Regulating and controlling the stepwise ESDPT channel of BP(OH)2DCEt2 using the strategy of solvent polarity and external electric field.

Excited state double proton transfer (ESDPT) has attracted great scientific interest because of its excellent luminescent properties. However, the complex process of ESDPT has plagued theoretical and experimental scientists for a long time and has become a hot issue. In this work, the ESDPT process of 2,2'-bipyridine-3,3'-diol-5,5'-dicarboxylic acid ethyl ester (BP(OH)2DCEt2) is systematically studied and the regulation of the ESDPT process is further realized. The potential energy curves indicate that BP(OH)2DCEt2 shows the characteristics of stepwise ESDPT in different polar solvents. The increase in solvent polarity will be beneficial to the stepwise ESDPT reaction. Regrettably, it is not possible to distinguish the specific stepwise transfer path of the BP(OH)2DCEt2 molecule due to the symmetry of the potential energy surface along the diagonal. On this basis, we proposed a method to control and regulate the stepwise ESDPT path using an external electric field. The results show that the increase of external electric field intensity is favorable to stepwise ESDPT. It is interesting to note that applying an external electric field in a specific direction will effectively distinguish stepwise ESDPT reaction paths. Therefore, this work not only helps to understand the mechanism of ESDPT, but also contributes to regulation and design of new luminescent materials with excellent luminescent properties.

Acute Necrotizing Pancreatitis Complicated With Sinistral Portal Hypertension And Mechanical Obstruction Of The Colon: A Case Report.

Acute necrotizing pancreatitis (ANP) is often associated with acute necrotic collection (ANC) or walled-off necrosis (WON). Due to the close anatomical connection between the pancreas, the spleen, and the transverse colon, necrotizing pancreatitis is often combined with spleen or colon involvement. Gastrointestinal dysfunction usually caused by pancreatitis leads to paralytic intestinal obstruction. However, pancreatitis combined with mechanical colonic obstruction is extremely rare. It can easily be misdiagnosed as malignant intestinal obstruction, and diagnosing the cause of intestinal obstruction becomes more critical when accompanied by Sinistral portal hypertension (SPH). Surgical resection is the primary method for the previous occurrence of colonic complications. In this case report, upon admission, a 37-year-old patient was diagnosed with acute necrotizing pancreatitis with sinistral portal hypertension. On the 6th day after admission, the patient developed a sudden colonic obstruction. After identifying the cause, the patient underwent a transanal decompression tube and minimally invasive necrosectomy, avoiding colon resection. In acute necrotizing pancreatitis combined with colonic mechanical obstruction, it is essential to clarify the etiology, and focus treatment on clearing the peripancreatic necrotic tissue, non-surgical treatment to deal with colonic obstruction is feasible, and the principle of individualized treatment should be used throughout the disease.

Effects of Twisted Intramolecular Charge Transfer Behavior on Excited-State Intramolecular Proton Transfer Reactions of Methyl Benzoate Derivatives in Water Solution.

Many methyl benzoate derivatives were found to show intramolecular charge transfer (ICT), intramolecular proton transfer, and other properties, which have extensive applications in lasing media, metal ion sensors, active materials, and fluorescence probe fields. However, the intrinsic relationship and reaction mechanism between the excited-state intramolecular proton transfer (ESIPT) and ICT between methyl benzoate derivatives with different substituents have not been explained. In this paper, the density functional theory and time-dependent density functional theory methods were used to study the ESIPT and ICT behaviors of p-aminosalicylic acid methyl ester and p-dimethylaminosalicylic acid methyl ester in water and obtain the intrinsic interaction between the two behaviors. The bond parameters, infrared spectra, reduced density gradient scatter plots, and topological analyses of these two molecules in the ground state and excited state were analyzed to confirm the enhancement of the excited-state intramolecular hydrogen bonds (IHBs). The simulated absorption and fluorescence spectra of these molecules agreed well with the experimental values. Based on the optimized structure, we also plotted the natural transition orbitals, electron density difference maps, and frontier molecular orbitals (FMOs), which showed the changes of the charge distribution of these molecules intuitively upon photoexcitation. In addition, we also found that the degree of IHB enhancement with -N(CH3)2 substituents was less than that with -NH2, reflecting an inhibition effect of twisted intramolecular charge transfer (TICT) on ESIPT reaction. This conclusion was confirmed by our calculated potential energy curves. This work may better deepen the comprehension of the intrinsic relationship between ESIPT and TICT behavior and sequentially provide better theoretical guidance for the synthesis of fluorescent molecules related to these two behaviors.

Substituent Effects on Excited-State Intramolecular Proton Transfer Reaction of 2-Aryloxazoline Derivatives.

Different substituents and benzene ring numbers had significant effects on the fluorescence phenomenon of 2-aryloxazoline derivatives as observed in an experiment. Here, we select five 2-aryloxazoline derivatives with different substituents and benzene ring numbers (2u, 2ad, 2af, 2ai, and 2ah) to analyze the effects on the fluorescence phenomena. For 2ad, 2ah, and 2ai, first, the geometric structures are optimized based on the density functional theory and time-dependent density functional theory methods. The analysis of the obtained bond parameters reveals the variation of hydrogen bond interactions from S0 to S1 states. Second, the calculated absorption and emission spectra are consistent with the experimental values, which proves that the theoretical method is feasible. Finally, through the analysis of the infrared vibrational spectrum, reduced density gradient isosurfaces, frontier molecular orbitals, and potential energy curves, the strengthening mechanism of the hydrogen bond interaction and the ability of the excited-state intramolecular proton transfer (ESIPT) reaction to occur are further explained. Since the proton transfer reactions of 2u and 2af occur spontaneously under photoexcitation, they have no stable structures in the S1 state. In conclusion, due to the different substituents, 2u is more prone to the proton transfer reaction than 2ad. For 2af, 2ai, and 2ah with different benzene ring numbers, the ESIPT reaction is more difficult to occur as the number of benzene rings increases. The ability of the ESIPT reaction to occur follows the order 2af → 2ah → 2ai. For 2-aryloxazoline derivatives with different substituents or different benzene ring numbers, the hydrogen bond strengthening mechanism has been authenticated, which promotes the occurrence of the ESIPT reactions.

Association of admission serum triglyceride levels with intensive care unit hospitalization rates in acute pancreatitis patients: A retrospective study.

Acute pancreatitis (AP) is a complex and unpredictable condition, of which hypertriglyceridemia (HTG) is the third most prevalent cause. This study aimed to conduct a retrospective analysis of clinical data from hospitalized AP patients to uncover a potential correlation between triglyceride (TG) levels and the necessity for intensive care unit (ICU) admission. This retrospective cohort study utilized the Medical Information Mart for Intensive Care IV 2.2 (MIMIC-IV) critical care dataset, incorporating data from 698 patients with hypertriglyceridemic acute pancreatitis (HTG-AP). The analysis employed the RCS model along with univariate and multivariate logistic regression methods to affirm the association between triglyceride levels and ICU admission. Subgroup analysis was performed to investigate specific populations. The study included 698 patients with AP, 42.41% of whom experienced HTG during hospitalization. RCS analysis revealed a linear association between TG levels and risk of ICU admission (p for nonlinear = .219, p for overall = .009). Multivariate logistic regression analysis indicated an increased risk of ICU admission in the TG range of 1.7-5.65 mmol/L (aOR = 1.83, 95% CI 1.12-2.99, P = .015) and TG >11.3 mmol/L (aOR = 5.69, 95% CI 2.36-13.74, P < .001) compared to the normal group. Similar results were observed across the various subgroups. As triglyceride levels increased, there was a corresponding increase in ICU admissions. Patients within the 1.7 to 5.65 mmol/L and > 11.3 mmol/L triglyceride groups exhibited higher rates of ICU admissions. Moreover, we observed a higher risk of ICU hospitalization even with mild TG elevation.

Effects of substitution and conjugation on photophysical properties of ESIPT-based fluorophores with the core of 4-aminophthalimide.

4-Aminophthalimide is a highly fluorescent signaling unit with excellent photophysical properties and wide application foregrounds. Based on this, a range of theoretical investigations are conducted on the fluorescent probe (E)-5-((2-hydroxybenzylidene) amino) isoindoline-1, 3-dione (HID) with the core of 4-aminophthalimide using density functional theory (DFT) and time-containing density functional theory (TD-DFT) methods in this paper. The optimized configurations, vertical excitation and emission energies, electronic characteristics and excited-state intramolecular proton transfer (ESIPT) behaviors of the probe HID are discussed in detail. Furthermore, to enhance the luminescent properties of HID, five novel compounds have been designed based on the structure of HID by introducing amino, methoxy and naphthalene groups (-NH2, -OMe and C10H8). Our work thoroughly explores how the property and position of substituents and conjugation affect photophysical characteristics and ESIPT processes. We find that the ESIPT dynamics can be modulated by the substitution and conjugation effects. Specifically, the introduction of amino and methoxy groups at the ortho-position and the introduction of the naphthalene group promote the ESIPT behavior of HID1, whereas the introduction of amino and methoxy groups at the meta-position exhibits the contrary impact. Therefore, we boldly infer that the introduction of electron-donating groups in the ortho-position and the introduction of the conjugated group make the ESIPT process more effortless to occur, whereas the introduction of substituents with opposing natures in the meta-position makes the ESIPT process more difficult to occur. In addition, the ionization potentials (IP), electron affinities (EA) and reorganization energies (λh and λe) of molecules are calculated to assess their potential as luminescent materials. Our work not only reveals the luminescence and ESIPT mechanism of the probe HID1, but also proposes to modulate the ESIPT process through the substitution and conjugation effects. In particular, the designed molecules have better photoelectric properties as a result of their red-shifted absorption and fluorescence spectra, smaller energy gaps, larger transferred charges and greater charge transferred distances, which offers some valuable ideas for the experimental development of more efficient organic luminescent materials with ESIPT properties.

Substituent effects on the ESIPT process and the potential applications in materials transport field of 2'-aminochalcone derivatives.

This work investigates the different charge transfer characteristics and excited state intramolecular proton transfer process (ESIPT) of 2'-aminochalcones derivatives carrying different electron-withdrawing groups. Four new molecules are designed in the experiment and named as 2c, 3c, 4c and 5c, respectively. (Dyes and Pigments, 2022, 202.) Based on these four molecules, the effect of substituents on the ESIPT process and the charge transfer process are discussed in detail in our work. According to the study of the related parameters at the hydrogen bond site, infrared vibration spectrum, interaction region indicator isosurface (IRI) and scatter plots, it is concluded that the hydrogen bond interaction is enhanced under photoexcitation, and the descending order of the excited state hydrogen bond strength is 3c > 5c > 4c > 2c. The hydrogen bond energy is calculated by atoms in moleculs (AIM) topological analysis and core-valence bifurcation (CVB) index. The potential energy curve reveals the ESIPT mechanism. Frontier molecular orbital and electron-hole analyses explain the reasons for the changes in the ESIPT process at the electronic level. In addition, the ionization potentials (IPa and IPv), affinity energies (EAa and EAv) and reorganization energies are calculated to evaluate the potential application value of organic molecules in material transport field.

[Gene mutation analysis of X-linked hypophosphatemic rickets].

OBJECTIVE: To investigate the frequency and type of PHEX gene mutations in children with X-linked hypophosphatemic rickets (XLH), the possible presence of mutational hot spots, and the relationship between genotype and clinical phenotype. METHODS: Clinical data of 10 children with XLH was retrospectively reviewed. The relationship between gene mutation type and severity of XLH was evaluated. RESULTS: PHEX gene mutations were detected in all 10 children with XLH, including 6 cases of missense mutation, 2 cases of splice site mutation, 1 case of frameshift mutation, and 1 case of nonsense mutation. Two new mutations, c.2048T>C and IVS14+1delAG, were found. The type of PHEX gene mutation was not associated with the degree of short stature and leg deformity (P=0.571 and 0.467), and the mutation site was also not associated with the degree of short stature and leg deformity (P=0.400 and 1.000). CONCLUSIONS: Missense mutation is the most common type of PHEX gene mutation in children with XLH, and c.2048T>C and IVS14+1delAG are two new PHEX gene mutations. The type and site of PHEX gene mutation are not associated with the severity of XLH.

[Clinical analysis and genetic diagnosis of short-limb inherited short stature diseases in children].

OBJECTIVE: To analyze the clinical manifestations, bone X-ray findings and genetic analysis results of three short-limb inherited short stature diseases: achondroplasia (ACH), hypochondroplasia (HCH) and pseudoachondroplasia (PSACH). METHODS: The clinical manifestations, bone X-ray findings, and genetic analysis results of 10 children with genetically confirmed short-limb inherited short stature diseases, including 4 cases of ACH 3 cases of HCH, and 3 cases of PSACH, were analyzed. RESULTS: The 10 patients had a mean body height of -3.69±1.79 SD, a mean sitting height/standing height ratio of 0.65±0.03, and a mean finger spacing/body height ratio of 0.93±0.04. Four ACH cases and 3 PSACH cases showed typical bone X-ray findings; one HCH case showed a smaller sciatic notch, and another HCH case showed no widening of interpedicular distance. G380R mutation in FGFR3 gene was detected in 3 of 4 ACH cases, and Y278C mutation in the other ACH case, N540K mutation in FGFR3 gene was detected in 3 HCH cases, and heterozygous mutations in COMP gene were detected in 3 PSACH cases. CONCLUSIONS: Children with ACH and PSACH have severer short stature and skeletal deformities than children with HCH, who have mild, atypical clinical manifestations. Bone X-ray and genetic analysis are helpful for the diagnosis and differential diagnosis of the three diseases. The mutational hotspots in two genes are involved in the three diseases, which is conducive to clinical genetic diagnosis.

Insights from computational analysis: Excited-state hydrogen-bonding interactions and ESIPT processes in phenothiazine derivatives.

Organic materials with Mechanofluorochromism (MFC) properties have potential application value. Phenothiazine derivatives are a class of substances with MFC properties that have been synthesized and reported in experiments (Dyes and Pigments 172 (2020) 107835). Dual fluorescence of a series of phenothiazine derivatives is observed in the experiment, which proved that the ESIPT process is carried out. In this work, we choose phenothiazine derivatives (C2PAHN, C4PAHN, C8PAHN) as models to theoretically analyze the influence of different alkyl chain lengths on the excited state intramolecular proton transfer (ESIPT). In addition, the shift value of fluorescence spectrum is related to the length of alkyl chain. The fluorescence shift of C2PAHN is the largest (6.31 nm), and that of C8PAHN is the smallest (2.40 nm). The theory of density functional theory (DFT) and time-dependent density functional theory (TD-DFT) are adopted to simulate the molecular dynamics in the ground state and excited state. The analysis of the optimized molecular geometry parameters and infrared vibrational spectroscopy (IR) illustrate the stronger hydrogen bonding of the excited state molecules, which is favorable for the progress of ESIPT. Fluorescence spectroscopy reveals that the appropriate increase or decrease of alkyl chains would change the photophysical properties of the molecules. Frontier molecular orbitals (FMOs) indicate that the rearrangement of electron density from electronic level to is the driving force of the ESIPT process. Reduction density gradient (RDG) surfaces and Natural Population Analysis (NPA) tentatively lead to the conclusion that alkyl chain length is inversely proportional to hydrogen bond strength. Finally, the data are qualitatively analyzed by scanning the potential energy curves, and it is concluded that the longer the alkyl chain, the weaker the hydrogen bonding effect and the more unfavorable the ESIPT process.

Unveiling the sensing mechanism and luminescence property of a new ESIPT-based fluorescent sensor for detecting Zn2.

Recently, based on the mechanism of excited-state intramolecular proton transfer (ESIPT), a new fluorescent probe named 3-(benzo[d]thiazol-2-yl)-5-bromosalicylaldehyde-4N-phenyl thiosemicarbazone (BTT) was successfully synthesized [Analyst 146 (2021) 4348-4356.]. However, the importance of ESIPT processes of BTT probe and the mechanism of detecting Zn2+ ions have not been studied in detail. In this study, the photochemical behavior of ESIPT-chromophore and the photophysical changes of detecting Zn2+ ions were explained at the molecular level for the first time. The calculated spectral values were in agreement with the experiment. We not only confirmed the excited state hydrogen-bond strengthening by interaction region indicator (IRI), but also scanned the potential energy curves of BTT molecule in different electronic states, which confirmed that the hydrogen proton is easier to transfer in the first excited state. In addition, we had given the reasonable structure of the BTT-Zn2+ complex (L1) by comparing the binding free energies. The hole-electron distribution and interfragment charge transfer (IFCT) methods proved the excitation type of intraligand charge transfer (ILCT). Finally, the photophysical phenomenon of BTT for detecting Zn2+ ions is explained by calculating the electronic spectra and the energy gap (Egap) between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).