RESUMEN
Magnetic lanthanide (Ln) metal complexes exhibiting magnetic bistability can behave as molecular nanomagnets, also known as single-molecule magnets (SMMs), suitable for storing magnetic information at the molecular level, thus attracting extensive interest in the quest for high-density information storage and quantum information technologies. Upon encapsulating Ln ion(s) into fullerene cages, endohedral metallofullerenes (EMFs) have been proven as a promising and versatile platform to realize chemically robust SMMs, in which the magnetic properties are able to be readily tailored by altering the configurations of the encapsulated species and the host cages. In this review, we present critical discussions on the molecular structures and magnetic characterizations of EMF-SMMs, with the focus on their peculiar molecular and electronic structures and on the intriguing molecular magnetism arising from such structural uniqueness. In this context, different families of magnetic EMFs are summarized, including mononuclear EMF-SMMs wherein single-ion anisotropy is decisive, dinuclear clusterfullerenes whose magnetism is governed by intramolecular magnetic interaction, and radical-bridged dimetallic EMFs with high-spin ground states that arise from the strong ferromagnetic coupling. We then discuss how molecular assemblies of SMMs can be constructed, in a way that the original SMM behavior is either retained or altered in a controlled manner, thanks to the chemical robustness of EMFs. Finally, on the basis of understanding the structure-magnetic property correlation, we propose design strategies for high-performance EMF-SMMs by engineering ligand fields, electronic structures, magnetic interactions, and molecular vibrations that can couple to the spin states.
RESUMEN
We report here a new type of metal fluoride cluster that can be stabilized inside fullerene via in situ fluorine encapsulation followed by exohedral trifluoromethylation, giving rise to rare-earth metal fluoride clusterfullerenes (FCFs) M2F@C80(CF3) (M = Gd and Y). The molecular structure of Gd2F@C80(CF3) was unambiguously determined by single-crystal X-ray analysis to show a µ2-fluoride-bridged Gd-F-Gd cluster with short Gd-F bonds of 2.132(7) and 2.179(7) Å. The 19F NMR spectrum of the diamagnetic Y2F@C80(CF3) confirms the existence of the endohedral F atom, which exhibits a triplet with a large 19F-89Y coupling constant of 74 Hz and a high temperature sensitivity of the 19F chemical shift of 0.057 ppm/K. Theoretical studies reveal the ionic Y-F bonding nature arising from the highest electronegativity of the F element and an electronic configuration of [Y2F]5+@[C80]5- with an open-shell carbon cage, which thus necessitates the stabilization of FCFs by exohedral trifluoromethylation.
RESUMEN
Coupling two magnetic anisotropic lanthanide ions via a direct covalent bond is an effective way to realize high magnetization blocking temperature of single-molecule magnets (SMMs) by suppressing quantum tunneling of magnetization (QTM), whereas so far only single-electron lanthanide-lanthanide bonds with relatively large bond distances are stabilized in which coupling between lanthanide and the single electron dominates over weak direct 4f-4f coupling. Herein, we report for the first time synthesis of short Dy(II)-Dy(II) single bond (3.61 Å) confined inside a carbon cage in the form of an endohedral metallofullerene Dy2@C82. Such a direct Dy(II)-Dy(II) covalent bond renders a strong Dy-Dy antiferromagnetic coupling that effectively quenches QTM at zero magnetic field, thus opening up magnetic hysteresis up to 25 K using a field sweep rate of 25 Oe/s, concomitant with a high 100 s magnetization blocking temperature (TB,100s) of 27.2 K.
RESUMEN
Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interest in electronics due to their (semi)conducting properties. Charge-neutral 2D c-MOFs also possess persistent organic radicals that can be viewed as spin-concentrated arrays, affording new opportunities for spintronics. However, the strong π-interaction between neighboring layers of layer-stacked 2D c-MOFs annihilates active spin centers and significantly accelerates spin relaxation, severely limiting their potential as spin qubits. Herein, we report the precise tuning of the charge transport and spin dynamics in 2D c-MOFs via the control of interlayer stacking. The introduction of bulky side groups on the conjugated ligands enables a significant dislocation of the 2D c-MOFs layers from serrated stacking to staggered stacking, thereby spatially weakening the interlayer interactions. As a consequence, the electrical conductivity of 2D c-MOFs decreases by 6 orders of magnitude, while the spin density achieves more than a 30-fold increase and the spin-lattice relaxation time (T1) is increased up to â¼60 µs, hence being superior to the reference 2D c-MOFs with compact stackings whose spin relaxation is too fast to be detected. Spin dynamics results also reveal that spinless polaron pairs or bipolarons play critical roles in the charge transport of these 2D c-MOFs. Our strategy provides a bottom-up approach for enlarging spin dynamics in 2D c-MOFs, opening up pathways for developing MOF-based spintronics.
RESUMEN
PURPOSE: To develop a specific self-management scale applicable to patients with indwelling double-J tube in urolithiasis, and to test its reliability and validity. METHODS: The construction and validation of our scale involved three stages. First, an initial version of the questionnaire was formed through literature analysis, group discussions, semi-structured interviews, and the Delphi method. Second, a pre-survey was conducted with 20 urolithiasis patients with indwelling double-J stent placement to test their understanding of the initial questionnaire items and its acceptability. Finally, a formal survey of 234 patients with indwelling double-J tube for urolithiasis was conducted, and the scale was tested for reliability and validity. RESULTS: After the three stages, a specific self-management scale for urolithiasis patients with indwelling double-J tube was developed, consisting of 30 items across five dimensions with a cumulative contribution rate of 52.541%. The content validity index for item level ranged from 0.8 to 1, and the content validity index for the questionnaire level was 0.93. The correlation between each item and its dimension was > 0.4. The Cronbach's alpha coefficient for the overall questionnaire was 0.910, and the Cronbach's alpha coefficients for each dimension ranged from 0.672 to 0.865. The split-half reliability of the overall questionnaire was 0.864, and the split-half reliabilities for each dimension ranged from 0.659 to 0.827. The test-retest reliability of the overall questionnaire was 0.840, and the test-retest reliabilities for each dimension ranged from 0.674 to 0.818. CONCLUSION: The specific self-management scale for urolithiasis patients with indwelling double-J tube has good reliability and validity, and it is a reliable and effective tool for evaluating and assessing the self-management level of patients with indwelling double-J tube in urolithiasis.
Asunto(s)
Automanejo , Urolitiasis , Humanos , Reproducibilidad de los Resultados , Urolitiasis/terapia , Pacientes , StentsRESUMEN
Identification of unique and specific biomarkers to better detect and quantify senescent cells remains challenging. By a global proteomic profiling of senescent human skin BJ fibroblasts induced by ionizing radiation (IR), the cellular level of pregnancy zone protein (PZP), a presumable pan-protease inhibitor never been linked to cellular senescence before, was found to be decreased by more than 10-fold, while the level of PZP in the conditioned medium was increased concomitantly. This observation was confirmed in a variety of senescent cells induced by IR or DNA-damaging drugs, indicating that high-level secretion of PZP is a novel senescence-associated secretory phenotype. RT-PCR examination verified that the transcription of the PZP gene is enhanced in various cells at senescence or upregulated following DNA damage treatment in a p53-independent manner. Moreover, pretreatment with late pregnancy serum containing a high level of PZP led to inhibition of doxorubicin-induced senescence in A549 cells, and depletion of PZP in the pregnancy serum could enhance such inhibition. Finally, the addition of immuno-precipitated PZP complexes into tissue culture attenuated the growth of A549 cells and promoted the spontaneous senescence. Therefore, we revealed that high-level secretion of PZP is a novel and unique feature associated with DNA damage-induced senescence, and secreted PZP is a positive regulator of cellular senescence, particularly during the late stage of gestation.
Asunto(s)
Senescencia Celular , Daño del ADN , Proteínas Gestacionales , Humanos , Biomarcadores/metabolismo , Senescencia Celular/genética , Proteómica , Piel/metabolismo , Proteínas Gestacionales/metabolismo , Fibroblastos , Células A549RESUMEN
Metal complexes bearing single-electron metal-metal bonds (SEMBs) exhibit unusual electronic structures evoking strong magnetic coupling, and such bonds can be stabilized in the form of dimetallofullerenes (di-EMFs) in which two metals are confined in a carbon cage. Up to now, only a few di-EMFs containing SEMBs are reported, which are all based on a high-symmetry icosahedral (Ih) C80 cage embedding homonuclear rare-earth bimetals, and a chemical modification of the Ih-C80 cage is required to stabilize the SEMB. Herein, by introducing 3d-block transition metal titanium (Ti) along with 4f-block lanthanum (La) into the carbon cage, we synthesized the first crystallographically characterized SEMB-containing 3d-4f heteronuclear di-EMFs based on pristine fullerene cages. Four novel La-Ti heteronuclear di-EMFs were isolated, namely, LaTi@D3h(5)-C78, LaTi@Ih(7)-C80, LaTi@D5h(6)-C80, and LaTi@C2v(9)-C82, and their molecular structures were unambiguously determined by single-crystal X-ray diffraction. Upon increasing the cage size from C78 to C82, the La-Ti distance decreases from 4.31 to 3.97 Å, affording fine-tuning of the metal-metal bonding and hyperfine coupling, as evidenced by an electron spin resonance (ESR) spectroscopic study. Density functional theory (DFT) calculations confirm the existence of SEMB in all four LaTi@C2n di-EMFs, and the accumulation of electron density between La and Ti atoms shifts gradually from the proximity of the Ti atom inside C78 to the center of the LaTi bimetal inside C82 due to the decrease of the La-Ti distance. The electronic properties of LaTi@C2n heteronuclear dimetallofullerenes differ apparently from their homonuclear La2@C2n counterparts, revealing the peculiarity of heteronuclear dimetallofullerenes with the involvement of 3d-block transition metal Ti.
RESUMEN
Vortex beams have attracted much attention due to their unique rotational Doppler effect. With the in-depth study of vortex beams, many new vortex beams have been proposed gradually, while the detection of fluid motion is of great significance for the study of ocean turbulence. Based on the rotational Doppler effect of the grafted perfect vortex beam, we propose a non-embedded optical method for real-time detection of the magnitude and direction of fluid velocity and establish a two-dimensional fluid model for simulation verification. It is proved that the grafted perfect vortex beam can detect the magnitude and direction of the fluid velocity at the same time, which may provide a new way and theoretical support for the detection of fluid motion direction.
RESUMEN
OBJECTIVE: Depression is one of the most common complications in patients with diabetes. Our previous study demonstrated puerarin, a dietary isoflavone, improved glucose homeostasis and ß-cell regeneration in high-fat diet (HFD)-induced diabetic mice. Here, we aim to evaluate the potential effect of puerarin on diabetes-induced depression. METHODS: The co-occurrence of diabetes and depression with related biochemical alterations were confirmed in HFD mice and db/db mice, respectively using behavioral analysis, ELISA and western blotting assay. Furthermore, impacts of puerarin on depression-related symptoms and pathological changes were investigated in HFD mice. RESULTS: The results showed that puerarin effectively alleviated the depression-like behaviors of HFD mice, down-regulated serum levels of corticosterone and IL-1ß, while up-regulated the content of 5-hydroxytryptamine. Simultaneously, puerarin increased the number of hippocampal neurons in HFD mice, and suppressed the apoptosis of neurons to protect the hippocampal neuroplasticity. GLP-1R expression in hippocampus of HFD mice was enhanced by puerarin, which subsequently activated AMPK, CREB and BDNF/TrkB signaling to improve neuroplasticity. Importantly, our data indicated that puerarin had an advantage over fluoxetine or metformin in treating diabetes-induced depression. CONCLUSION: Taken together, puerarin exerts anti-depressant-like effects on HFD diabetic mice, specifically by improving hippocampal neuroplasticity via GLP-1R/BDNF/TrkB signaling. Puerarin as a dietary supplement might be a potential candidate in intervention of diabetes with comorbid depression.
Asunto(s)
Diabetes Mellitus Experimental , Isoflavonas , Ratones , Animales , Factor Neurotrófico Derivado del Encéfalo/metabolismo , Diabetes Mellitus Experimental/complicaciones , Diabetes Mellitus Experimental/tratamiento farmacológico , Diabetes Mellitus Experimental/metabolismo , Dieta Alta en Grasa/efectos adversos , Depresión/etiología , Depresión/inducido químicamente , Isoflavonas/farmacología , Hipocampo/metabolismoRESUMEN
Herein, we report divergent additions of 2,2'-diazidobiphenyls to C60 and Sc3 N@Ih -C80 . In stark contrast to that of the previously reported bis-azide additions, the unexpected cascade reaction leads to the dearomative formation of azafulleroids 2 fused with a 7-6-5-membered ring system in the case of C60 . In contrast, the corresponding reaction with Sc3 N@Ih -C80 switches to the C-H insertion pathway, thereby resulting in multiple isomers, including a carbazole-derived [6,6]-azametallofulleroid 3 and a [5,6]-azametallofulleroid 4 and an unusual 1,2,3,6-tetrahydropyrrolo[3,2-c]carbazole-derived metallofullerene 5, whose molecular structures have been unambiguously determined by single-crystal X-ray diffraction analyses. Among them, the addition type of 5 is observed for the first time in all reported additions of azides to fullerenes. Furthermore, unexpected isomerizations from 3 to 5 and from 4 to 5 have been discovered, providing the first examples of the isomerization of an azafulleroid to a carbazole-derived fullerene rather than an aziridinofullerene. In particular, the isomerism of the [5,6]-isomer 4 to the [5,6]-isomer 5 is unprecedented in fullerene chemistry, contradicting the present understanding that isomerization generally occurs between [5,6]- and [6,6]-isomers. Control experiments have been carried out to rationalize the reaction mechanism. Furthermore, representative azafulleroids have been applied in organic solar cells, thereby resulting in improved power conversion efficiencies.
RESUMEN
To design molecular spin qubits with enhanced quantum coherence, a control of the coupling between the local vibrations and the spin states is crucial, which could be realized in principle by engineering molecular structures via coordination chemistry. To this end, understanding the underlying structural factors that govern the spin relaxation is a central topic. Here, we report the investigation of the spin dynamics in a series of chemically designed europium(II)-based endohedral metallofullerenes (EMFs). By introducing a unique structural difference, i. e. metal-cage binding site, while keeping other molecular parameters constant between different complexes, these manifest the key role of the three low-energy metal-displacing vibrations in mediating the spin-lattice relaxation times (T1 ). The temperature dependence of T1 can thus be normalized by the frequencies of these low energy vibrations to show an unprecedentedly universal behavior for EMFs in frozen CS2 solution. Our theoretical analysis indicates that this structural difference determines not only the vibrational rigidity but also spin-vibration coupling in these EMF-based qubit candidates.
RESUMEN
A concise and effective ruthenium-catalyzed asymmetric transfer hydrogenation of ß-substituted α-oxobutyrolactones has been developed, delivering a series of cis-ß-substituted α-hydroxybutyrolactone derivatives with excellent yields, enantioselectivities, and diastereoselectivities. Two consecutive stereogenic centers were constructed in one step through dynamic kinetic resolution under basic conditions. The reaction could be conducted on a gram scale without loss of activity and enantioselectivity. The reductive products could be easily transformed into useful building blocks.
RESUMEN
Embedding coherent spin motifs in reproducible molecular building blocks is a promising pathway for the realization of quantum technologies. Three-dimensional (3D) MOFs are a versatile platform for the rational design of extended structures employing coordination chemistry. Here, we report the synthesis and characterization of a gadolinium(III)-based MOF, [Gd(bipyNO)4](TfO)3·xMeOH (bipyNO = bipyridine,N,N'-dioxide; TfO = triflate; and MeOH = methanol) (quMOF-1), which presents a unique coordination geometry that leads to a tiny magnetic anisotropy (in terms of D, an equivalent zero-field splitting would be achieved by D = 0.006 cm-1) even compared with regular Gd(III) complexes. Pulsed electron paramagnetic resonance experiments on its magnetically diluted samples confirm the preservation of quantum coherence of single Gd(III) qubit units in this 3D extended molecular architecture (T2 = 612 ns and T1 = 66 µs at 3.5 K), which allows for the detection of Rabi oscillations at 40 K.
RESUMEN
At present, saccharides as hydrophilic matrixes, have been gradually used in amorphous solid dispersions (ASD) for dispersing poorly water-soluble drugs without surfactants. In this study, an amorphous chitosan oligosaccharide (COS) was applied as a water-soluble matrix to form surfactant-free ASD via the ball milling to vitrify quercetin (QUE) and enhance the dissolution and bioavailability. Solid-state characterization (DSC, XRPD, FTIR, SEM and PLM) and physical stability assessments verified that the prepared ASDs showed excellent physical stability with complete amorphization due to potential interactions between QUE and COS. In vitro sink dissolution tests suggested all QUE-COS ASDs (w:w, 1:1, 1:2 and 1:4) significantly enhanced the dissolution rate of QUE. Meanwhile, in vitro non-sink dissolution exhibited that the maximum supersaturated concentration ranged from 112.62 to 138.00 µg/mL for all QUE-COS ASDs, which was much higher than that of pure QUE. Besides, the supersaturation of QUE-COS ASD kept for at least 24 h. In rat pharmacokinetics, the oral bioavailability of QUE-COS ASDs showed 1.64 â¼ 2.25 times increase compared to the pure QUE (p < .01). Hence, the present study confirms the amorphous COS could be applied as a promising hydrophilic matrix in QUE-COS ASDs for enhancing dissolution performance and bioavailability of QUE.
Asunto(s)
Quercetina , Tensoactivos , Animales , Disponibilidad Biológica , Interacciones Hidrofóbicas e Hidrofílicas , Ratas , SolubilidadRESUMEN
An anisotropic high-spin qubit with long coherence time could scale the quantum system up. It has been proposed that Grover's algorithm can be implemented in such systems. Dimetallic aza[80]fullerenes M2@C79N (M = Y or Gd) possess an unpaired electron located between two metal ions, offering an opportunity to manipulate spin(s) protected in the cage for quantum information processing. Herein, we report the crystallographic determination of Gd2@C79N for the first time. This molecular magnet with a collective high-spin ground state (S = 15/2) generated by strong magnetic coupling (JGd-Rad = 350 ± 20 cm-1) has been unambiguously validated by magnetic susceptibility experiments. Gd2@C79N has quantum coherence and diverse Rabi cycles, allowing arbitrary superposition state manipulation between each adjacent level. The phase memory time reaches 5 µs at 5 K by dynamic decoupling. This molecule fulfills the requirements of Grover's searching algorithm proposed by Leuenberger and Loss.
RESUMEN
Two Sm@C82 isomers have been well characterized for the first time by means of (13)C NMR spectroscopy, and their structures were unambiguously determined as Sm@C2v(9)-C82 and Sm@C3v(7)-C82, respectively. A combined study of single crystal X-ray diffraction and theoretical calculations suggest that in Sm@C2v(9)-C82 the preferred Sm(2+) ion position shall be located in a region slightly off the C2 axis of C2v(9)-C82. Moreover, the electrochemical surveys on these Sm@C82 isomers reveal that their redox activities are mainly determined by the properties of their carbon cages.
RESUMEN
Although a non-IPR fullerene cage is common for endohedral cluster fullerenes, it is very rare for conventional endofullerenes M@C2n, probably because of the minimum geometry fit effect of the endohedral single metal ion. In this work, we report on a new non-IPR endofullerene Sm@C2v(19138)-C76, including its structural and electrochemical features. A combined study of single-crystal X-ray diffraction and DFT calculations not only elucidates the non-IPR cage structure of C2v(19138)-C76 but also suggests that the endohedral Sm(2+) ion prefers to reside along the C2 cage axis and close to the fused pentagon unit in the cage framework, indicative of a significant metal-cage interaction, which alone can stabilize the non-IPR cage. Furthermore, electrochemical studies reveal the fully reversible redox behaviors and small electrochemical gap of Sm@C2v(19138)-C76, which are comparable to those of IPR species Sm@D3h-C74.
Asunto(s)
Fulerenos/química , Níquel/química , Cationes Bivalentes , Cristalografía por Rayos X , Técnicas Electroquímicas , Isomerismo , Estructura Molecular , Oxidación-Reducción , Teoría CuánticaRESUMEN
OBJECTIVE: Fear of cancer recurrence is one of the psychological distresses for patients with cancer and cancer survivors, which poses a physical and psychological threat. There is scant evidence on the effectiveness of cognitive-behavioural therapy in reducing fear of cancer recurrence. Therefore, we conducted a systematic review and meta-analysis to assess the effectiveness of cognitive-behavioural therapy for fear of cancer recurrence. METHOD: The review was reported according to Preferred Reporting Items for Systematic Review and Meta-analyses statement. Seven databases were systematically searched from inception to 31 March 2023. Randomised controlled trials implementing cognitive-behavioural therapy interventions and studies reporting fear of cancer recurrence were included. The methodological quality of included studies was assessed using the Cochrane Risk of Bias Tool 2. RESULTS: A total of 32 randomised controlled trials involving 1515 cancer survivors and 1845 patients with cancer undergoing treatment were included. The meta-analysis indicated a significant effect of cognitive-behavioural therapy on fear of cancer recurrence in patients with cancer and cancer survivors compared with controls (g=-0.65; 95% CI=-0.86, -0.44; p<0.001). The results of the overall risk of bias indicated some concerns in 4 studies and a high risk in 28 studies. CONCLUSION: The study indicated the effectiveness of cognitive-behavioural therapy intervention for fear of cancer recurrence in patients with cancer and cancer survivors, which should inform future clinical practice of interventions for the treatment of fear of cancer recurrence. PROSPERO REGISTRATION NUMBER: CRD42023404948.
RESUMEN
BACKGROUND: Fear of cancer recurrence is one of the psychological distresses that seriously affects the quality of life of breast cancer patients. However, the evidence for cognitive behavioral therapy on fear of cancer recurrence in breast cancer is limited. OBJECTIVE: The aim of this study was to evaluate the effectiveness of cognitive behavioral therapy in reducing breast cancer patients' fear of cancer recurrence. METHODS: Seven databases were searched for randomized controlled studies on cognitive behavioral therapy for fear of cancer recurrence in cancer patients from the inception of the database to April 30, 2023, with no language restrictions. Meta-analysis was performed using Stata MP 17. The Cochrane Risk of Bias Tool version 2 was used to assess the quality of the included studies. The quality of evidence was assessed using the Grading of Recommendations, Assessment, Development and Evaluation method. RESULTS: This review includes a total of 13 randomized controlled trials with 1447 breast cancer patients and survivors. When compared with controls, meta-analysis revealed that cognitive behavioral therapy significantly reduced the fear of cancer recurrence (g = -0.44; 95% confidence interval, -0.75 to -0.13; P < .001), whereas subgroup analysis revealed that only mindfulness-based cognitive therapy was significant. The overall risk of bias was high. The Grading of Recommendations, Assessment, Development and Evaluation assessment showed a low overall quality of evidence. CONCLUSIONS: Cognitive behavioral therapy may be effective in reducing fear of cancer recurrence in breast cancer patients, and mindfulness-based cognitive therapy is particularly worthy of implementation. IMPLICATIONS FOR PRACTICE: Mindfulness-based cognitive therapy may be used as an additional strategy to help manage breast cancer patients' fears of cancer recurrence.
RESUMEN
BACKGROUND: Malnutrition is associated with clinical outcomes in several diseases. However, the role of malnutrition in the risk of delirium in elderly patients in intensive care units (ICU) remains unclear. This study aimed to elucidate the association between the Geriatric Nutritional Risk Index (GNRI) and the risk of delirium in elderly patients in the ICU. METHODS: Elderly patients from the Medical Information Mart for Intensive Care IV (MIMIC-IV) and the eICU Collaborative Research Database (eICU-CRD) were included in this study, totaling 11,310 and 5,627, respectively. All subjects were stratified according to their GNRI score: those with no nutritional risk (GNRI > 98), mild nutritional risk (92 ≤ GNRI ≤ 98), moderate nutritional risk (82 ≤ GNRI ≤ 92), and severe nutritional risk (GNRI < 82). The primary outcome was delirium. RESULTS: The GNRI in MIMIC-IV and eICU-CRD were 93.82 (84.88, 101.26) and 83.39 (75.95, 89.35), respectively. Compared to the cohort without nutritional risk, there was an increased risk of delirium in patients with mild nutritional risk (OR: 1.39, 95 % CI: 1.23-1.58), moderate nutritional risk (OR: 1.72, 95 % CI: 1.52-1.95), and severe nutritional risk (OR: 2.07, 95 % CI: 1.79-2.39). Inclusion of the GNRI score in the multivariate models improved the prediction of delirium. Similar results were found in the eICU-CRD database. CONCLUSIONS: Nutritional assessment using the GNRI may be an independent predictor of the development of delirium in elderly patients in the ICU. The addition of the GNRI score to the delirium prediction model improves its predictive accuracy.