Intuition and we-ness in Bion and post-Bionian field theory.

"Intuition" is probably the most frequently used term in all Bion's writings. However, in order to understand its role in his thought it is essential to give it the clearest possible definition. The thesis of this article is that by intuition Bion means a "specific" psychoanalytic concept. It is thus possible to extract intuition from the vague and mystifying reading of it by some authors, whic runs the risk of falling into an empty "intuitionism". For Bion, intuition is a psychoanalytic function of the analyst, the principal factors of which are the various expressions of dream-thought and insight. Furthermore, within the frame of the post-Bionian theory of the analytic field, the author suggests adding to these factors the use of the "we" vertex (or we-ness), i.e. to regard virtually every fact of analysis as co-created. The aim is to make the very concept of "field" more accessible. Compared with the metaphor of the analytic field, the concept of we-ness has both greater clinical versatility and greater pregnancy on the metapsychological plane. Indeed, it more directly reflects a radically social conception of human subjectivity: what is known in contemporary speculative thought - in J-L. Nancy, for example - as the "ontology of we".

Anti-Cancer Mechanisms of Diarylpentanoid MS17 (1,5-Bis(2-hydroxyphenyl)-1,4-pentadiene-3-one) in Human Colon Cancer Cells: A Proteomics Approach.

Diarylpentanoids are synthesized to overcome curcumin's poor bioavailability and low stability to show enhanced anti-cancer effects. Little is known about the anti-cancer effects of diarylpentanoid MS17 (1,5-bis(2-hydroxyphenyl)-1,4-pentadiene-3-one) in colon cancer cells. This study aimed to elucidate molecular mechanisms and pathways modulated by MS17 in colon cancer based on proteomic profiling of primary SW480 and metastatic SW620 colon cancer cells. Cytotoxicity and apoptotic effects of MS17 were investigated using MTT assay, morphological studies, and Simple Western analysis. Proteomic profiling using LC/MS analysis identified differentially expressed proteins (DEPs) in MS17-treated cells, with further analysis in protein classification, gene ontology enrichment, protein-protein interaction network and Reactome pathway analysis. MS17 had lower EC50 values (SW480: 4.10 µM; SW620: 2.50 µM) than curcumin (SW480: 17.50 µM; SW620: 13.10 µM) with a greater anti-proliferative effect. MS17 treatment of 1× EC50 induced apoptotic changes in the morphology of SW480 and SW620 cells upon 24 h treatment. A total of 24 and 92 DEPs (fold change ≥ 1.50) were identified in SW480 and SW620 cells, respectively, upon MS17 treatment of 2× EC50 for 24 h. Pathway analysis showed that MS17 may induce its anti-cancer effects in both cells via selected DEPs associated with the top enriched molecular pathways. RPL and RPS ribosomal proteins, heat shock proteins (HSPs) and ubiquitin-protein ligases (UBB and UBC) were significantly associated with cellular responses to stress in SW480 and SW620 cells. Our findings suggest that MS17 may facilitate the anti-proliferative and apoptotic activities in primary (SW480) and metastatic (SW620) human colon cancer cells via the cellular responses to stress pathway. Further investigation is essential to determine the alternative apoptotic mechanisms of MS17 that are independent of caspase-3 activity and Bcl-2 protein expression in these cells. MS17 could be a potential anti-cancer agent in primary and metastatic colon cancer cells.

Enantio- and Diastereodivergent Cyclopropanation of Allenes by Directed Evolution of an Iridium-Containing Cytochrome.

Alkylidene cyclopropanes (ACPs) are valuable synthetic intermediates because of their constrained structure and opportunities for further diversification. Although routes to ACPs are known, preparations of ACPs with control of both the configuration of the cyclopropyl (R vs S) group and the geometry of the alkene (E vs Z) are unknown. We describe enzymatic cyclopropanation of allenes with ethyl diazoacetate (EDA) catalyzed by an iridium-containing cytochrome (Ir(Me)-CYP119) that controls both stereochemical elements. Two mutants of Ir(Me)-CYP119 identified by 6-codon (6c, VILAFG) saturation mutagenesis catalyze the formation of (E)-ACPs with -93% to >99% ee and >99:1 E/Z ratio with just three rounds of 96 mutants. By four additional rounds of mutagenesis, an enzyme variant was identified that forms (Z)-ACPs with up to 94% ee and a 28:72 E/Z ratio. Computational studies show that the orientation of the carbene unit dictated by the mutated positions accounts for the stereoselectivity.

Conformational Analysis of 1,5-Diaryl-3-Oxo-1,4-Pentadiene Derivatives: A Nuclear Overhauser Effect Spectroscopy Investigation.

1,5-Diaryl-3-Oxo-1,4-Pentadiene derivatives are intriguing organic compounds with a unique structure featuring a pentadiene core, aryl groups, and a ketone group. This study investigates the influence of fluorine atoms on the conformational features of these derivatives in deuterated chloroform (CDCl3) solution. Through nuclear magnetic resonance (NMR) spectroscopy and quantum chemical calculations, we discerned variations in interatomic distances and established predominant conformer proportions. The findings suggest that the non-fluorinated entity exhibits a uniform distribution across various conformer groups. The introduction of a fluorine atom induces substantial alterations, resulting in the predominance of a specific conformer group. This structural insight may hold the key to their diverse anticancer activities, previously reported in the literature.

Diatomic iron nanozyme with lipoxidase-like activity for efficient inactivation of enveloped virus.

Enveloped viruses encased within a lipid bilayer membrane are highly contagious and can cause many infectious diseases like influenza and COVID-19, thus calling for effective prevention and inactivation strategies. Here, we develop a diatomic iron nanozyme with lipoxidase-like (LOX-like) activity for the inactivation of enveloped virus. The diatomic iron sites can destruct the viral envelope via lipid peroxidation, thus displaying non-specific virucidal property. In contrast, natural LOX exhibits low antiviral performance, manifesting the advantage of nanozyme over the natural enzyme. Theoretical studies suggest that the Fe-O-Fe motif can match well the energy levels of Fe2 minority ß-spin d orbitals and pentadiene moiety π* orbitals, and thus significantly lower the activation barrier of cis,cis-1,4-pentadiene moiety in the vesicle membrane. We showcase that the diatomic iron nanozyme can be incorporated into air purifier to disinfect airborne flu virus. The present strategy promises a future application in comprehensive biosecurity control.

Weaving deceptive webs and untangling emotional truths.

This paper explores how the allure of magical thinking and groupthink contrasts with intuition of emotional truth. Since truth can terrify, the author suggests that a longer learning curve is needed to apprehend what Bion (1970a) called the "evolving O" of the analytic session. Traumatized patients are described as dream weavers who spin webs of partial truths and lies around their true selves. For the analyst, untangling these webs involves what Bion (1970b) calls an "act of faith." Clinical material is presented to show how groupthink and other concretions of thought can, under favorable circumstances, be transformed on the wings of psychic truth. Alternatively, uncontained violent emotions can become calcified, creating a carapace over the chrysalis of the patient's true self. The author concludes that the analyst's desire for a particular treatment outcome can unwittingly lead to the formation of an adhesive web where healthy analytic culture becomes a cult. Paradoxically, it is only when there is equal attention to emotional truth and lies that a trajectory of growth is likely to evolve.

Regio- and Stereoselective Allylation of Anilines with Aryl Allenes in Hexafluoroisopropanol Solvent.

A regio- and stereoselective allylation of N-unsubstituted anilines has been developed that explores aryl allenes as masked allyl synthons and a combination of Mg(OTf)2/HFIP as an effective proton source. The protocol is operationally simple and scalable and offers high yields of diverse p-allyl anilines bearing an olefin motif with exclusive E-geometry. The methodology was also suitable for the regioselective allylation of indole and can be advanced in a three-component reaction mode using NIS activator. The alteration of the catalytic system with TfOH resulted in the regioselective difunctionalization of allenes, which follows an allylation/hydroarylation cascade.

Cyclic Allene Approach to the Manzamine Alkaloid Keramaphidin B.

We report an approach to the core of the manzamine alkaloid keramaphidin B that relies on the strain-promoted cycloaddition of an azacyclic allene with a pyrone trapping partner. The cycloaddition is tolerant of nitrile and primary amide functional groups and can be complemented with a subsequent retro-Diels-Alder step. These efforts demonstrate that strained cyclic allenes can be used to build significant structural complexity and should encourage further studies of these fleeting intermediates.

A Metapsychology of the Unrepresented.

The terms unrepresented and unrepresented states are increasingly being referred to in psychoanalytic discourse, without our having established a generally agreed upon consensus about their definition, use or meaning. While these particular designations were never used by Freud, a careful reading of his work reveals them to be qualities that characterize the initial state of both the drive and perception. This paper attempts to place these terms in a clinically useful, metapsychological perspective by reviewing their conceptual origin in Freud and examining their elaboration and clinical relevance in the work of Bion, Winnicott, and Green. These concepts should prove especially useful for understanding and addressing problems presented by non-neurotic patients and psychic organizations and will help expand the reach and efficacy of psychoanalytic understanding and technique to increasing numbers of contemporary patients.

Organogermanium Analogues of Alkenes, Alkynes, 1,3-Dienes, Allenes, and Vinylidenes.

In this review, the latest achievements in the field of multiply bonded organogermanium derivatives, mostly reported within the last two decades, are presented. The isolable Ge-containing analogues of alkenes, alkynes, 1,3-dienes, allenes, and vinylidenes are discussed, and for each class of unsaturated organogermanium compounds, the most representative examples are given. The synthetic approaches toward homonuclear multiply bonded combinations solely consisting of germanium atoms, and their heteronuclear variants containing germanium and other group 14 elements, both acyclic and cyclic, are discussed. The peculiar structural features and nonclassical bonding nature of the abovementioned compounds are discussed based on their spectroscopic and structural characteristics, in particular their crystallographic parameters (double bond length, trans-bending at the doubly bonded centers, and twisting about the double bond). The prospects for the practical use of the title compounds in synthetic and catalytic fields are also briefly discussed.

Design, Synthesis and Antifungal Activity of Novel 1,4-Pentadiene-3-one Containing Quinazolinone.

Twenty 1,4-pentadiene-3-one derivatives containing quinazolinone (W1-W20) were designed and synthesized. The bioactivity test results showed that some compounds had antifungal activities in vitro. W12 showed excellent bioactivity against Sclerotinia sclerotiorum (S. sclerotiorum) and Phomopsis sp., with EC50 values of 0.70 and 3.84 µg/mL, which are higher than those of the control drug azoxystrobin at 8.15 and 17.25 µg/mL. In vivo activity tests were carried out on oilseed rape and kiwifruit. The protective effect of W12 on oilseed rape infected with S. sclerotiorum (91.7 and 87.3%) was better than that of azoxystrobin (90.2 and 79.8%) at 100 and 50 µg/mL, respectively, and the protective effect on kiwifruit infected with Phomopsis sp. (96.2%) was better than that of azoxystrobin (94.6%) at 200 µg/mL. Scanning electron microscopy results showed the hyphae of S. sclerotiorum treated with compound W12 abnormally collapsed and shriveled, inhibiting the growth of mycelium and, thus, laying the inhibiting effect on S. sclerotiorum. The results of the mechanism research showed that the action of W12 changed the mycelial morphology of S. sclerotiorum, affected the permeability of cells, increased the leakage of cytoplasm and allowed the cell membrane to break down. This study shows that 1,4-pentadiene-3-one derivatives containing quinazolinone have good effects on plant fungi and the potential for becoming new fungicides.

Oxygenation of Anandamide by Lipoxygenases.

The endocannabinoids anandamide and 2-arachidonoylglycerol are not only metabolized by serine hydrolases, such as fatty acid amide hydrolase, monoacylglycerol lipase, and α,ß-hydrolases 6 and 12, but they also serve as substrates for cyclooxygenases, cytochrome P450s, and lipoxygenases. These enzymes oxygenate the 1Z,4Z-pentadiene system of the arachidonic acid backbone of endocannabinoids, thereby giving rise to an entirely new array of bioactive lipids. Hereby, a protocol is provided for the enzymatic synthesis, purification, and characterization of various oxygenated metabolites of anandamide generated by lipoxygenases, which enables the biological study and detection of these metabolites.

Working with patients with disruptions in symbolic capacity.

This article focuses on understanding and working with patients who have poorly developed symbolic capacity, or for whom symbolic capacity has been disrupted due to trauma, particularly as it pertains to the use of reverie and interpretation in the analytic process. Many patients who present for Jungian analysis will initially present with deficits in symbolic functioning. This situation results in necessary limitations or modifications in utilizing traditional Jungian techniques such as dream analysis, active imagination, sand tray and other expressive art techniques. The initial phase of analytic work with these patients requires a focus on developing their symbolic capacity before traditional Jungian techniques can be utilized effectively. During the paper Jung's concept of 'the symbolic attitude' will be examined as well as the conceptual models of Wilfred Bion and other post-Bionians who outline theories and method for cultivating symbolic capacity and reflective functioning in patients for whom these capacities are impaired or poorly developed.

Cet article se concentre sur la compréhension et le travail avec des patients dont la capacité symbolique est mal développée, ou pour qui la capacité symbolique a été perturbée par le traumatisme. Ceci concerne tout particulièrement l'utilisation de la rêverie et de l'interprétation dans le processus analytique. Beaucoup de patients qui viennent pour une analyse Jungienne montrent initialement des déficits dans le fonctionnement symbolique. Ceci a pour conséquence des limitations nécessaires ou des modifications dans l'utilisation de techniques traditionnelles Jungiennes telles l'analyse des rêves, l'imagination active, la thérapie par le jeu de sable et autres techniques d'expression par l'art. La phase initiale du travail analytique avec ces patients requiert de mettre l'accent sur le développement de leur capacité symbolique avant que les techniques Jungiennes traditionnelles puissent être utilisée de manière efficace. Dans l'article, le concept Jungien 'd'attitude symbolique' sera étudié ainsi que les modèles conceptuels de Wilfred Bion et d'autres post-Bioniens qui présentent des théories et une méthode pour cultiver la capacité symbolique et le fonctionnement réfléchi chez des patients pour qui ces capacités sont déficientes ou mal développées.

El presente artículo se focaliza en la comprensión y trabajo con pacientes que han tenido un desarrollo limitado de su capacidad simbólica, o para quienes, la capacidad simbólica se ha visto perturbada debido a un trauma, particularmente en lo que se refiere al uso del reverie y de la interpretación en el proceso analítico. Muchos pacientes que se presentan para un análisis Junguiano, presentan inicialmente deficitis en su funcionamiento simbólico. Esta situación tiene como resultado limitaciones necesarias o modificaciones en la utilización de técnicas Junguianas tradicionales como el análisis de sueños, la imaginación activa, la caja de arena y otras técnicas artísticas y expresivas. La fase inicial del trabajo analítico con estos pacientes requiere hacer foco en el desarrollo de su capacidad simbólica antes de que técnicas Junguianas tradicionales puedan utilizarse efectivamente. Durante el escrito se examina el concepto de Jung de `actitud simbólica`, así como los modelos conceptuales de Wilfred Bion y otros post-Bionianos quienes describen teorías y métodos para cultivar la capacidad simbólica y el funcionamiento reflexivo en pacientes para quienes estas capacidades se encuentran perturbadas o poco desarrolladas.

Organocatalytic synthesis of axially chiral tetrasubstituted allenes.

Asymmetric organocatalysis is a growing method for the synthesis of axially chiral tetrasubstituted allenes, the most challenging one among allene syntheses. In this method, chiral organocatalysts such as phase-transfer catalysts, peptides, disulfonimides, and binaphthyl/bispiro phosphoric acids have displayed remote control of regio- and stereoselectivity. Highly functionalized enantiopure allenes including those with an adjacent tertiary or quaternary stereocenter have been efficiently prepared with high levels of regio-, diastereo-, and enantioselectivity using this method. Several mechanistic pathways, including electrophilic addition to cumulenolate or zwitterionic enolate intermediates, alkynylogous Mukaiyama aldol reaction, nucleophilic addition to quinone methides, and dearomative addition to imino esters, were proposed. The method is necessary for providing access to axially chiral tetrasubstituted allenes, which can be utilized for the preparation of novel ligands, natural products, and organic materials, particularly those having complex structures. This review covers the enantioselective organocatalytic synthesis of these tetrasubstituted allenes and the mechanistic insights into the formation of the chiral axis up to July 2022.

Ru(II)-Catalyzed Regioselective Annulation of 2-Hydroxystyrenes with Allenyl Acetates via Vinylic C-H Activation.

Herein, we disclose an unprecedented and robust Ru(II)-catalyzed non-oxidative [5+1] annulation of 2-hydroxystyrenes with allenyl acetates to access biologically relevant chromene skeletons. The heteroatom on allene plays a pivotal role in controlling the regioselectivity of migratory insertion, and the reaction proceeds through a Ru-σ-allyl pathway, which has been elusive so far in C-H activation reactions with allenes. The protocol is sustainable in nature as it proceeds at room temperature and avoids the use of any toxic metal oxidants. In addition, the synthetic utility of the protocol was also demonstrated by late stage functionalization and modular synthesis of various natural product conjugates.

Nickel-Catalyzed Asymmetric Propargylation for the Synthesis of Axially Chiral 1,3-Disubstituted Allenes.

The general enantioselective catalytic synthesis of axially chiral 1,3-disubstituted allenes from readily available racemic propargylic alcohol derivatives remains a long-standing challenge in organic synthesis. Here we report an efficient nickel-catalyzed asymmetric propargylic substitution reaction/Myers rearrangement of racemic propargylic carbonates that furnishes a series of enantioenriched 1,3-disubstituted allenes using newly designed N-sulfonylhydrazone reagents as efficient diazo surrogates. This reaction proved to be remarkably general with regard to substrate scope, affording a diverse range of 1,3-disubstituted allenic compounds in good yields with excellent enantioselectivities. Additionally, applications of this powerful strategy for the enantioselective synthesis of methyl (S)-8-hydroxyocta-5,6-dienoate, (S)-laballenic acid, (S)-phlomic acid, and (S)-Δ9,10-pentacosadiene are described, further highlighting the broad potential of these new reagents for the discovery of novel reactions.

A strained intramolecular P/Al-FLP and its reactivity toward allene.

FLPs featuring aluminum-phosphane interactions, spring-loaded by a rigid biphenylene linker, have been accessed through a route where trimethyltin units at phosphane-functionalized organic backbones are exchanged by an AlCl2 moiety. Upon contact with substrates like CO2 these are readily bound by the Al/P site with release of strain. The system could also be utilized for a unique reactivity, namely the activation of allene.

Synthesis of Isomeric 3-Benzazecines Decorated with Endocyclic Allene Moiety and Exocyclic Conjugated Double Bond and Evaluation of Their Anticholinesterase Activity.

Transformations of 1-methoxymethylethynyl substituted isoquinolines triggered by terminal alkynes in alcohols were studied and new 3-benzazecine-containing compounds synthesized, such as 6-methoxymethyl-3-benzazecines incorporating an endocyclic C6-C8 allene fragment and the -ylidene derivatives 6-methoxymethylene-3-benzazecines. The reaction mechanisms were investigated and a preliminary in vitro screening of their potential inhibitory activities against human acetyl- and butyrylcholinesterases (AChE and BChE) and monoamine oxidases A and B (MAO-A and MAO-B) showed that the allene compounds were more potent than the corresponding -ylidene ones as selective AChE inhibitors. Among the allenes, 3e (R3 = CH2OMe) was found to be a competitive AChE inhibitor with a low micromolar inhibition constant value (Ki = 4.9 µM), equipotent with the corresponding 6-phenyl derivative 3n (R3 = Ph, Ki = 4.5 µM), but 90-fold more water-soluble.

Substrate Facilitating Roles in Rare-Earth-Catalyzed C-H Alkenylation of Pyridines with Allenes: Mechanism and Origins of Regio- and Stereoselectivity.

Although considerable progress has been achieved in C-H functionalization by cationic rare-earth alkyl complexes, the potential facilitating roles of heteroatom-containing substrates during the catalytic cycle remain highly underestimated. Herein, theoretical studies on the model reaction of C(sp2)-H addition of pyridines to allenes by scandium catalyst were carefully carried out to reveal the detailed mechanism. A coordinating pyridine substrate as a ligand can effectively stabilize some key structures. An obvious facilitating role delivered by the coordinating pyridine was found for allene insertion, while the pyridine-free mechanism prefers to occur for C(sp2)-H activation processes. Importantly, the elusive role of heteroatom-containing substrates was systematically revealed for the C-H activation event by designing a metal/ligand combination of catalysts and substrates. We found that the pyridyl C(sp2)-H activation would be switched to the pyridine-coordinated mechanism in the cases of the designed Y and La catalysts. To date, this is the first time to realize the potential substrate-facilitating role in cationic rare-earth-catalyzed C-H activation processes. Moreover, theoretical predictions show that similar switchable mechanisms also work for other types of C-H bonds and other heteroatom-involved substrates by fine-adjusting the steric surroundings of catalysts. The two C-H activation mechanisms are mainly the result of the delicate balance between electronic and steric factors. In general, the catalytic system with less steric hindrance prefers to undergo the substrate-coordinated mechanism. In contrast, the substrate-free mechanism is favorable due to steric repulsion. These results are helpful for us to better understand the variant mechanisms in rare-earth-catalyzed C-H functionalization at the atomistic level and may help guide the rational design of new catalytic reactions. In addition, the origins of the regio- and stereoselectivity were discussed through geometric parameters and distortion/interaction analysis.