Effect of diazocine combined with sufentanil analgesia after radical operation for esophageal cancer on the release of neurotransmitters and stress mediators

Objective:To study the effect of diazocine combined with sufentanil analgesia after radical operation for esophageal cancer on release of neurotransmitters and stress mediators.Methods:A total of 170 cases of patients with primary esophageal cancer who underwent surgical treatment in this hospital between September 2015 and May 2017 were divided into control group (n=85) and study group (n=85) by random number table method. Control group received postoperative sufentanil analgesia, and study group received postoperative diazocine combined with sufentanil analgesia. The differences in the perioperative contents of monoamine neurotransmitters, amino acid neurotransmitters and stress mediators were compared between the two groups.Results: Before operation, there was no statistically significant difference in the serum contents of monoamine neurotransmitters, amino acid neurotransmitters and stress mediators between the two groups. 12 h after surgery, 24 h after surgery and 36 h after surgery, serum monoamine neurotransmitters DA, NE and 5-HT contents of study group were lower than those of control group;amino acid neurotransmitters Ach, GABA and Glu contents were higher than those of control group;serum stress mediators ACTH, ALD and Cor contents were lower than those of control group.Conclusion: diazocine combined with sufentanil analgesia after radical operation for esophageal cancer can effectively optimize the secretion of neurotransmitters and inhibit the synthesis of stress mediators to alleviate the patients' pain perception.

π-Fused Diazocines with Controllable Photoswitching Properties as Molecular Tweezers

Diazocines,a type of photoswitch molecules,are distinguished by their unique conformation and photochromic properties.Molecular engineering of diazocines,especially theπ-extended ones,remains challenging due to limited synthetic methods.Here,we developed threeπ-fused diazocines(BAZO-1,BAZO-2,and BAZO-3)via Bischler–Napieralski cyclization.Their isomerizations(Z⇆E)were switchable under visible light sources(427 and 630 nm).The size of theirπ-extension exerted a significant influence on the isomerization process,whereby the biggest fourfold ring-closure diazocine(BAZO-3)showed the fastest conversion rate(Z→E).Notably,the half-life(t1/2)of the E isomer of BAZO-3 was 14.6 times higher than that of the twofold ring-closure BAZO-1.Thus,BAZO-3 acted as a molecular tweezer based on double N-embedded pyrene units,allowing it to bind to pyrene through supramolecular interactions.This work may pave the way for designing novel photoswitches with long half-lives and lightcontrolled properties.

Catalytic Asymmetric Synthesis of Inherently Chiral Saddle- Shaped Dibenzo[b,fI[1,5]diazocines

Dibenzo[b,fi[1,5]diazocines are a class of eight-membered heterocycles,which exhibit unique rigid saddle-shaped structure and possess inherent chirality.In this study,we report a convenient and straightforward method for the catalytic enantioselective synthesis of these unique chiral molecules through chiral phosphoric acid-catalyzed dimerization of 2-acylbenzoisocyanates.Notably,the addition of corresponding 2-acylaniline as the co-catalyst significantly improved the efficiency of these reactions,and a simple phase separation operation resulted in products with excellent enantiopurity.Experimental studies were performed to elucidate the mechanism behind these reactions,leading to the proposal of a plausible reaction mechanism based on the study findings.

Inherently Chiral 6,7-Diphenyldibenzo [e,g][1,4]diazocine: Enantioselective Synthesis and Application as a Ligand Platform

Inherently chiral 6,7-diphenyldibenzo[e,g][1,4]diazocine(DDD)has been synthesized enantioselectively for the first time via chiral phosphoric acid(CPA)-catalyzed cyclocondensation of readily available[1,1′-biphenyl]-2,2′-diamine(1a)and benzil(2a)in 82%yield,with 98%ee under mild reaction conditions.The strategy could also be applied to racemic biaryl diamines through kinetic resolution.The unexpectedly high interconversion energy barriers between the enantiomers(ΔG=39.5 kcal/mol)and the chemical stability rendered DDD an ideal platform for developing new chiral ligands and catalysts.Unique inherently chiralDDD-based phosphoramidites,phosphoric acid,mono-and diphosphine ligands were prepared from optically pure diphenol derivative DDDOL as a common precursor.Preliminary asymmetric reactions catalyzed by Pd or Rh in the presence of newly developed ligands exhibited comparable or even better enantioselectivities than the corresponding BINOLor SPINOL-derived ligands.Density functional theory calculation revealed the origin of the enantioselectivity during the process.

Diazocine as a Versatile Building Block Enables Excellent Photoswitching and Chromic Properties in Self-Assembled Organogels

Novel types of photoresponsive organogelators containing a diazocine moiety have been synthesized,and their gelation behaviors have been characterized systematically.Subtle changes in the pendant structure of these bent-core molecules cause significant changes in the molecular packing mode in their self-assembled gels.By making use of the unconventional conformational and photochromic properties of the diazocine core,the obtained gels exhibited excellent photoswitching and-chromic properties.For the first time,the diazocine unit has been demonstrated as a versatile building block to construct photoresponsive supramolecular gels.The sensitive interconversion between multiple states of these chromic gels highlights their promising applications in fabricating logic gates with appropriate addressing mode(stimulated by visible light or heating).

Synthesis of Novel Scolopendra-type Polydodecyloxybenzoyl[1,5]-diazocine as New Material for Optical Sensor

A new scolopendra-type polymer of polydodecyloxybenzoyl[1,5]-diazocine（PDBD） was designed and prepared using 2,5-bis（4-（dodecyloxy）-benzoyl）terephthaloyl azide with trifluoroacetic acid（TFA） via one-pot reaction in good yields. The structure of polymer was characterized using ~1 H-NMR, ^（13） C-NMR and MALDI-TOF spectra. The polymer PDBD exhibits good thermal stability as measured by TGA and DSC, and can be dissolved well in common organic solvents such as chloroform and tetrahydrofuran. In addition, UV-Vis spectral studies indicate that the polymer PDBD shows unique optical property changes（protonation/deprotonation） in the different trifluoroacetic acid environments. The new polymer is expected to be utilized as an optical functional material for fabricating optical sensors in environmental and biological fields.

A New Saddle-Shaped Aza Analog of Tetraphenylene: Atroposelective Synthesis and Application as a Chiral Acylating Reagent

(Z)-7-Aryl-5-acyldibenzo[e,g][1,4]diazocin-6(5H)-one,a unique saddle-shaped bridged biaryl containing synchronized aryl–aryl and N-aryl stereogenic axes,was constructed for the first time in good yields with up to 96%enantiomeric excess(ee).The threecomponent coupling reaction,involving aryl iodide,2,2′-diisocyano-1,1′-biphenyl,and carboxylate,constructs the eight-membered ring in an atroposelective manner through palladium-catalyzed double isocyanide insertion followed by C–Obond formation during reductive elimination and amide formation after acyl transfer.