A new selective chromo-fluorogenic probe for Fe(3+), Cr(3+) and Al(3+) is reported. Detection limits are in the μM range fluorogenic sensing ability could be observed by naked eye when illuminated with UV-light. No response divalent cations.

Abstract The membrane translocation of hydrophilic substances constitutes a challenge for their application as therapeutic compounds and labelling probes 1–4 . To remedy this, charged amphiphilic molecules have been classically used carriers 3,5 However, such may cause aggregation non-specific lysis 6,7 Here we show that globular dodecaborate clusters, prominently B 12 Br 2− , can function anionic inorganic broad range cargo (with molecular mass 146–4,500 Da). We cationic neutral peptides,...

The membrane transport mechanisms of cell-penetrating peptides (CPPs) are still controversial, and reliable assays to report on their internalization in model membranes required. Herein, we introduce a label-free, fluorescence-based method monitor real time. For this purpose, macrocyclic host fluorescent dye forming host–dye reporter pair encapsulated inside phospholipid vesicles. Internalization peptides, which can bind the supramolecular host, leads displacement from resulting fluorescence...

Cobalt bisdicarbollides (COSANs) are inorganic boron-based anions that have been previously reported to permeate by themselves through lipid bilayer membranes, a propensity is related their superchaotropic character. We now introduce use as selective and efficient molecular carriers of otherwise impermeable hydrophilic oligopeptides both artificial cellular without causing membrane lysis or poration at low micromolar carrier concentrations. COSANs transport not only arginine-rich but also...

Polyoxometalates (POMs) are known antitumoral, antibacterial, antiviral, and anticancer agents considered as next-generation metallodrugs. Herein, a new biological functionality in neutral physiological media, where selected mixed-metal POMs sufficiently stable able to affect membrane transport of impermeable, hydrophilic, cationic peptides (heptaarginine, heptalysine, protamine, polyarginine) is reported. The uptake observed both, model membranes well cells, attributed the superchaotropic...

Abstract Two chromo‐fluorogenic probes, each based on the boron dipyrromethene core, have been developed for detection of nerve‐agent mimics. These chemosensors display both a color change and significant enhancement fluorescence in presence diethylcyanophosphonate (DCNP) diisopropylfluorophosphate (DFP). No interference from other organophosphorus compounds or acids has observed. portable chemosensor kits tested to demonstrate its practical application real‐time monitoring.

Abstract Phosphorylation and dephosphorylation of peptides by kinases phosphatases is essential for signal transduction in biological systems, many diseases involve abnormal activities these enzymes. Herein, we introduce amphiphilic calixarenes as key components supramolecular, phosphorylation‐responsive membrane transport systems. Dye‐efflux experiments with liposomes demonstrated that are highly active counterion activators established cell‐penetrating peptides, EC 50 values the low...

Two new Eu3+ and Au3+ BODIPY-complexes capable of chromo-fluorogenically detecting micromolar concentrations V-type nerve agent surrogates by a simple displacement assay are described.

Abstract Gram-negative porins are the main entry for small hydrophilic molecules. We studied translocation of structurally related cephalosporins, ceftazidime (CAZ), cefotaxime (CTX) and cefepime (FEP). CAZ is highly active on E. coli producing OmpF (Outer membrane protein F) but less efficient cells expressing OmpC C), whereas FEP CTX kill bacteria regardless porin expressed. This matches with different capacity to accumulate into bacterial as quantified by LC-MS/MS (Liquid Chromatography...

We report on the discovery of first two examples cationic palladium(II)-oxo clusters (POCs) containing f-metal ions, [Pd

Abstract Perhalogenated closo ‐borates represent a new class of membrane carriers. They owe this activity to their chaotropicity, which enables the transport hydrophilic molecules across model membranes and into living cells. The efficiency cluster carriers depends on careful balance between affinity cargo, varies with chaotropicity. However, structure–activity parameters that define chaotropic remain be elucidated. Here, we have studied modulation by decoupling halogen composition from...

Boron clusters are applied in medicinal chemistry because of their high stability biological environments and intrinsic ability to capture neutrons. However, intermolecular interactions with lipid membranes, which is critical for cellular delivery biocompatibility, have not been comprehensively investigated. In this study, we combine different experimental methods - Langmuir monolayer isotherms at the air-water interface, calorimetry (DSC, ITC), scattering techniques (DLS, SAXS) MD...

A novel colorimetric probe (P4) for the selective differential detection of DFP (a Sarin and Soman mimic) DCNP Tabun was prepared. Probe P4 contains three reactive sites; i.e. (i) a nucleophilic phenol group able to undergo phosphorylation with nerve gases, (ii) carbonyl as site cyanide; (iii) triisopropylsilyl (TIPS) protecting that is known react fluoride. The reaction in acetonitrile resulted both phenoxy release cyanide, which produce colour modulation from pink orange. In contrast,...

Lysine (K) is an important target residue for protein and peptide delivery across membranes. K the most frequently exposed in proteins, leading to high demand development of K-compatible transport activators. However, designing activators K-rich peptides proteins more challenging than arginine-rich species because kosmotropic nature its recognition difficulty. In this study, we designed a new amphiphilic sulfonatocalix[5]arene (sCx5-6C) as activator. sCx5-6C was tailored with two key...

Intracellular protein delivery has the potential to revolutionize cell-biological research and medicinal therapy, with broad applications in bioimaging, disease treatment, genome editing. Herein, we demonstrate successful of a functional protein, cytochrome c (CYC), by using boron cluster anion as molecular carrier superchaotropic type (B 12 Br 11 OPr 2– ). CYC was delivered into lipid bilayer vesicles well living cells, cellular uptake ratio approaching 90%. Mechanistic studies showed that...

Efficient neutralization of nerve-agent simulants by 1,3-diindolylureas in a neutral medium was investigated (see scheme; DCP=diethylchlorophosphate, DCNP=diethylcyanophosphonate). The rate hydrolysis the found to increase as much 45 % presence these compounds. A mechanism based on simulant complexation established. Detailed facts importance specialist readers are published "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted...

Off–on two channel BODIPY-based chemosensors, highly sensitive for trivalent cations. Selective sensing of Al³⁺ and Cr³⁺<italic>versus</italic> Fe³⁺ has been achieved.

Parallel artificial membrane permeability assay (PAMPA) is a screening tool for the evaluation of drug across various biological systems in microplate format. In PAMPA, candidate allowed to pass through lipid layer particular well during an incubation period of, typically, 10-16 hours. second step, samples each are transferred UV-Vis compatible and optically measured (applicable only analytes with sufficient absorbance) or sampled by mass-spectrometric analysis. The required period, sample...

A BODIPY-containing Cu(II) -bipyridine complex for the simple selective fluorogenic detection of NO in air and live cells is reported. The mechanism based on NO-promoted to Cu(I) reduction, followed by demetallation complex, which results clearly enhanced emission boron dipyrromethene (BODIPY) unit.

A new photosensitizer (1) based on the 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) scaffold has been synthesized. 1 is water soluble and showed an intense absorption band at 490 nm (ɛ=77,600 cm(-1) m(-1)) emission 514 nm. In vitro toxicity of in presence light darkness studied with HeLa, HaCaT, MCF-7, SCC-13 cell lines. Moreover, internalization studies these lines were also performed. These results suggested that more toxic for HeLa carcinoma cells than HaCaT non-cancerous immortal...

Abstract Die Phosphorylierung und Dephosphorylierung von Peptiden durch Kinasen Phosphatasen ist ein allgegenwärtiger Mechanismus der Signaltransduktion in biologischen Systemen. Eine unnatürlich hohe oder niedrige Aktivität dieser Enzyme steht im Zusammenhang mit vielen Krankheiten. Hier führen wir amphiphile Calixarene als supramolekulare Schlüsselkomponenten für einen Membrantransport ein, sich regulieren lässt. Mithilfe farbstoffbeladenen Liposomen zeigen wir, dass diese Gegenionen...

Boron clusters are applied in medicinal chemistry because of their high stability biological environments and intrinsic ability to capture neutrons. However, intermolecular interactions with lipid membranes, which is critical for cellular delivery biocompatibility, have not been comprehensively investigated. In this study, we combine different experimental methods – Langmuir monolayer isotherms at the air‐water interface, calorimetry (DSC, ITC), scattering techniques (DLS, SAXS) MD...

A gold(<sc>iii</sc>)–amino alcohol complex induces the P–S bond cleavage in organophosphorous pesticides giving rise to less toxic compounds.