CC-2654 relative to wild-type CC-124. The empty boxes are the mitochondrial genes and the empty arrows above the genes indicate their transcription directions. The crossed solid lines denote the homologous recombination region between the CC-2654 mtDNA and expression vector pBsLPNCB.</p

Western blotting analysis of the transformants MT-B using monoclonal anti-BLE antibody.

<p>The soluble protein of CC-2654 (2) were used as control, the soluble protein of transformants MT-B (1) was detected by Western blotting.</p

The expression levels of the <i>Sh ble</i> gene and the mitochondrial genes in transgenic MT-B.

<p>A: The gene organization of MT-B mitochondrial genome: B: RT-PCR results of <i>Sh ble</i> gene and the mitochondrial genes with rrnL7 as internal control; C: Relative mRNA levels analysis using BIO-RAD image software.</p

Facile Route to Rare Heterobimetallic Aluminum–Copper and Aluminum–Zinc Selenide Clusters

Heterobimetallic aluminum–copper and aluminum–zinc clusters were prepared from the reaction of LAl­(SeH)₂ [<b>1</b>; L = HC­(CMeNAr)₂ and Ar = 2,6-<i>i</i>Pr₂C₆H₃] with (MesCu)₄ and ZnEt₂, respectively. The resulting clusters with the core structures of Al₂Se₄Cu₄ and Al₂Se₄Zn₃ exhibit unique metal–organic frameworks. This is a novel pathway for the synthesis of aluminum–copper and aluminum–zinc selenides. The products have been characterized by spectroscopic methods and single-crystal X-ray structural characterization

<i>Sh ble</i> gene transcripts in transformant MT-B.

<p>Panal A is the RT-PCR analysis of MT-B strains and PCR amplification with total RNA. M: DL2000 marker, Lane 1: cDNA of negative control CC-2654 used as template; 2–4: total RNA isolated from different MT-B strains used as template; lane 5–7: cDNA of different MT-B strains used as template. Panal B is the Northern blot analysis of <i>C. reinhardtii</i> MT-B. Lane 1, total RNA of MT-B was detected with <i>Sh ble</i> probe; lane 2. total RNA of CC-2654 was used as negative control.</p

Growth of transformants MT-Bs on the TAP media with 3 µg/mL Zeomycin (A) and PCR analysis with B1/B2 primers (B).

<p>M, DL2000 marker; lanes1-6, different clones of MT-B; lanes 7–8, negative controls CC-2654 and CC-124; lane 9, water used as negative control.</p

Sensitivity analysis of transgenic strains MT-Bs to Zeomycin.

<p>a: wild-type strain CC-124; b: respiratory deficient strain CC-2654; c: transgenic strain MT-B; d: empty control.</p