[2 + 2] Photocyclization converts thermally induced spin crossover effect into "hidden hysteresis" one.

The light induced [2 + 2] cyclization of the flexible coumarin-based ligand (L) converts the spin crossover active HS1 ⇆ LS1 mononuclear system [Fe(L)](BF)·4CHCN (1) into the high spin 1D coordination polymer (2). The contribution of the resulting high spin form HS2 is directly related to the degree of photoconversion and, at the same time, practically does not affect the properties of the remaining thermally active spin crossover centers (HS1). The origin of such a fundamental change in properties is an appearance of strain caused by ligand dimerization, which acts directly on the metal chromophores and is transmitted to the crystal lattice.

-Difluorovinyl and trifluorovinyl Michael acceptors in the synthesis of α,β-unsaturated fluorinated and nonfluorinated amides.

The incorporation of fluorine atoms within the structure of organic compounds is known to exert a significant impact on their electronic properties, thereby modulating their reactivity in diverse chemical transformations. In the context of our investigation, we observed a striking illustration of this phenomenon. A Michael addition involving -difluorovinyl and trifluorovinyl acceptors was successfully achieved, demonstrating high stereoselectivity.

Expanding the dimensionality of bis(tetrazolyl)alkane-based Fe(II) coordination polymers by the application of dinitrile coligands.

Reactions between 1,2-di(tetrazol-2-yl)ethane (ebtz), 1,6-di(tetrazol-2-yl)hexane (hbtz) or 1,1'-di(tetrazol-1-yl)methane (1ditz) and Fe(BF) in the presence of adiponitrile (ADN), glutaronitrile (GLN) or suberonitrile (SUN) resulted in the formation of coordination polymers [Fe(μ-ebtz)(μ-ADN)](BF) (1), [Fe(μ-hbtz)(μ-ADN)](BF) (2), [Fe(μ-1ditz)(GLN)](BF)·GLN (3) and [Fe(μ-1ditz)(μ-SUN)](BF)·SUN (4). It was established that the application of dinitriles allows an increase in the dimensionality of the ebtz and hbtz based systems while maintaining the structure of the polymeric units characteristic of previously studied mononitrile based analogues. In 3 and 4, regardless of the type of dinitrile coligand, the motif of 2D polymeric layers constituted by 1ditz molecules remains preserved.

Extremely Slow Thermally-Induced Spin Crossover in the Two-Dimensional Network [Fe(bbtr) ](BF ).

Cooling [Fe(bbtr) ](BF ) (bbtr=1,4-di(1,2,3-triazol-1-yl)butane) triggers very slow spin crossover below 80 K (T =76 K). The spin crossover (SCO) is accompanied by a hysteresis loop (T =89 K). In contrast to isostructural perchlorate analogue [Fe(bbtr) ](ClO ) in which spin crossover during cooling is preceded by phase transition at T =126 K in tetrafluoroborate phase transition does not occur to the beginning of spin crossover (80 K).

Synthesis of fluorinated and nonfluorinated sugar alkenylphosphonates via highly stereoselective Horner-Wadsworth-Emmons olefination.

New fluorinated and nonfluorinated sugar alkenylphosphonates were obtained. In all cases 1,2;5,6-di-O-isopropylidene-α-d-glucofuranose was used as the starting material. The synthesis of alkenylphosphonates was based on Horner-Wadsworth-Emmons olefination.

Dipeptide analogues of fluorinated aminophosphonic acid sodium salts as moderate competitive inhibitors of cathepsin C.

In this paper, we present the solvolysis reaction of dipeptide analogues of fluorinated aminophosphonates with simultaneous quantitative deprotection of the amino group. To the best of our knowledge, this work is the first reported example of the application of fluorinated aminophosphonates in cathepsin C inhibition studies. The new molecules show moderate inhibition of the cathepsin C enzyme, which opens the door to consider them as potential therapeutic agents.

Horner-Wadsworth-Emmons reaction as an excellent tool in the synthesis of fluoro-containing biologically important compounds.

Selective introduction of a double bond motif into a multifunctional organic compound is always a big challenge. The Horner-Wadsworth-Emmons reaction is one of the most reliable, simple, and stereoselective olefination methods, widely used in organic chemistry. To the best of our knowledge, no review article on the application of HWE reaction in the synthesis of fluoroorganic compounds with direct biological interest has been published in recent years.

Design and Synthesis of New α-hydroxy β-fluoro/β-trifluoromethyl and Unsaturated Phosphonates from Carbohydrate-Derived Building Blocks via Pudovik and Horner-Wadsworth-Emmons Reactions.

Herein, we present the application of fluorinated carbohydrate-derived building blocks for α-hydroxy β-fluoro/β-trifluoromethyl and unsaturated phosphonates synthesis. Pudovik and Horner-Wadsworth-Emmons reactions were applied to achieve this goal. The proposed pathway of the key reactions is supported by the experimental results, as well as quantum chemical calculations.

The Arousal-motor Hypothesis of Dopamine Function: Evidence that Dopamine Facilitates Reward Seeking in Part by Maintaining Arousal.

Dopamine facilitates approach to reward via its actions on dopamine receptors in the nucleus accumbens. For example, blocking either D1 or D2 dopamine receptors in the accumbens reduces the proportion of reward-predictive cues to which rats respond with cued approach. Recent evidence indicates that accumbens dopamine also promotes wakefulness and arousal, but the relationship between dopamine's roles in arousal and reward seeking remains unexplored.

Deoxyfluorinating reagents as tools for γ-amino-α-hydroxyphosphonate modification.

Herein, we would like to present deoxyfluorinating reagents such as DAST and PyFluor and their successful use as tools for selective modification of γ-amino-α-hydroxyphosphonates. Depending on the deoxyfluorinating reagent applied, an intramolecular cyclization leading to phosphonates containing the 1,3-oxazinan-2-one moiety or direct nucleophilic deoxyfluorination yielding the α-fluorinated derivatives of γ-aminophosphonates was observed. The obtained compounds may be used as precursors in the preparation of medicinally important compounds , dipeptide analogues or scaffolds containing the 1,3-oxazinan-2-one group.

The Role of Interhemispheric Interactions in Cortical Plasticity.

Despite the fact that there is a growing awareness to the callosal connections between hemispheres the two hemispheres of the brain are commonly treated as independent structures when peripheral or cortical manipulations are applied to one of them. The contralateral hemisphere is often used as a within-animal control of plastic changes induced onto the other side of the brain. This ensures uniform conditions for producing experimental and control data, but it may overlook possible interhemispheric interactions.

Three-Dimensional Interfacing of Cells with Hierarchical Silicon Nano/Microstructures for Midinfrared Interrogation of In Situ Captured Proteins.

Label-free optical detection of biomolecules is currently limited by a lack of specificity rather than sensitivity. To exploit the much more characteristic refractive index dispersion in the mid-infrared (IR) regime, we have engineered three-dimensional IR-resonant silicon micropillar arrays (Si-MPAs) for protein sensing. By exploiting the unique hierarchical nano- and microstructured design of these Si-MPAs attained by CMOS-compatible silicon-based microfabrication processes, we achieved an optimized interrogation of surface protein binding.

Spatiotemporal Studies of the One-Dimensional Coordination Polymer [Fe(ebtz) (C H CN) ](BF ) : Tug of War between the Nitrile Reorientation Versus Crystal Lattice as a Tool for Tuning the Spin Crossover Properties*.

Reaction of 1,2-di(tetrazol-2-yl)ethane (ebtz) with Fe(BF ) ⋅6 H O in different nitriles yields one-dimensional coordination polymers [Fe(ebtz) (RCN) ](BF ) ⋅nRCN (n=2 for R=CH (1) and n=0 for R=C H (2) C H (3), C H (4), CH Cl (5)) exhibiting spin crossover (SCO). SCO in 1 and 3-5 is complete and occurs above 160 K. In 2, it is shifted to lower temperatures and is accompanied by wide hysteresis (T =78 K, T =123 K) and proceeds extremely slowly.

Two ways of spin crossover in an iron(ii) coordination polymer associated with conformational changes of a bridging ligand.

1,4-Di(1-ethyl-1,2,3-triazol-5-yl)butane (bbtre) was prepared by lithiation of 1-ethyl-1,2,3-triazole, followed by alkylation with 1,4-dibromobutane. The ligand bbtre forms a three-dimensional network with Fe(ii), [Fe(bbtre)3](ClO4)2·2CH3CN, that exhibits thermally induced spin crossover (SCO). A change of temperature or change of spin state results in various types of structural transformation, leading to different structures that are stable in strictly defined temperature ranges.

Efficient synthesis of dipeptide analogues of α-fluorinated β-aminophosphonates.

Herein, we present an efficient synthesis of dipeptide analogues of α-fluorinated β-aminophosphonates. Each step of the synthesis was optimized to provide excellent yields. Moreover, the absolute configuration of the obtained compounds was determined by X-ray analysis, which proved the stereochemistry that was proposed based on NMR studies.

Direct Access to Substituted 4-CF β-Lactams at the C-3 Position.

Mono- and disubstituted 4-CF β-lactams at the C-3 position have been obtained stereoselectively under basic conditions. A wide range of function such as alcohols, alkyls, aryls, esters, and double and triple bonds have been introduced.

Functionalization of α-hydroxyphosphonates as a convenient route to -tosyl-α-aminophosphonates.

Direct conversion of the α-hydroxyl group by -toluenesulfonamide to yield α-(-tosyl)aminophosphonates is reported. α-Aminophosphonates 23a,b-37a,b were obtained from the corresponding α-hydroxyphosphonates 6a,b-21a,b in the presence of KCO, the retro-Abramov reaction of the appropriate aldehydes, 1-5. The subsequent formation of imines with simultaneous addition of diethyl phosphite provided access to the α-sulfonamide phosphonates 23a,b-37a,b with better diastereoselectivity than in the case of the Pudovik reaction.

Pejvakin, a Candidate Stereociliary Rootlet Protein, Regulates Hair Cell Function in a Cell-Autonomous Manner.

Mutations in the () gene are thought to cause auditory neuropathy and hearing loss of cochlear origin by affecting noise-induced peroxisome proliferation in auditory hair cells and neurons. Here we demonstrate that loss of pejvakin in hair cells, but not in neurons, causes profound hearing loss and outer hair cell degeneration in mice. Pejvakin binds to and colocalizes with the rootlet component TRIOBP at the base of stereocilia in injectoporated hair cells, a pattern that is disrupted by deafness-associated mutations.

Conditional deletion of pejvakin in adult outer hair cells causes progressive hearing loss in mice.

Mutations in the Pejvakin (Pjvk) gene cause autosomal recessive hearing loss DFNB59 with audiological features of auditory neuropathy spectrum disorder (ANSD) or cochlear dysfunction. The precise mechanisms underlying the variable clinical phenotypes of DFNB59 remain unclear. Here, we demonstrate that mice with conditional ablation of the Pjvk gene in all sensory hair cells or only in outer hair cells (OHCs) show similar auditory phenotypes with early-onset profound hearing loss.

Progressive Hearing Loss in Mice Carrying a Mutation in Usp53.

Unlabelled: Disordered protein ubiquitination has been linked to neurodegenerative disease, yet its role in inner ear homeostasis and hearing loss is essentially unknown. Here we show that progressive hearing loss in the ethylnitrosourea-generated mambo mouse line is caused by a mutation in Usp53, a member of the deubiquitinating enzyme family. USP53 contains a catalytically inactive ubiquitin-specific protease domain and is expressed in cochlear hair cells and a subset of supporting cells.

Evaluation of Markers of Inflammation and Oxidative Stress in COPD Patients with or without Cardiovascular Comorbidities.

Background: Although both chronic obstructive pulmonary disease (COPD) and cardiovascular diseases (CVD) are characterised by chronic, systemic inflammation, their reciprocal interactions are poorly understood. The purpose of this study was to determine the concentrations of both inflammatory and oxidative stress biomarkers in the serum and exhaled breath condensate (EBC) of COPD patients, either with coexisting CVD or without cardio-vascular comorbidities.

Methods: Twenty-four COPD patients with CVD were allocated to group A, 20 COPD patients without CVD were assigned to group B and 16 healthy patients were included as a control.

Correlation of inflammatory markers with echocardiographic parameters of left and right ventricular function in patients with chronic obstructive pulmonary disease and cardiovascular diseases.

Introduction:  Inflammation and oxidative stress play an essential role in the pathogenesis of chronic obstructive pulmonary disease (COPD) and cardiovascular disease (CVD).

Objectives:  The aim of the study was to evaluate the echocardiographic parameters of the left and right ventricular functions in patients with COPD with or without CVD and in healthy controls, and to establish their relationships with biomarkers of inflammation and oxidative stress.

Patients And Methods:  The study included 24 patients with COPD and CVD, 20 patients with COPD, and 16 healthy controls.

Influence of fluorine substituents on the NMR properties of phenylboronic acids.

The paper presents results of a systematic NMR studies on fluorinated phenylboronic acids. All possible derivatives were studied. The experimental (1)H, (13)C, (19)F, (11)B, and (17)O spectral data were compared with the results of theoretical calculations.

External pH modulates EAG superfamily K+ channels through EAG-specific acidic residues in the voltage sensor.

The Ether-a-go-go (EAG) superfamily of voltage-gated K(+) channels consists of three functionally distinct gene families (Eag, Elk, and Erg) encoding a diverse set of low-threshold K(+) currents that regulate excitability in neurons and muscle. Previous studies indicate that external acidification inhibits activation of three EAG superfamily K(+) channels, Kv10.1 (Eag1), Kv11.