Synthesis and Structural Characterization of Macrocyclic α-ABpeptoids and Their DNA-Encoded Library.

The first synthesis of macrocyclic α-ABpeptoids with varying lengths is described. X-ray crystal structures reveal that cyclic trimer displays a chair-like conformation with a cct amide sequence and cyclic tetramer has a saddle-like structure with an uncommon cccc amide arrangement. The creation of a DNA-encoded combinatorial library of macrocyclic α-ABpeptoids is described.

Uncovering Nitrosyl Reactivity at N-Heterocyclic Carbene Center.

N-heterocyclic carbenes (NHCs) have garnered much attention due to their unique properties, such as strong σ-donating and π-accepting abilities, as well as their transition-metal-like reactivity toward small molecules. In 2015, we discovered that NHCs can react with nitric oxide (NO) gas to form radical adducts that resemble transition metal nitrosyl complexes. To elucidate the analogy between NHC and transition metal NO adducts, here we have undertaken a systematic investigation of the electron- and proton-transfer chemistry of [NHC-NO]⋅ (N-heterocyclic carbene nitric oxide radical) compounds. We have accessed a suite of compounds, comprised of [NHC-NO]+ , [NHC-NO]- , [NHC-NOH]0 , and [NHC-NHOH]+ species. In particular, [NHC-NO]- was isolated as potassium and lithium ion adducts. Most interestingly, a monomeric potassium [NHC-NO]- compound was isolated with the assistance of 18-crown-6, which is the first instance of a monomeric alkali N-oxyl compound to the best of our knowledge. Our results demonstrate that [NHC-NO]⋅ exhibits redox behavior broadly similar to metal nitrosyl complexes, which opens up more possibilities for utilizing NHCs to build on the known reactivity of metal complexes.

Formation of Highly Stable 1,2-Dicarbonyl Organic Radicals from Cyclic (Alkyl)(amino)carbenes.

Two air-stable organic radicals derived from oxalyl chloride and cAAC were synthesized, resulting in the unexpected formation of a known (amino)(carboxy) radical cation ([2]BF4) and the oxidative formation of a 1,2-dicarbonyl radical cation ([3]BF4) from a neutral 3-oxetanone compound (4). The highly strained and newly discovered 4 was obtained by a single-electron reduction of [3]BF4 with a mild reducing agent. This result differs from the generation of NHC-based 1,2-dicarbonyl radicals, indicating the uniqueness of cAAC.

Clinical study of colorectal cancer operation: Survival analysis.

Purpose: Overall 5-year survival rates for colon and rectal cancer reported recently by the American Cancer Society were 89%, 90% for localized disease, 71%, 71% for regional disease, and 14%, 15% for distant disease. But the results of survival rate of colorectal cancer in a single institution were very rare. The aim of this study is to evaluate surgical results and survival rates of colorectal cancer. Methods: We conducted a retrospective study with patients who underwent curative resection for a primary colorectal adenocarcinoma between 2009 and 2018. Results: Five-year overall and disease-free survival were 79.5% and 69.9%, respectively. The overall 5-year survival by stages was 94.7% in stage I, 88.4% in stage II, 74.3% in stage III and 31.5% in stage IV. Five-year disease-free survival was 91% in stage I, 79.8% in stage II, 63.3% in stage III, and 18.9% in stage IV. The overall 5-year survival in rectal cancer was superior to colon cancer (P=0.014) while there was no difference in 5-year disease-free survival (P=0.338). Overall survival in female patients was better than male patient (P=0.029). Overall survival by age was worst in group of less than 40 years old (62.5%), and best in group between 41 and 65 years old (86.5%). Postoperative mortality within 30 days was 0.4%, and the recurrence rate was 19.2%. Conclusion: With the development of surgical skills and various treatments, postoperative outcome of colorectal cancer is expected to improve. It may be helpful for surgeons to improve their surgical outcomes when they review their data and conduct active researches.

Hourglass-like constriction neuropathy of the suprascapular nerve detected by high-resolution magnetic resonance neurography: report of three patients.

Hourglass-like constriction neuropathy is a neurological condition caused by non-traumatic, non-compressive fascicular constrictions of one or more individual peripheral nerves. Based on clinical manifestations, it is very difficult to differentiate hourglass-like constriction neuropathy from idiopathic neuralgic amyotrophy. Focal hourglass-like constriction neuropathy may be erroneously diagnosed as idiopathic neuralgic amyotrophy. Previous studies demonstrated hourglass-like constrictions of peripheral nerves in the surgical exploration of patients diagnosed with idiopathic neuralgic amyotrophy. Recently, high-resolution ultrasound or magnetic resonance neurography (MRN) have been introduced to detect focal hourglass-like constrictions of peripheral nerves in spontaneous nerve palsy. We present a series of three cases in which the suprascapular nerve was affected by hourglass-like constrictions, which were visualized by high-solution MRN, including a nerve-selective morphological MR pulse sequence with strong fat- and water-signal suppression.

Phenylacylphenol derivatives with anti-melanogenic activity from Stewartia pseudocamellia.

Three new phenylacylphenol derivatives, stewartianol (1), deoxystewartianol-4'-O-arabinoglucoside (2), and stewartianol-3-O-glucoside (3), along with nine known compounds, methylesculin (4), fraxoside (5), fraxetin (6), scopletin (7), (+)-dihydromyricetin (8), (+)-taxifolin-7-O-ß-D-glucose (9), (+)-taxifolin (10), (+)-dihydrokaempferol-7-O-ß-D-glucose (11), and 3-acetyl-ursolic acid (12), were isolated from the twigs of Stewartia pseudocamellia; commonly used as folk medicine in Korea. The structures of the isolated compounds were identified using spectroscopic analysis, including 1D, 2D NMR, MS and compared with published data. The compounds were tested for their anti-melanogenic activity in cultured murine B16 melanoma cells. Stewartianol (1) and stewartianol-3-O-glucoside (3) showed an inhibitory effect significantly on melanogenesis in a concentration-dependent manner.

Triterpene glycosides with stimulatory activity on melanogenesis from the aerial parts of Weigela subsessilis.

Three new triterpene glycosides (Lonicerosides K, L and M) and 11 known compounds were isolated from the aerial parts of Weigela subsessilis. Among the known isolated compounds, loniceroside A, sweroside, kaempferol-3-O-glucopyranoside 6″-(3-hydroxy-3-methylglutarate), kaempferol-3-O-acetylglucoside and grandifloroside were reported for the first time in a Weigela genus plant. Their chemical structures were identified using extensive spectroscopic analysis including two-dimensional (2D)-NMR experiments, HR-ESI-QTOF-MS and comparison with reported data. Among these compounds, lonicerosides A and L had potent melanogenesis stimulatory activity in murine B16F0 melanoma cells. The structural relationship of active compounds was discussed.

High altitude remains associated with elevated suicide rates after adjusting for socioeconomic status: a study from South Korea.

There have been several studies supporting a possible relationship between high suicide rate and high altitude. However socioeconomic status may confound this association because low socioeconomic status, which is known to be related to a high suicide rate, is also associated with living at high altitude. This study aims to explore whether the relationship between high altitude and high suicide rate remains after adjusting for socioeconomic status in South Korea. We collected demographic data of completed suicides, the mean altitude of the district where each suicide took place, and the mean income of each district. We analyzed the data using regression analysis before and after adjustment for mean income. We found that there is a positive correlation between altitude and suicide rate, even after adjustment for mean income. Thus, altitude appears to be an independent risk factor for suicide.