Multiphoton-excited DUV photolithography for 3D nanofabrication

Light-matter interactions in the deep ultraviolet (DUV) wavelength region exhibits a variety of optical effects such as luminescence, photoisomerization, and polymerization in many materials. Despite the rich photochemistry and high spatial resolution due to the short wavelength, the notorious lack of DUV-compatible optical components and devices precludes use of DUV light in microscopy and lithography as a routine laboratory tool. Here, we present the use of two-photon excitation with visible laser light to realizes photo-polymerization of molecules with an excitation energy equivalent to DUV light. Using standard optics for visible light, methacrylate oligomers were polymerized with 400 nm femtosecond pulses without any addition of photo-initiators and sensitizers. By scanning the laser focus in 3D, a series of fine 3D structures were created with the smallest resolved line-space features of 80 nm. We found DUV polymerizations induced by two-photon absorption is surprisingly efficient and requires laser intensity only on the order of 100 kW/cm^2. With the variety of successful demonstrations including organic- and inorganic-material-made-structures presented, our direct nano-3D-printing method would be a valuable tool for nanofabrication in 3D

First Asymmetric Total Syntheses of Fawcettimine-Type <i>Lycopodium</i> Alkaloids, Lycoposerramine-C and Phlegmariurine-A

A successful asymmetric total synthesis of lycoposerramine-C involving such key steps as a cobalt-mediated Pauson−Khand reaction and vinyl Claisen rearrangement and its biomimetic transformation to phlegmariurine-A are described

First Asymmetric Total Syntheses of Fawcettimine-Type <i>Lycopodium</i> Alkaloids, Lycoposerramine-C and Phlegmariurine-A

A successful asymmetric total synthesis of lycoposerramine-C involving such key steps as a cobalt-mediated Pauson−Khand reaction and vinyl Claisen rearrangement and its biomimetic transformation to phlegmariurine-A are described

Total Synthesis of [Ψ[C(NH)NH]Tpg⁴]Vancomycin and its (4-Chlorobiphenyl)methyl Derivative: Impact of Peripheral Modifications on Vancomycin Analogues Redesigned for Dual d‑Ala‑d‑Ala and d‑Ala‑d‑Lac Binding

The total synthesis of two key analogues of vancomycin containing single-atom exchanges in the binding pocket (residue 4 amidine and thioamide) are disclosed as well as their peripherally modified (4-chlorobiphenyl)­methyl (CBP) derivatives. Their assessment indicates that combined pocket amidine and CBP peripherally modified analogues exhibit a remarkable spectrum of antimicrobial activity (VSSA, MRSA, VanA and VanB VRE) and impressive potencies (MIC = 0.06–0.005 μg/mL) against both vancomycin-sensitive and -resistant bacteria and likely benefit from two independent and synergistic mechanisms of action. Like vancomycin, such analogues are likely to display especially durable antibiotic activity not prone to rapidly acquired clinical resistance

Stereoselective Syntheses of <i>trans</i>-Anhydromevalonic Acid and <i>trans</i>-Anhydromevalonyl Group-Containing Natural Products

Collective total syntheses of trans-anhydromevalonic acid (tAHMA) and trans-anhydromevalonyl (tAHM) group-containing natural products (pestalotiopin A, pestalotiopamide C, pestalotiopamide D, farinomalein E, eleutherazine B, and trichocyclodipeptide A) were achieved using tAHMA esters as key intermediates. To this end, tAHMA tert-butyl ester was newly prepared by Z-vinyltosylation of tert-butyl 3-oxo-5-((triisopropylsilyl)­oxy)­pentanoate followed by the Negishi cross-coupling reaction with Me2Zn. tAHMA esters were converted to the target natural products via esterification or amidation. Comparison of the spectroscopic data of synthetic and natural products confirmed the E-configuration of the tAHM moieties in the natural products

First Total Syntheses of Beauvericin A and <i>allo</i>-Beauvericin A

The first total syntheses of beauvericin A and allo-beauvericin A were achieved. N-Methyl-l-phenylalanine, (2R)-hydroxylvaleric acid, and (2R,3S)- or (2R,3R)-2-hydroxy-2-methylpentanoic acid were linked and cyclized to form the target natural products. The structure of synthetic beauvericin A was confirmed by X-ray crystallographic analysis. NMR data of the synthetic beauvericins were identical with those of the reported natural products. These results secure the structures of natural products, as originally proposed in the isolation studies

Univariate analysis.

Preoperative nutritional status is an important prognostic factor in gastric cancer patients. This study will evaluate whether preoperative oral dysfunction is associated with prognostic nutrition index (PNI). This case-control study analyzed 95 patients who underwent oral function management. We assessed the following parameters: body mass index, stage of gastric cancer, C-reactive protein, total lymphocyte count, albumin, and prognostic nutritional index. The patients were divided into groups with prognostic nutritional indexes 45. Logistic regression analysis was used to assess the association between the measurements of oral function and the prognostic nutritional index. Univariate analysis of factors associated with decreased oral function and prognostic nutritional index showed significant differences between the two groups in C-reactive protein, neutrophils, and tongue pressure (p</div

Multivariate logistic regression: Logistic regression analysis with oral hypofunction as the objective variable.

Multivariate logistic regression: Logistic regression analysis with oral hypofunction as the objective variable.</p

Patient background.

Preoperative nutritional status is an important prognostic factor in gastric cancer patients. This study will evaluate whether preoperative oral dysfunction is associated with prognostic nutrition index (PNI). This case-control study analyzed 95 patients who underwent oral function management. We assessed the following parameters: body mass index, stage of gastric cancer, C-reactive protein, total lymphocyte count, albumin, and prognostic nutritional index. The patients were divided into groups with prognostic nutritional indexes 45. Logistic regression analysis was used to assess the association between the measurements of oral function and the prognostic nutritional index. Univariate analysis of factors associated with decreased oral function and prognostic nutritional index showed significant differences between the two groups in C-reactive protein, neutrophils, and tongue pressure (p</div

Flow diagram of exam selection.

Preoperative nutritional status is an important prognostic factor in gastric cancer patients. This study will evaluate whether preoperative oral dysfunction is associated with prognostic nutrition index (PNI). This case-control study analyzed 95 patients who underwent oral function management. We assessed the following parameters: body mass index, stage of gastric cancer, C-reactive protein, total lymphocyte count, albumin, and prognostic nutritional index. The patients were divided into groups with prognostic nutritional indexes 45. Logistic regression analysis was used to assess the association between the measurements of oral function and the prognostic nutritional index. Univariate analysis of factors associated with decreased oral function and prognostic nutritional index showed significant differences between the two groups in C-reactive protein, neutrophils, and tongue pressure (p</div