The intermarriage of neutral and tripodal imidazole ligand, tris(4‐(1H‐imidazol‐1‐yl)phenyl)amine (TIPA), with zinc phosphite yields two hybrid phosphites, Zn2(HPO3)2(TIPA)⋅2 H2O (1) and ...Zn3(HPO3)3(TIPA)⋅6 H2O (2). Compound 1 has a hybrid sheet with neutral zinc‐phosphite chains as supramolecular building blocks (SBBs), whereas 2 exhibits a 3D hybrid architecture with other neutral zincophosphite chains as supramolecular building blocks. The structural discrepancy between 1 and 2 is mainly due to the distinct linkage modes between organic TIPA ligands and inorganic zincophosphite chains. Interestingly, compounds 1 and 2 feature fast photochromism in response to UV light irradiation under ambient conditions. The discrepancy of photochromic performance between 1 and 2 is mainly due to the different geometrical configuration of the TIPA ligand. Different to majority of reported hybrid photochromic compounds driven by photochromic active units, the photochromism in 1 and 2 is derived from the electron transfer (ET) between phosphite and non‐photochromic triimidazole‐derivative ligand TIPA. Compared with the widely explored nonphotochromic polypyridine‐derivative as electron acceptors (EAs), our work provides a new EA model for the design of hybrid photochromic materials based on the ligand‐to‐ligand ET mechanism. A multiple anti‐counterfeiting application based on 1 and 2 was investigated.
A new electron‐acceptor: We provide a new category of electron acceptors (EAs), the tri(imidazole)‐derivative moiety, for the design of crystalline hybrid photochromic materials. The new unit differs clearly from other broadly investigated photoactive units and that are being explored as EAs for nonphotoactive polypyridine‐derivative units.
The photogeneration of stable radicals is important but still challenging in the field of optical switching, displays, and other devices. Herein, crystalline 9-anthracene carboxylic acid (
9-AC
) and ...a mononuclear complex constructed from this ligand were for the first time discovered to show radical-induced photochromism and photomagnetism after Xe lamp light irradiation. This study finds a simple radical-actuated photochromic molecule for constructing a novel system of photochromic materials.
The crystalline 9-anthracene carboxylic acid and the constructed mononuclear complex were for the first time discovered to show radical-induced photochromism and photomagnetism after Xe lamp light irradiation.
Abstract
Background
Dysphagia prevalence in the acute setting is 30%. Managing dysphagia can reduce mortality, length of stay and increase overall quality of life. Use of thickener for patients with ...dysphagia should be the last alternative. However, in the acute setting due the patient’s respiratory or cognitive status, thickener use is required to manage the risk of aspiration and ensure patients improve clinically. The goal is for discharge prescriptions to contain all the necessary information for patients. The aim of this audit is to investigate the rate of prescription of thickener on patient’s discharge.
Methods
Two retrospective chart audits of discharge prescriptions were completed (December 2022 and May 2023); pre and post implementation of a new communication strategy for thickener being prescribed. All patients discharged from hospital on thickened fluids were included as identified via Speech and Language Therapy database. The audit investigated the rate of thickener on discharge prescription and documentation in the Kardex.
Results
Initial audit was completed in December 2022. 20 patients were included. 0% of patients had thickener prescribed on discharge with no (0%) documentation in the Kardex. Re-audit was completed in May 2023, following the implementation of a new communication strategy involving SLTs place a sticker on the Kardex, included 13 patients 77% (10 patients) had thickener prescribed on discharge with the same number (77%; 10 patients) having documentation in the Kardex.
Conclusion
Improved communication between healthcare professionals results in better patient outcomes and reduces the risk of re-admission. The use of instrumental assessment has enabled SLTs to truly identify those who require thickener, particularly during an acute admission. The SLT department is striving to reduce the use of thickener for patients, however, in those who do require this management option, it is imperative that it is included on their discharge prescription.
Prior studies have demonstrated that correlated variability changes with cognitive processes that improve perceptual performance. We tested whether correlated variability covaries with subjects' ...performance-whether performance improves quickly with attention or slowly with perceptual learning. We found a single, consistent relationship between correlated variability and behavioral performance, regardless of the time frame of correlated variability change. This correlated variability was oriented along the dimensions in population space used by the animal on a trial-by-trial basis to make decisions. That subjects' choices were predicted by specific dimensions that were aligned with the correlated variability axis clarifies long-standing paradoxes about the relationship between shared variability and behavior.
Luminescent metal clusters have attracted great interest in current research; however, the design synthesis of Al clusters with color‐tunable luminescence remains challenging. Herein, an ...Al8(OH)8(NA)16 (Al8, HNA = nicotinic acid) molecular cluster with dual luminescence properties of fluorescence and room‐temperature phosphorescence (RTP) is synthesized by choosing HNA ligand as phosphor. Its prompt photoluminescence (PL) spectrum exhibits approximately white light emission at room temperature. Considering that halogen atoms can be used to regulate the RTP property by balancing the singlet and triplet excitons, different CdX2 (X− = Cl−, Br−, I−) are introduced into the reactive system of the Al8 cluster, and three new Al8 cluster‐based metal‐organic frameworks, {Al8Cd3Cl5(OH)8(NA)17H2O·2HNA}n (CdCl2‐Al8), {Al8Cd4Br7(OH)8(NA)16CH3CN·NA·HNA}n (CdBr2‐Al8) and {Al8Cd8I16(OH)8(NA)16}n (CdI2‐Al8) are successfully obtained. They realize the color tunability from blue to yellow at room temperature. The origination of fluorescence and phosphorescence has also been illustrated by structure‐property analysis and theoretical calculation. This work provides new insights into the design of multicolor luminescent metal cluster‐based materials and develops advanced photo‐functional materials for multicolor display, anti‐counterfeiting, and encryption applications.
By fixing a phosphor of nicotinic acid into crystalline state, an Al8 cluster with dual luminescent properties of fluorescence and room‐temperature phosphorescence (RTP) is obtained. Introducing CdX2 into the reactive system of the Al8 cluster to regulate RTP by balancing the singlet and triplet excitons, three heterometallic Al8‐based metal‐organic frameworks are obtained. They realize the luminescent color tunability from blue to yellow.
Programmed cell death protein-1 (PD-1) blockade therapies have demonstrated durable responses and prolonged survival in a variety of malignancies. Treatment is generally well tolerated although ...immune-related adverse events (irAEs) can occur. Autoimmune thyroid dysfunction is among the most common irAE, but an assessment of the clinical, mechanistic, and immunologic features has not been previously described.
Patients with advanced non-small-cell lung cancer (NSCLC) treated with pembrolizumab at Memorial Sloan Kettering Cancer Center (n=51) as part of KEYNOTE-001 (NCT01295827) were included. Thyroid function test and anti-thyroid antibodies were assessed prospectively at each study visit, beginning before the first treatment. Frequency of development of thyroid dysfunction, association with anti-thyroid antibodies, clinical course, and relationship with progression-free survival and overall survival to treatment with pembrolizumab was evaluated.
Of 51 patients treated, 3 were hypothyroid and 48 were not at baseline. Ten of 48 21%, 95% confidence interval (CI) 10% to 35% patients developed thyroid dysfunction requiring thyroid replacement. Anti-thyroid antibodies were present in 8 of 10 patients who developed thyroid dysfunction, compared with 3 of 38 who did not (80% versus 8%,P<0.0001). Thyroid dysfunction occurred early (median, 42 days) in the pembrolizumab course, and a majority (6 of 10 patients) experienced brief, transient hyperthyroidism preceding the onset of hypothyroidism; no persistent hyperthyroidism occurred. Both hyperthyroidism and hypothyroidism were largely asymptomatic. Overall survival with pembrolizumab was significantly longer in subjects who developed thyroid dysfunction (hazard ratio, 0.29; 95% CI 0.09–0.94;P = 0.04).
Thyroid dysfunction during pembrolizumab treatment of NSCLC is common and is characterized by early-onset, frequently preceded by transient hyperthyroidism, closely associated with anti-thyroid antibodies, and may be associated with improved outcomes. The presence of antibody-mediated toxicity in T-cell-directed therapy suggests an under-recognized impact of PD-1 biology in modulating humoral immunity.
A hybrid mathematical model has been developed in which the flow field of a viscous incompressible medium is calculated by the method of lattice Boltzmann equations using the Bhatnagar–Gross–Krook ...approximation and a two-dimensional nine-velocity scheme, and free convective heat transfer is calculated by the finite difference method. The formulated approach to solving thermogravitational-convection problems has been verified on numerical and experimental data of other researchers. From a comparative analysis, it has been established that the computational efficiency of the hybrid mathematical model is 50 times higher than that of the traditional approach, which is based on the finite difference method and transformed "vorticity–stream function" variables.
Hybrid photochromic materias (HPMs), especially crystalline HPMs (CHPMs), have been widely investigated due to their feasibility in maintaining the advantages of each constituent and genearating ...captivating photomodulated functionality. Metal-organic complexes (MOCs), as promising candidates for fabricating CHPMs, have attracted the interest of researchers. The molecular predesign of ligands plays a crucial role in yielding MOC-based CHPMs with tunable photochromic functionality. Hitherto, a great majority of CHPMs are driven by photosensitive ligands. However, the complicated synthesis and high cost of photosensitive ligands obviously prevent the macro-synthesis and future application of these CHPMs. Thus, it is indispensable to explore novel branches of CHPMs. Herein, we report a series of photochromic solid materials bearing modulated photochromic properties by hybridizing metal chlorides with a nonphotosensitive coplanar dipyridine unit 1,10-phenanthroline (phen) and its derivative 5-chloro-1,10-phenanthroline (5-Cl-phen). The resulting hybrids, ZnCl
2
(phen) (
1
), CdCl
2
(phen) (
2
), PbCl
2
(phen) (
3
), ZnCl(H
2
O)(5-Cl-phen)
2
Cl·2H
2
O (
4
), Cd
2
Cl
4
(5-Cl-phen)
2
(
5
) and Pb
2
Cl
4
(5-Cl-phen)
2
(
6
), exhibit distinct structures from the isolated molecular complexes (
1
and
4
) to the hybrid chain (
2
,
3
,
5
and
6
) because of the distinct coordination mode of central metal ions and chloride ions. After photo-irradiation with a Xe-lamp, all complexes, as expected, exhibited apparent color change because of the photoinduced electron transfer (ET) between coordinated chloride ions (Cl
−
) as electron donors (EDs) and the coordinated coplanar phen and 5-Cl-phen species as electron acceptors (EAs). More importantly, the photochromic performance of the title complexes could be modulated by phen and 5-Cl-phen. This study provides a general and facile way for modulating the structure and photochromic performance of hybrid metal chlorides with phen or phen-based derivatives under the synergy of crystalline engineering strategy and ET mechanism.
We provide a general method for modulating the structure and photochromic performance of hybrid metal chlorides with 1,10-phenanthroline and its substituted derivative under the synergy of electron transfer and coordination assembly strategies.
MET exon 14 alterations are actionable oncogenic drivers. Durable responses to MET inhibitors are observed in patients with advanced MET exon 14-altered lung cancers in prospective trials. In ...contrast, the activity of immunotherapy, PD-L1 expression and tumor mutational burden (TMB) of these tumors and are not well characterized.
Patients with MET exon 14-altered lung cancers of any stage treated at two academic institutions were identified. A review of clinicopathologic and molecular features, and an analysis of response to single-agent or combination immune checkpoint inhibition were conducted. PD-L1 immunohistochemistry was carried out and TMB was calculated by estimation from targeted next-generation sequencing panels.
We identified 147 patients with MET exon 14-altered lung cancers. PD-L1 expression of 0%, 1%–49%, and ≥50% were 37%, 22%, and 41%, respectively, in 111 evaluable tumor samples. The median TMB of MET exon 14-altered lung cancers was lower than that of unselected non-small-cell lung cancers (NSCLCs) in both independently evaluated cohorts: 3.8 versus 5.7 mutations/megabase (P<0.001, n=78 versus 1769, cohort A), and 7.3 versus 11.8 mutations/megabase (P<0.001, n=62 versus 1100, cohort B). There was no association between PD-L1 expression and TMB (Spearman’s rho=0.18, P=0.069). In response-evaluable patients (n=24), the objective response rate was 17% (95% CI 6% to 36%) and the median progression-free survival was 1.9months (95% CI 1.7–2.7). Responses were not enriched in tumors with PD-L1 expression ≥50% nor high TMB.
A substantial proportion of MET exon 14-altered lung cancers express PD-L1, but the median TMB is lower compared with unselected NSCLCs. Occasional responses to PD-1 blockade can be achieved, but overall clinical efficacy is modest.