Effects of laser pulse duration on the formation dynamics of laser-induced periodic nanostructures.

Formation dynamics of laser-induced periodic surface structures (LIPSSs) on the SiC substrates were described with varying pulse numbers and pulse duration. As the number of laser pulses increases, two significant transformations become evident in the progression of structural formations. First from surface roughening with nanoparticles to LIPSS with the period that is slightly shorter than the laser wavelength. Second it turns to LIPSS with a period less than half the laser wavelength. It is found that maintaining the crystallinity is the key to changing the structures. In the cases of longer pulse width than sub-nanoseconds, no LIPSS formations are observed or LSFL does not change to HSFL because the irradiated area is poly-crystallized.

>50 MW peak power, high brightness Nd:YAG/Cr4+:YAG microchip laser with unstable resonator.

We demonstrated a flat-convex unstable cavity Nd:YAG/Cr4+:YAG ceramic air-cooled microchip laser (MCL) generating a record 37.6 and 59.2 MW peak power pulses with an energy of 17.0 and 24.1 mJ and a width of 452 and 407 ps at 20 Hz by using a uniform power square and hexagon pump, respectively. For hexagon pump, the near field hexagon donut beam was changed in to a Bessel-like beam in far field, whose beam quality was estimated as 2nd moment M2 of 7.67. The brightness scale of unstable resonator MCL was achieved up to 88.9 TW/(sr·cm2) in contrast with flat-flat cavity MCL. However, the high intense center part of Bessel-like beam increased its brightness effectively more than 8 times, up to 736 TW/(sr·cm2).

Serum copeptin levels at day two after pituitary surgery and ratio to baseline predict postoperative central diabetes insipidus.

PURPOSE: Central diabetes insipidus is a complication that may occur after pituitary surgery and has been difficult to predict. This study aimed to identify the cutoff levels of serum copeptin and its optimal timing for predicting the occurrence of central diabetes insipidus in patients who underwent transsphenoidal surgery. METHODS: This was a prospective observational study of patients who underwent transsphenoidal surgery for pituitary gland or stalk lesions. Copeptin levels were measured before surgery, 1 h after extubation, and on postoperative days 1, 2, 7, and 90. RESULTS: Among 73 patients, 14 (19.2%) and 13 (17.8%) patients developed transient and permanent central diabetes insipidus, respectively. There was no significant difference in copeptin levels before surgery and 1 h after extubation; copeptin levels on postoperative days 1, 2, 7, and 90 were significantly lower in patients with permanent central diabetes insipidus than in those without central diabetes insipidus. Copeptin measurement on postoperative day 2 exhibited the highest performance for predicting permanent central diabetes insipidus among postoperative days 1, 2, and 7 (area under the curve [95% confidence interval] = 0.754 [0.632-0.876]). Serum copeptin level at postoperative day 2(< 3.1 pmol/L) showed a sensitivity of 92.3% and a negative predictive value of 97.1%. The ratio of copeptin at postoperative day 2 to baseline (< 0.94) presented a sensitivity of 84.6% and a negative predictive value of 94.9%. The copeptin levels > 3.4 and 7.5 pmol/L at postoperative day 2 and 7 may have ruled out the occurrence of CDI with a negative predictive value of 100%. CONCLUSION: The copeptin level at postoperative day 2 and its ratio to baseline can predict the occurrence of permanent central diabetes insipidus after pituitary surgery.

Classification of Granite Soils and Prediction of Soil Water Content Using Hyperspectral Visible and Near-Infrared Imaging.

Soil water content is one of the most important physical indicators of landslide hazards. Therefore, quickly and non-destructively classifying soils and determining or predicting water content are essential tasks for the detection of landslide hazards. We investigated hyperspectral information in the visible and near-infrared regions (400-1000 nm) of 162 granite soil samples collected from Seoul (Republic of Korea). First, effective wavelengths were extracted from pre-processed spectral data using the successive projection algorithm to develop a classification model. A gray-level co-occurrence matrix was employed to extract textural variables, and a support vector machine was used to establish calibration models and the prediction model. The results show that an optimal correct classification rate of 89.8% could be achieved by combining data sets of effective wavelengths and texture features for modeling. Using the developed classification model, an artificial neural network (ANN) model for the prediction of soil water content was constructed. The input parameter was composed of Munsell soil color, area of reflectance (near-infrared), and dry unit weight. The accuracy in water content prediction of the developed ANN model was verified by a coefficient of determination and mean absolute percentage error of 0.91 and 10.1%, respectively.

Synthesis and Properties of Pentafluorosulfanyl Group (SF5)-Containing Meta-Diamide Insecticides.

Herein, we describe novel pentafluorosulfanyl (SF5) group-containing meta-diamide insecticides. For the facile preparation of the SF5-based compounds 4a-d, practical synthetic methods were applied. Among newly synthesized compounds, 3-benzamido-N-(2,6-dimethyl-4-(pentafluoro-λ6-sulfanyl)phenyl)-2-fluorobenzamide 4d showed (i) a high insecticidal activity, (ii) an excellent selectivity to insects, and (iii) good levels of water solubility and log P values. In this study, we demonstrated that the pentafluorosulfanyl moiety could serve as an attractive functionality for the discovery of a new scope of crop-protecting agents.

High peak power Nd:YAG/Cr:YAG ceramic microchip laser with unstable resonator.

A doughnut mode microchip laser was demonstrated by introducing a monolithic ceramic Nd:YAG/Cr4+:YAG chip in an unstable resonator to deliver laser pulses with an energy of 13.2 mJ and a pulse width of 476 ps, corresponding to a record peak power of 27.7 MW. The laser beam quality was characterized by M2∼6 at 10 Hz repetition rate. No significant degradation or change of beam pattern, pulse width, and M2 was confirmed during energy scaling in the case of the unstable cavity, promising for further brightness improving. In comparison with a flat-flat cavity, pulse broadening and M2 increase was observed up to ∼1.2 ns and ∼10, respectively, during energy scaling up to 18 mJ due to the beam pattern degradation. The doughnut beam was observed to have an Airy disk at the focal point, which was suitable for laser induced breakdown in air. The measured breakdown threshold of doughnut beam was comparable to a near-Gaussian beam (M2=1.3).

Synthesis, Physicochemical Properties, and Biological Activities of 4-(S-Methyl-N-(2,2,2-Trifluoroacetyl)Sulfilimidoyl) Anthranilic Diamide.

Novel anthranilic diamides with sulfilimidoyl and sulfoximidoyl functionalities were successfully prepared. Among newly-prepared organosulfur compounds, 3-bromo-1-(3-chloropyridin-2-yl)-N-(2-methyl-6-(methylcarbamoyl)-4-(methylthio)phenyl)-1H-pyrazole-5-carboxamide and (S,E)-3-bromo-1-(3-chloropyridin-2-yl)-N-(2-methyl-4-(S-methyl-N-(2,2,2-trifluoroacetyl)sulfinimidoyl)-6-(methylcarbamoyl)phenyl)-1H-pyrazole-5-carboxamide showed good levels of efficacy and a strong correlation between insecticidal activities and physical properties, respectively. In particular, available data indicated that the N-trifluoroacetyl sulfilimine moiety could be an appealing structural scaffold for the discovery of a new crop-protecting agent.

Broadly Applicable Stereoselective Syntheses of Serrulatane, Amphilectane Diterpenes, and Their Diastereoisomeric Congeners Using Asymmetric Hydrovinylation for Absolute Stereochemical Control.

A stereogenic center, placed at an exocyclic location next to a chiral carbon in a ring to which it is attached, is a ubiquitous structural motif seen in many bioactive natural products, including di- and triterpenes and steroids. Installation of these centers has been a long-standing problem in organic chemistry. Few classes of compounds illustrate this problem better than serrulatanes and amphilectanes, which carry multiple methyl-bearing exocyclic chiral centers. Nickel-catalyzed asymmetric hydrovinylation (AHV) of vinylarenes and 1,3-dienes such as 1-vinylcycloalkenes provides an exceptionally facile way of introducing these chiral centers. This Article documents our efforts to demonstrate the generality of AHV to access not only the natural products but also their various diastereoisomeric derivatives. Key to success here is the availability of highly tunable phosphoramidite Ni(II) complexes useful for overcoming the inherent selectivity of the chiral intermediates. The yields for hydrovinylation (HV) reactions are excellent, and selectivities are in the range of 92-99% for the desired isomers. Discovery of novel, configurationally fluxional, yet sterically less demanding 2,2'-biphenol-derived phosphoramidite Ni complexes (fully characterized by X-ray) turned out to be critical for success in several HV reactions. We also report a less spectacular yet equally important role of solvents in a metal-ammonia reduction for the installation of a key benzylic chiral center. Starting with simple oxygenated styrene derivatives, we iteratively install the various exocyclic chiral centers present in typical serrulatane [e.g., a (+)- p-benzoquinone natural product, elisabethadione, nor-elisabethadione, helioporin D, a known advanced intermediate for the synthesis of colombiasin and elisapterosin] and amphilectane [e.g., A-F, G-J, and K,L pseudopterosins] derivatives. A concise table showing various synthetic approaches to these molecules is included in the Supporting Information. Our attempts to synthesize a hitherto elusive target, elisabethin A, led to a stereoselective, biomimetic route to pseudopterosin A-F aglycones.

One-pot sequential synthesis of tetrasubstituted thiophenes via sulfur ylide-like intermediates.

Herein, we describe a novel approach for the practical synthesis of tetrasubstituted thiophenes 8. The developed method was particularly used for the facile preparation of thienyl heterocycles 8. The mechanism for this reaction is based on the formation of a sulfur ylide-like intermediate. It was clearly suggested by (i) the intramolecular cyclization of ketene N,S-acetals 7 to the corresponding thiophenes 8, (ii) 1H NMR studies of Meldrum's acid-substituted aminothioacetals 9, and (iii) substitution studies of the methoxy group on Meldrum's acid containing N,S-acetals 9b. Notably, in terms of structural effects on the reactivity and stability of sulfur ylide-like intermediates, 2-pyridyl substituted compound 7a exhibited superior properties over those of others.

Sub-nanosecond laser induced air-breakdown with giant-pulse duration tuned Nd:YAG ceramic micro-laser by cavity-length control.

We first demonstrated a continuously and widely giant-pulse duration tunable laser based on a short monolithic Nd:YAG/Cr:YAG ceramic by cavity-length control in 100 Hz operation. The tuning range of pulse duration τ was from 0.5 to 9 ns as keeping peak powers of over 0.5 MW up to 6 MW. The characteristics of the ceramic laser was discussed in detail such as cavity-length dependent beam pattern and divergence, pulse shape, pulse energy due to the transverse and longitudinal modes, and an elliptical polarization status. Laser induced breakdown in laboratory air was investigated as a function of τ in sub-nanosecond region using the developed laser. Air-breakdown threshold intensity Ith was measured using three different focusing conditions. We confirmed that 1) the measured Ith was almost constant at the longer τ than τCI named as limit-pulse-duration of cascade ionization (CI), 2) Ith had ~τ-2 scaling for τ < τCI, 3) the increase of Ith is not connected to a specific intensity level, and 4) τCI was not constant and depended on focusing conditions. These phenomena were discussed with considering temporal-spatial intensity of laser.

Mild one-pot Horner-Wadsworth-Emmons olefination and intramolecular N-arylation for the syntheses of indoles, all regio-isomeric azaindoles, and thienopyrroles.

The syntheses of various N-protected aromatic-ring fused pyrrole-2-carboxylate derivatives have been accomplished using mild one-pot Horner-Wadsworth-Emmons olefination and Cu-catalyzed intramolecular N-arylation reactions. The optimized mild one-pot reaction conditions of various 2-bromo arylcarboxaldehydes with commercially available N-protected phosphonoglycine trimethylesters gave the desired aromatic-ring fused pyrrole-2-carboxylates, such as substituted indole-, all regio-isomeric azaindole-, and thienopyrrole-2-carboxylates, in good to excellent yields. These conditions showed broad substrate compatibility, without the loss of the protecting group.

Parasitic-light-suppressed quasi-phase-matched optical parametric oscillation device.

Nonlinear absorption - such as green-induced infrared absorption (GRIIRA) - increases the risk of the catastrophic damage during high peak- power wavelength conversion. We propose a novel concept to suppress parasitic green second-harmonic generation (SHG) in optical parametric oscillation (OPO) using specially engineered quasi-phase-matched (QPM) structures. This selective suppression was achieved by relative π-phase shift in only SHG not OPO. Compared with a periodic device, a parasitic-light-suppressed (PLS) QPM device produced smaller normalized conversion efficiency in green and maintained singly resonant OPO performance.

Thermal characteristics of second harmonic generation by phase matched calorimetry.

We analyze a solution of the heat equation for second harmonic generation (SHG) with a focused Gaussian beam and simulate the temperature rise in SHG materials as a function of the second harmonic power and the focusing conditions. We also propose a quantitative value of the heat removal performance of SHG devices, referred to as the effective heat capacity Cα in phase matched calorimetry. We demonstrate the inverse relation between Cα and the focusing parameter ξ, and propose the universal quantity of the product of Cα and ξ for characterizing the thermal property of SHG devices. Finally, we discuss the strategy to manage thermal dephasing in SHG using the results from simulations.

Multi-source remote sensing-based landslide investigation: the case of the August 7, 2020, Gokseong landslide in South Korea.

Landslides pose a growing concern worldwide, emphasizing the need for accurate prediction and assessment to mitigate their impact. Recent advancements in remote sensing technology offer unprecedented datasets at various scales, yet practical applications demand further case studies to fully integrate these technologies into landslide analysis. This study presents a case study approach to fully leverage variety of multi-source remote sensing technologies for analyzing the characteristics of a landslide. The selected case is a landslide with a long runout debris flow that occurred in Gokseong County, South Korea, on August 7, 2020. The chosen multi-source technologies encompass digital photogrammetry using RGB and multi-spectral imageries, 3D point clouds acquired by light detection and ranging (LiDAR) mounted on an unmanned aerial vehicle (UAV), and satellite interferometric synthetic aperture radar (InSAR). The satellite InSAR analysis identifies the initial displacement, triggered by rainfall and later transforming into a debris flow. The utilization of digital photogrammetry, employing UAV-RGB and multi-spectral image data, precisely delineates the extent affected by the landslide. The landslide encompassed a runout distance of 678 m, featuring an initiation zone characterized by an average slope of 35°. Notably, the eroded and deposited areas measured 2.55 × 104 m2 and 1.72 × 104 m2, respectively. The acquired UAV-LiDAR data further reveal the eroded and deposited landslide volumes approximately measuring 5.60 × 104 m3 and 1.58 × 104 m3, respectively. This study contributes a valuable dataset on a rainfall-induced landslide with a long runout debris flow, underscoring the effectiveness of multi-source remote sensing technology in monitoring and comprehending complex landslide events.

Preoperative Serum Copeptin Can Predict Delayed Hyponatremia after Pituitary Surgery in the Absence of Arginine Vasopressin Deficiency.

BACKGRUOUND: Delayed postoperative hyponatremia (DPH) is the most common cause of readmission after pituitary surgery. In this study, we aimed to evaluate the cutoff values of serum copeptin and determine the optimal timing for copeptin measurement for the prediction of the occurrence of DPH in patients who undergo endoscopic transsphenoidal approach (eTSA) surgery and tumor resection. METHODS: This was a prospective observational study of 73 patients who underwent eTSA surgery for pituitary or stalk lesions. Copeptin levels were measured before surgery, 1 hour after extubation, and on postoperative days 1, 2, 7, and 90. RESULTS: Among 73 patients, 23 patients (31.5%) developed DPH. The baseline ratio of copeptin to serum sodium level showed the highest predictive performance (area under the curve [AUROC], 0.699), and its optimal cutoff to maximize Youden's index was 2.5×10-11, with a sensitivity of 91.3% and negative predictive value of 92.0%. No significant predictors were identified for patients with transient arginine vasopressin (AVP) deficiency. However, for patients without transient AVP deficiency, the copeptin-to-urine osmolarity ratio at baseline demonstrated the highest predictive performance (AUROC, 0.725). An optimal cutoff of 6.5×10-12 maximized Youden's index, with a sensitivity of 92.9% and a negative predictive value of 94.1%. CONCLUSION: The occurrence of DPH can be predicted using baseline copeptin and its ratio with serum sodium or urine osmolarity only in patients without transient AVP deficiency after pituitary surgery.

Discovery of selective LATS inhibitors via scaffold hopping: enhancing drug-likeness and kinase selectivity for potential applications in regenerative medicine.

Due to its essential roles in cell proliferation and apoptosis, the precise regulation of the Hippo pathway through LATS presents a viable biological target for developing new drugs for cancer and regenerative diseases. However, currently available probes for selective and highly drug-like inhibition of LATS require further improvement in terms of both activity, selectivity and drug-like properties. Through scaffold hopping aided by docking studies and AI-assisted prediction of metabolic stabilities, we successfully identified an advanced LATS inhibitor demonstrating potent kinase activity, exceptional selectivity against other kinases, and superior oral pharmacokinetic profiles.

NUAK2 Inhibitors, KHKI-01128 and KHKI-01215, Exhibit Potent Anticancer Activity Against SW480 Colorectal Cancer Cells.

BACKGROUND/AIM: NUAK family kinase 2 (NUAK2) is a promising target for cancer therapeutics due to its reported role in protein phosphorylation, a critical process in cancer cell survival, proliferation, invasion, and senescence. This study aimed to identify novel inhibitors that disrupt NUAK2 activity. We have already identified two KRICT Hippo kinase inhibitor (KHKI) compounds, such as KHKI-01128 and KHKI-01215. Our aim was to evaluate the impact of KHKI-01128 and KHKI-01215 on NUAK2 activity and elucidate its mechanism in colorectal cancer cells. MATERIALS AND METHODS: To evaluate anticancer properties of these inhibitors, four in vitro assays in the SW480 cell line (time-resolved fluorescence resonance energy transfer assay, KINOMEscan kinase profiling, viability, and apoptosis assays) and two pharmacological mechanism analyses (Gene Set Enrichment Analysis and western blotting) were performed. RESULTS: KHKI-01128 and KHKI-01215 exhibited potent inhibitory activity against NUAK2 (half-maximal inhibitory concentration=0.024±0.015 µM and 0.052±0.011 µM, respectively). These inhibitors suppressed cell proliferation, with half-maximal inhibitory concentrations of 1.26±0.17 µM and 3.16±0.30 µM, respectively, and induced apoptosis of SW480 cells. Gene Set Enrichment Analysis revealed negative enrichment scores of -0.84 for KHKI-01128 (false-discovery rate=0.70) and 1.37 for KHKI-01215 (false-discovery rate=0.18), indicating that both effectively suppressed the expression of YES1-associated transcriptional regulator (YAP) target genes. CONCLUSION: These results suggest that KHKI-01128 and KHKI-01215 are potent NUAK2 inhibitors with promising potential for pharmaceutical applications.

The Asian project for collaborative derivation of reference intervals: (2) results of non-standardized analytes and transference of reference intervals to the participating laboratories on the basis of cross-comparison of test results.

BACKGROUND: The 2009 Asian multicenter study for derivation of reference intervals (RIs) featured: 1) centralized measurements to exclude reagent-dependent variations; 2) inclusion of non-standardized analytes (hormones, tumor makers, etc.) in the target; and 3) cross-check of test results between the central and local laboratories. Transferability of centrally derived RIs for non-standardized analytes based on the cross-check was examined. METHODS: Forty non-standardized analytes were centrally measured in sera from 3541 reference individuals recruited by 63 laboratories. Forty-four laboratories collaborated in the cross-check study by locally measuring aliquots of sera from 9 to 73 volunteers (average 22.2). Linear relationships were obtained by the major-axis regression. Error in converting RIs using the regression line was expressed by the coefficient of variation of slope b [CV(b)]. CV(b) <10% was set as the cut-off value allowing the conversion. The significance of factors for partitioning RIs was determined similarly as in the first report. RESULTS: Significant sex-, age-, and region-related changes in test results were observed in 17, 15, and 11 of the 40 analytes, respectively. In the cross-comparison study, test results were not harmonized in the majority of immunologically measured analytes, but their average CV(b)s were <10% except for total protein, cystatin C, CA19-9, free thyroxine, and triiodothyronine. After conversion, 74% of centrally derived RIs were transferred to each local laboratory. CONCLUSIONS: Our results point to the feasibility of: 1) harmonizing test results across different laboratories; and 2) sharing centrally derived RIs of non-standardized analytes by means of comparative measurement of a set of commutable specimens.

Intramolecular cyclization of N-cyano sulfoximines by N-CN bond activation.

Metal-free halogenated anhydrides promote the intramolecular cyclization of N-cyano sulfoximines. Trifluoro- or trichloroacetic anhydride (TFAA or TCAA, respectively) activate the N-cyano groups of N-cyano sulfoximines, leading to the intramolecular cyclization of 2-benzamide-N-cyano sulfoximines 1. This method results in excellent yields of thiadiazinone 1-oxides 2. A full intramolecular cyclization pattern was suggested by (i) labeling experiments with 13C, (ii) isolating of N-trifluoroacetyl sulfoximine 1ac, and (iii) confirming the generation of the intermediate 1ad by LC/MS analysis.

N-Cyano sulfilimine functional group as a nonclassical amide bond bioisostere in the design of a potent analogue to anthranilic diamide insecticide.

To explore the potential of the N-cyano sulfilimine group as an amide bond isostere, a derivative of the blockbuster anthranilic diamide, chlorantramiliprole, was synthesized and evaluated with regard to its physicochemical properties, permeability, and biological activity. Given the combination of N-cyano sulfilimine chlorantraniliprole 1 and its strong hydrogen bond acceptor character, high permeability, and excellent insecticidal activity, the N-cyano sulfilimine functional group could be considered as an amide bond isostere.