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Angewandte Chemie (International Ed. in... Jul 2024The condensation of amino acids into peptides plays a crucial role in protein synthesis and is thus essential for understanding the origins of life. However, the...
The condensation of amino acids into peptides plays a crucial role in protein synthesis and is thus essential for understanding the origins of life. However, the spontaneous formation of peptides from amino acids in bulk aqueous media is energetically unfavorable, posing a challenge for elucidating plausible abiotic mechanisms. In this study, we investigate the formation of amide bonds between amino acids within highly supersaturated aerosol droplets containing dicyandiamide (DCD), a cyanide derivative potentially present on primordial Earth. Metastable states, i.e. supersaturation, within individual micron-sized droplets are studied using both an optical trap and a linear quadrupole electrodynamic balance. When irradiated with intense visible light, amide bond formation is observed to occur and can be monitored using vibrational bands in Raman spectra. The reaction rate is found to be strongly influenced by droplet size and kinetic modelling suggests that it is driven by the photochemical product of a DCD self-reaction. Our results highlight the potential of atmospheric aerosol particles as reaction environments for peptide synthesis and have potential implications for the prebiotic chemistry of early Earth.
PubMed: 38954428
DOI: 10.1002/anie.202409788 -
Insights Into Imaging Jul 2024This study investigated the quantitative assessment and application of Synthetic MRI (SyMRI) for preoperative brain development in children with congenital heart disease...
OBJECTIVES
This study investigated the quantitative assessment and application of Synthetic MRI (SyMRI) for preoperative brain development in children with congenital heart disease (CHD).
METHODS
Forty-three CHD patients aged 2-24 months were prospectively included in the observation group, and 43 healthy infants were included in the control group. The SyMRI scans were processed by postprocessing software to obtain T1, T2, and PD maps. The values of T1, T2, and PD in different brain regions were compared with the scores of the five ability areas of the Gesell Development Scale by Pearson correlation analysis.
RESULTS
In the observation group, the T1 values of the posterior limb of the internal capsule (PLIC), Optic radiation (PTR), cerebral peduncle, centrum semiovale, occipital white matter, temporal white matter, and dentate nucleus were greater than those in the control group. In the observation group, the T2 values of the PLIC, PTR, frontal white matter, occipital white matter, temporal white matter, and dentate nucleus were greater than those in the control group. Pearson correlation analysis revealed that the observation group had significantly lower Development Scale scores. In the observation group, the T2 value of the splenium of the corpus callosum was significantly positively correlated with the personal social behavior score. The AUCs for diagnosing preoperative brain developmental abnormalities in children with CHD using T1 values of the temporal white matter and dentate nucleus were both greater than 0.60.
CONCLUSIONS
Quantitative assessment using SyMRI can aid in the early detection of preoperative brain development abnormalities in children with CHD.
CRITICAL RELEVANCE STATEMENT
T1 and T2 relaxation values from SyMRI can be considered as a quantitative imaging marker to detect abnormalities, allowing for early clinical evaluation and timely intervention, thereby reducing neurodevelopmental disorders in these children.
KEY POINTS
T1 and T2 relaxation values by SyMRI are related to myelin development. Evaluated development quotient markers were lower in the observation compared to the control group. SyMRI can act as a reference indicator for brain development in CHD children.
PubMed: 38954290
DOI: 10.1186/s13244-024-01746-0 -
Bioresources and Bioprocessing Jul 2024Regioselective and enantioselective hydroxylation of propargylic C-H bonds are useful reactions but often lack appropriate catalysts. Here a green and efficient...
Regioselective and enantioselective hydroxylation of propargylic C-H bonds are useful reactions but often lack appropriate catalysts. Here a green and efficient asymmetric hydroxylation of primary and secondary C-H bonds at propargylic positions has been established. A series of optically active propargylic alcohols were prepared with high regio- and enantioselectivity (up to 99% ee) under mild reaction conditions by using P450tol, while the C≡C bonds in the molecule remained unreacted. This protocol provides a green and practical method for constructing enantiomerically chiral propargylic alcohols. In addition, we also demonstrated that the biohydroxylation strategy was able to scaled up to 2.25 mmol scale with the production of chiral propargyl alcohol 2a at a yield of 196 mg with 96% ee, which's an important synthetic intermediate of antifungal drug Ravuconazole.
PubMed: 38954282
DOI: 10.1186/s40643-024-00771-7 -
Discover Nano Jul 2024Light-emitting diodes (LEDs) are an indispensable part of our daily life. After being studied for a few decades, this field still has some room for improvement. In this... (Review)
Review
Light-emitting diodes (LEDs) are an indispensable part of our daily life. After being studied for a few decades, this field still has some room for improvement. In this regard, perovskite materials may take the leading role. In recent years, LEDs have become a most explored topic, owing to their various applications in photodetectors, solar cells, lasers, and so on. Noticeably, they exhibit significant characteristics in developing LEDs. The luminous efficiency of LEDs can be significantly enhanced by the combination of a poor illumination LED with low-dimensional perovskite. In 2014, the first perovskite-based LED was illuminated at room temperature. Furthermore, two-dimensional (2D) perovskites have enriched this field because of their optical and electronic properties and comparatively high stability in ambient conditions. Recent and relevant advancements in LEDs using low-dimensional perovskites including zero-dimensional to three-dimensional materials is reported. The major focus of this article is based on the 2D perovskites and their heterostructures (i.e., a combination of 2D perovskites with transition metal dichalcogenides, graphene, and hexagonal boron nitride). In comparison to 2D perovskites, heterostructures exhibit more potential for application in LEDs. State-of-the-art perovskite-based LEDs, current challenges, and prospects are also discussed.
PubMed: 38954158
DOI: 10.1186/s11671-024-04044-2 -
Journal of Molecular Modeling Jul 2024In this study, we evaluate the geometrical, absorption, optoelectronic, electronic, nonlinear optical (NLO) and thermodynamic properties of dibenzo[b,def]chrysene...
Impact of doping with organic dopants and mixed doping with alkali metals and organic dopants on the absorption, electronic, optoelectronic, thermodynamic and nonlinear optical properties of dibenzo[b,def]chrysene in gaseous media: DFT and TD-DFT studies.
CONTEXT
In this study, we evaluate the geometrical, absorption, optoelectronic, electronic, nonlinear optical (NLO) and thermodynamic properties of dibenzo[b,def]chrysene molecule derivatives by means of DFT and TD-DFT simulations. In view of the aim of producing new high-performance materials for non-linear optics (NLO) by doping test, two types of doping were used. We obtained six derivatives by doping with organic dopants (Nitro, amide and ticyanoethenyl) and mixed alkali metal (potassium) and organic dopants. Doping with organic dopants produced molecules A, B and C, respectively when substituting one hydrogen with nitro (NO), amide (CONH) and tricyanoethenyl (CN) groups, while mixed doping involved considering A, B and C and then substituting two hydrogens with two potassiums to obtain compounds D, E and F respectively. The negative values of the various interaction energies calculated for all the doped molecules show that they are all stable, but also that molecules C and F are the most stable in the case of both dopings. The gap energies calculated at the B3LYP level of theory are all below 3 eV, which means that all the molecules obtained are semiconductors. Better still, compounds C and F, with gap energies of 1.852 eV and 1.204 eV, respectively, corresponding to decreases of 35.67% and 58.18% in gap energy compared with the pristine molecule, are more reactive than the other doped molecules. Mixed doping is therefore a highly effective way of narrowing the energy gap and boosting the semiconducting character and reactivity of organic materials. Optoelectronic properties have also been improved, with refractive index values higher than those of the reference material, glass. This shows that our compounds could be used under very high electric field conditions of the order of 4.164 10 V.m for C and 7.410 10 V.m for F the highest values at the B3LYP level of theory. The maximum first-order hyperpolarizability values for both types of doping are obtained at the CAM-B3LYP level of theory by C: 10esu and by F: 10esu, and second-order values are also given by these same compounds. These values are higher than the reference value, which is urea, making our compounds potential candidates for high-performance NLO applications. In dynamic mode and at a frequency of 1064 nm, at the CAM-B3LYP level of theory, the highest dynamic hyperpolarizability coefficients were obtained by C and F. Hyper-Rayleigh scattering , coefficients of the electro-optical Pockel effect (EOPE), EFISHG, third-order NLO-response degree four-wave mixing , quadratic nonlinear refractive index n2 were also calculated. The maximum values of n are obtained by C (6.13 10 m/W) and F (6.60 10 m/W), these values are 2.24 times higher than that of fused silica which is the reference for degenerate four-wave mixing so our molecules could also have applications in optoelectronics as wavelength converters, optical pulse modulators and optical switches.
METHODS
Using the DFT method, we were able to determine the optimized and stable electronic structures of doped dibenzo[b,def]chrysene derivatives in the gas phase. We limited ourselves to using the proven B3LYP and CAMB3LYP levels of theory for calculating electronic properties, and non-linear optics with the 6-311G + + (d,p) basis set, which is a large basis set frequently used for these types of compound. Gaussian 09 software was used to run our calculations, and Gauss View 6.0.16 was used to visualize the output files. TD-DFT was also used to determine absorption properties at the B3LYP level of theory, using the same basis set.
PubMed: 38954155
DOI: 10.1007/s00894-024-06026-8 -
World Journal of Microbiology &... Jul 2024The aim of the present study is to develop a pH-sensing biopolymer film based on the immobilization of red cabbage extract (RCE) within bacterial cellulose (BC) to...
The aim of the present study is to develop a pH-sensing biopolymer film based on the immobilization of red cabbage extract (RCE) within bacterial cellulose (BC) to detect contamination and gamma radiation exposure in cucumbers. The results obtained show a sensitivity to pH changes for RCE in its aqueous form and that incorporated within BC films (RCE-BC), both showed color change correlated to bacterial growth (R = 0.91), this was supported with increase in pH values from 2 to 12 (R = 0.98). RCE and RCE-BC exposure to gamma radiation (0, 2.5, 5, 10, 15, 20, 25 kGy) resulted in gradual decrease in color that was more evident in RCE aqueous samples. To sense bacterial contamination of cucumbers, the total count was followed at 0, 5, 10 and 15 days in cold storage conditions and was found to reach 9.13 and 5.47 log cfu/mL for non-irradiated and 2 kGy irradiated samples, respectively. The main isolates detected throughout this storage period were identified as Pseudomonas fluorescens, Erwinia sp. Pantoea agglomerans using matrix assisted laser desorption ionization-time of flight-ms (MALDI-TOF-MS). Bacterial growth in stored irradiated cucumbers was detected by color change within 5 and 10 days of storage, after which there was no evident change. This is very useful since contamination within the early days of storage cannot be sensed with the naked eye. This study is the first to highlight utilizing RCE and RCE-BC as eco-friendly pH-sensing indicator films for intelligent food packaging to detect both food contamination and gamma preservation for refrigerator stored cucumbers.
Topics: Brassica; Cellulose; Gamma Rays; Cucumis sativus; Hydrogen-Ion Concentration; Plant Extracts; Food Microbiology; Bacteria; Food Packaging; Food Contamination; Food Storage; Food Irradiation; Colony Count, Microbial
PubMed: 38954148
DOI: 10.1007/s11274-024-04047-2 -
International Ophthalmology Jul 2024To compare early changes in the corneal biomechanical parameters after photorefractive keratectomy (PRK) and small incision lenticule extraction (SMILE) and their...
PURPOSE
To compare early changes in the corneal biomechanical parameters after photorefractive keratectomy (PRK) and small incision lenticule extraction (SMILE) and their correlations with corneal shape parameters.
METHODS
One hundred twenty four eyes received myopic PRK and SMILE for similar amounts of myopia. Corneal tomography with Pentacam HR, biomechanical parameters using Corvis ST, and Ocular Response Analyzer (ORA) were evaluated before and 2 weeks after surgery. The change in each parameter was compared between groups, while the difference in central corneal thickness and cornea-compensated intraocular pressure measured before and after surgery were considered as covariates.
RESULTS
A significant reduction was seen in the corneal stiffness parameter at first applanation, and an increase in deformation amplitude ratio (DAR), and integrated inverse radius (IIR) in both groups after surgery (p < 0.001) Changes in DAR, and IIR were significantly greater in the SMILE than in the PRK group (p < 0.001) Corneal hysteresis (CH) and corneal resistance factor (CRF) decreased in both SMILE and PRK groups after surgery, (p < 0.001) with no statistically significant difference between groups (p > 0.05) Among new Corvis ST parameters, DAR showed a significant correlation with changes in Ambrosio relational thickness in both groups (p < 0.05).
CONCLUSIONS
Both techniques caused significant changes in corneal biomechanics in the early postoperative period, with greater elastic changes in the SMILE group compared to the PRK group, likely due to lower tension in the SMILE cap and thinner residual stromal bed in SMILE. There were no differences in viscoelastic changes between them, so the lower CH may reflect the volume of tissue removed.
Topics: Humans; Photorefractive Keratectomy; Myopia; Cornea; Female; Male; Adult; Elasticity; Biomechanical Phenomena; Young Adult; Lasers, Excimer; Intraocular Pressure; Corneal Surgery, Laser; Refraction, Ocular; Corneal Topography; Corneal Stroma; Postoperative Period; Visual Acuity; Prospective Studies; Follow-Up Studies
PubMed: 38954134
DOI: 10.1007/s10792-024-03169-8 -
Journal of Fluorescence Jul 2024Quantum chemical calculations of 3-aminosalicylic acid (3ASA) (monomer and dimer forms) have been performed using DFT and TD-DFT theories with B3LYP/6-311 G(d,p)...
Quantum chemical calculations of 3-aminosalicylic acid (3ASA) (monomer and dimer forms) have been performed using DFT and TD-DFT theories with B3LYP/6-311 G(d,p) functional level in the ground and excited states. Using TD-DFT with IEF-PCM model, the electronic spectra of 3ASA in solvents were computed and correlated with the experimental data. The theoretically calculated absorption and emission maxima of 3ASA (monomer) are observed in the range of 343 - 347 nm (S → S transition) and 429 - 448 nm (S → S transition), respectively. The natural bond orbital (NBO) analysis shows that charge transfer interaction contributes significantly to stabilize the molecular system. In the case of dimer, hydrogen bonding plays a dominant role in stabilizing the molecular framework. Additionally, the obtained nonlinear optical (NLO) properties: polarizability (13.86 × 10 e.s.u for monomer and 29.46 × 10 e.s.u. for dimer), first-order hyperpolarizability (4.21 × 10 e.s.u for monomer and 0.18 × 10 e.s.u for dimer) and second-order hyperpolarizability (7.44 × 10 e.s.u. for monomer and 14.32 × 10 e.s.u. for dimer) were found to be larger than those of standard organic compounds suggesting that 3ASA has a significant NLO character for optoelectronic applications. The NLO properties of dimer may differ from monomer due to dimerization. Further, the radiative lifetime, light harvesting efficiency and band gap energy were calculated, and proposed that 3ASA may be useful in photovoltaics and wide bandgap power devices. HIGHLIGHTS: • DFT and TD-DFT theories were employed to calculate structural and molecular properties of 3ASA (monomer and dimer) in ground and excited states. • HOMO-LUMO study shows monomer and dimer of 3ASA are good reactive. • NBO analysis reflects that charge transfer interactions stabilized the 3ASA molecule. • Electronic absorption/emission spectra in solvents calculated by IEF-PCM/TD-DFT method correlate with experimental results. • Calculated NLO parameters suggested that 3ASA is a potential candidate for NLO material.
PubMed: 38954083
DOI: 10.1007/s10895-024-03781-y -
Molecular Diversity Jul 2024Proviral Integrations of Moloney-2 (PIM-2) kinase is a promising target for various cancers and other diseases, and its inhibitors hold potential for treating related...
Proviral Integrations of Moloney-2 (PIM-2) kinase is a promising target for various cancers and other diseases, and its inhibitors hold potential for treating related diseases. However, there is currently no clinically available PIM-2 inhibitor. In this study, we constructed a generative model for de novo PIM-2 inhibitor design based on artificial intelligence, performed molecular docking and molecular dynamics (MD) simulations to develop an efficient PIM-2 inhibitor generative model and discover potential PIM-2 inhibitors. First, we designed a generative model based on a Bi-directional Long Short-Term Memory (BiLSTM) framework combined with a transfer learning strategy and generated a new PIM-2 small molecule library using existing active drug databases. The generated compound library was then virtually screened by molecular docking and scaffold similarity comparison, identifying 10 initial hit compounds with better performance. Next, using the inhibitor in the crystal structure as a positive control, we performed two rounds of MD simulations, with lengths of 100 ns and 500 ns, respectively, to study the dynamic stability of the protein-ligand systems of the 10 compounds with PIM-2. Analyzed the interactions with key hinge region residues, binding free energies, and changes in the ATP pocket size. The generative model demonstrates good molecular generation capability and can generate efficient novel molecules with similar physicochemical properties as active PIM-2 drugs. Among the 10 initially selected hit compounds, 5 compounds C3 (- 29.69 kcal/mol), C4 (- 33.31 kcal/mol), C5 (- 28.59 kcal/mol), C8 (- 34.68 kcal/mol), and C9 (- 25.88 kcal/mol) have higher binding energies with PIM-2 than the positive drug 3YR (- 26.18 kcal/mol). The MD simulation results are consistent with the docking analysis, these compounds have lower and more stable RMSD values for the complex systems with the reported positive drug 3YR and PIM-2 complex system. They can form long-term stable interactions with active site and the hinge region of PIM-2, which suggests these compounds are likely to have potent inhibitory effects on PIM-2. This study provides an efficient generative model for PIM-2 inhibitor research and discovers 5 potential novel PIM-2 inhibitors.
PubMed: 38954072
DOI: 10.1007/s11030-024-10916-7 -
International Ophthalmology Jul 2024Investigate the most appropriate mathematical formula to objectively express upper eyelid contour symmetry.
PURPOSE
Investigate the most appropriate mathematical formula to objectively express upper eyelid contour symmetry.
METHODS
62 eyes of 31 patients were included in the study. The upper eyelid contour symmetry of the patients was classified subjectively (independent of MRD1) as poor, acceptable, and good by three oculoplastic specialists (senior, expert, and junior surgeon). Bézier curves of the upper lid contour were drawn with ImageJ software (NIH, Bethesda, MA, USA). Using the algorithms created by Author SKC in Spyder (Python 3.7.9.), the symmetry of the Bézier curves of the left eyelids were obtained according to the y-axis, and the mid-pupils of both eyes were superimposed. The lower curve moved vertically to the equal height of the other curve to equalize MRD1's. R (Coefficient of determination), RMSE (Root-mean-square error), MSE (Mean squared error), POC (Percentage of co-efficiency), and MAE (Mean absolute error) were calculated. We evaluated the correlation between these objective formulas and the subjective grading of three surgeons using Spearman's rho (ρ).
RESULTS
The correlation coefficient of RMSE and MSE were the same for all surgeons grading. There was a strong correlation between the senior surgeon's subjective scoring (N; poor = 8, acceptable = 16, good = 8) and R, RMSE, POC, MAE (ρ = 0.643, p < 0.001, ρ = -0.607, p < 0.001, ρ = 0.562, p < 0.001, ρ = -0.517, p < 0.001, respectively). We found a strong relationship between the expert surgeon's subjective scoring (N; poor = 9, acceptable = 13, good:10) and R (ρ = 0.611, p < 0.001), RMSE (ρ = -0.549, p < 0.001), POC (ρ = 0.511, p < 0.001), and MAE (ρ = -0.450, p < 0.05). We found a strong correlation between junior surgeon's subjective scoring (N; poor = 6, acceptable = 18, good = 8) and R, RMSE, and POC (ρ: -0.517, p < 0.001; ρ: -0.470, p < 0.001; ρ: 0.521, p < 0.001; respectively) and moderate correlation between MAE (ρ:-0.394, p < 0.05). The highest correlation is observed with R.
CONCLUSIONS
RMSE, MSE, POC, MAE, and especially R, may quantitatively express upper eyelid contour symmetry, comparable with the oculoplastic surgeon. The highest correlation was observed between the senior surgeon and R, and decreases with the experience of the surgeon.
Topics: Humans; Eyelids; Female; Male; Middle Aged; Algorithms; Aged; Adult; Blepharoplasty
PubMed: 38954051
DOI: 10.1007/s10792-024-03157-y