Knowledge about the membrane transport of antibiotics and other pharmacologically relevant molecules in bacteria is crucial towards understanding and overcoming antibiotic resistance. In this review, methods for the detection and quantification of membrane transport of pharma-molecules in bacteria are discussed.

The use of hyperpolarized ¹²⁹Xe has the potential to revolutionize clinical imaging, offering a non-ionizing contrast of organ function complementary to that of CT imaging and conventional MRI. In this Review, the physics of spin-exchange optical pumping (SEOP) is discussed, production modalities of hyperpolarized ¹²⁹Xe are explained, and biomedical applications to lung imaging and beyond are described.

Die chemische Reaktivität ionischer Flüssigkeiten und stark eutektischer Lösungsmittel kann als synthetisches Werkzeug genutzt werden, um anorganische Materialien herzustellen, die über konventionelle Syntheserouten schwierig oder sogar überhaupt nicht zugänglich sind. Dieser Aufsatz fasst neuere Entwicklungen im Gebiet der anorganischen Synthese unter Nutzung von Reaktionen mit ionischen Flüssigkeiten oder stark eutektischen Lösungsmitteln zusammen.

We report here an asymmetric decarboxylative allylation reaction initiated by the hydrocarboxylation reaction of heteroatom-substituted allene. The reaction works particularly well with heteroatom-substituted allenes such as alkoxyallenes and amidoallenes. A number of aryl and alkyl β-keto acids as well as malonic acid mono-phenyl ester participates in the reaction to generate γ,δ-unsaturated carbonyl compounds possessing stereogenic heteroatom substituents at the β-position.

Biosynthetic instructions contained within congener biosynthetic gene clusters (BGCs) have been used to guide the synthesis of improved antibiotic analogues. ρ-Aminobenzoic acid encoding BGCs cloned from soil metagenomes have guided the synthesis of albicidin and cystobactamid analogues that show increased potency, different spectra of activity, as well as the ability to circumvent resistance conferred by endopeptidase cleavage enzymes.

A method for facile synthesis of highly substituted allenols and fluoroalkyl allenes via iron-catalyzed cross-coupling reaction of propargyl ethers with Grignard reagents is disclosed. Various tri- and tetrasubstituted fluoroalkyl allenes and β-/γ-allenols were obtained in good to excellent yields. The reaction was demonstrated to be stereospecific occurring with syn-S_N2′ displacement of the methoxy group by the Grignard reagent.

An intermolecular Pd-catalyzed dearomative methoxyallylation of 3-nitroindoles with readily available allyl carbonates was reported. Good yields (up to 86 %) and diastereoselectivity (up to >20:1 dr) are obtained for a wide range of substrates. The compatibility of gram-scale synthesis and the relatively low catalyst loading (down to 1 mol % of [Pd]) enhance the practicality of this method.

Co-substituted Mn-rich Prussian Blue Analog (PBA) hollow spheres (CoMn-PBA HSs) are rationally designed and synthesized through an efficient self-templating approach. Benefiting from the hollow structure and partial Co substitution, the CoMn-PBA HSs electrode exhibits enhanced zinc ion storage performance with high capacity, favorable rate capability, and impressive cycling stability.

Two photoresponsive olefin polymerization systems were rationally designed. Light can be used to tune their properties in ethylene polymerization and copolymerization with polar comonomers, enabling light-induced control of the polymerization processes, polymer microstructures and polymer properties.

Isolable chiral rhodium(I) complexes bearing a helical aryl-substituted 1,3,5-hexatriene chain were synthesized by one-pot reactions of [Rh(nbd)Cl]2 with aryl boronic acids and diphenylacetylenes in the presence of 50 % aqueous KOH (see scheme). The persistent helical chirality of the complexes enabled their separation into enantiomers by HPLC on a chiral stationary phase. The complexes served as bench-stable catalysts for living polymerization of phenylacetylene.

An unnatural amino acid, Asn(OH), mimics P1-Asn in the substrates of asparaginyl ligases, enabling efficient cyclization of P1-Asn(OH) peptides. The hydroxamic acid functionality in Asn(OH) is a metal-ion chelator for metalloenzyme inhibition, and Asn(OH) can be converted into native Asp by periodate oxidation (see scheme).

Unique physical interaction facilitated by 1D topologies of molecular cluster-integrated polymers is applied for the design of impact-resistant materials with exceptional energy dissipation capability and strong rate-dependent mechanical strengths, enabling the simultaneous achievement of promising impact resistance and processability/recoverability.

The Truce–Smiles rearrangement has proven to be a powerful tool for the synthesis of new sp³-aryls via ipso substitution. The reaction has been applied to the strain-release ring-opening of 3-aminocyclobutanone oximes, giving cyanide-free access to β-amino nitriles under metal-free, room temperature conditions. The reaction displays a wide scope of migrating arenes.

A highly enantioselective lactonization of unactivated allylic alcohols is reported under mild conditions. The transformation is catalyzed by a Pd^II⋅StackPhos complex and facilitates the substitution of a poor leaving group with what would ostensibly be a better leaving group in the product without selectivity issues arising from racemization.

Three-dimensional covalent organic frameworks (COFs) decorated with nitroxyl radicals are successfully prepared and employed as mild, efficient, and recyclable catalysts for selective oxidation of alcohols to aldehydes or ketones.

Chiral trisubstituted epoxides were synthesized by boron–Lewis acid-catalyzed Darzens-type epoxidation of diazoesters in high yields with excellent enantio- and diastereoselectivity. The developed reaction provides an efficient synthetic route to various chiral compounds such as epoxy γ-butyrolactone, tertiary β-hydroxy ketone, and epoxy diester.

Through the proposed long-short axis molecular design, an HLCT-type ultraviolet emitter is reported. Benefiting from the features of the low-lying LE emissive state and high-lying reverse intersystem crossing process, the ultraviolet OLED furnishes a record-high EQE of 10.79 %, accompanied by a satisfactory color purity and a small efficiency roll-off.

Thermal transformations under pressure of AA′BB′O₆ double double perovskites, where both A and B sites have 1:1 cation order, to (A_0.5A′_0.5)₂BB′O₆ double perovskites with disordered A/A′ cations are demonstrated for CaMnMnWO₆ and SmMnMnTaO₆, leading to a dramatic switch in magnetic properties from ferrimagnetic order to spin glass behaviour in the former.

A universal method is developed to activate near-infrared-excited multicolor afterglow of carbon dots-based RTA materials (CDAMs) through radiative energy transfer from NaYF₄:Yb,Tm upconversion materials (UMs). The resulting UM/CDAMs demonstrate bright and persistent afterglow from blue to orange under NIR CW laser excitation at 980 nm.

Nitride perovskites are extremely rare and challenging to synthesise, but an azide-mediated high-pressure route has been used to prepare LaReN₃ which can be topotactically reduced to layered LaReN₂.

Lamellar MXene (Ti₃C₂T_x)@PSS membranes with specific size exclusion and Li⁺ identification property show excellent mono/multi-valent ions separation performance. Compared with the traditional 2D membranes, the selectivity of Li⁺/Na⁺, Li⁺/K⁺, and Li⁺/Mg²⁺ through such membranes is five to ten times improved.

Forrestiacids A (1) and B (2), comprising a rearranged spiro-lanostane unit fused with an abietene by a Diels–Alder cycloaddition, represent a novel class of pentaterpenoids obtained from Pseudotsuga forrestii. Chemical computations demonstrate to be an effective strategy in the structure elucidation of complex molecules. Both 1 and 2 showed potent ACL inhibitory effects, and 1 even significantly attenuated the de novo lipogenesis in HepG2 cells.

A facile and spontaneous strategy is presented for synthesizing Ru-nanoparticle-anchored metal–organic framework nanohybrids on Ni foam. The nanohybrids exhibit excellent HER performance at all pH values owing to the optimized adsorption free energies of intermediates by the interfacial-bond-induced electron redistribution.

We report on a first demonstration for a catalyst comprising metal NPs and amorphous MOF in a gas-phase reaction. Cu/amorphous UiO-66 exhibited 3-fold catalytic activity for CO₂ hydrogenation into methanol over Cu/crystalline UiO-66. Amorphous UiO-66 coating on Cu-ZnO nanocomposites showed 1.5-fold catalytic activity enhancement over that of Cu/amorphous UiO-66.

It turns out there is nothing special about potassium after all: Sodium and lithium metal reduce Al^III iodide precursors to the M₂[Al(NON^Dipp)]₂ aluminyls (M=Li, Na). Addition of Et₂O afforded the monomeric ion pairs (NON^Dipp)Al-M(Et₂O)₂ containing unsupported Al−Li and Al−Na bonds. All species activate dihydrogen, albeit at significantly different rates of reaction.

The superatom-in-superatom concept was demonstrated for the first time. A rhodium hydride (RhH) superatom could be incorporated into a cluster superatom to generate a stable superatom-in-superatom [RhH@Ag₂₄(SR)₁₈]²⁻ nanocluster. The Rh atom with open d-shells ([Kr]4d⁸5s¹) could be incorporated into the Ag₂₄(SR)₁₈ framework by forming the RhH superatom resembling the closed d-shell Pd atom ([Kr]4d¹⁰).

We report the synthesis of the first example of a molecular compound featuring a Li−Al bond and a systematic analysis of the bonding in this and related Mg and Zn systems through structural, quantum-chemical, and reactivity probes.

A high yielding and scalable metal-free four-step linear domino reaction results in functionalized triarylbenzene (TAB) and opens the door for making a broad variety of synthetically challenging hexaarylbenzene (HAB) molecules with six different aryl groups.

The in situ encapsulation of protein by self-assembly of hydrogen-bonded organic frameworks (HOFs) enables the formation of nanoscale protein@TA-HOFs under mild conditions. Moreover, this strategy is generally applicable to proteins with different surface charge and molecular weight, facilitating the cellular internalization of proteins for efficient enzyme catalysis inside living cells.

The chemical structures of fragments that are composed of CMS strands from varied polyimide precursors are similar, however, the texture or morphology structure is greatly affected by precursors, determining CMS membrane separation performance. The CMS properties can be tuned via controlling the strand′s structure, thereafter the plate and cellular structures, by designing precursor polymer chemical structure and pyrolysis conditions.

By means of designing a crosslink of superposed fast and slow dynamics, we show the quantitative control of the association/dissociation rate constants of this crosslink over 5 orders of magnitude. With this crosslink, we achieved precise control over viscoelasticity and mechanical response of polymer networks.

The strong metal-support interaction (SMSI) of well-defined Pd-TiO₂ catalysts under high temperature oxidation was studied via in situ atmospheric pressure TEM. On the different facets of TiO₂ supports there were significant differences in the encapsulation behaviors with a facet-dependent SMSI. Obvious cover layers were observed on Pd NPs supported on TiO₂ (101) and (100) facets, while no such phenomenon appeared on TiO₂ (001) facets.

An iron-catalyzed reductive cyclization of 2-vinylanilides to prepare a variety of N-heterocycles is reported. The reaction, which usually occurs at room temperature over a short reaction time, employs an inexpensive and bench-stable iron catalyst and EtMgBr as a hydride source. The breadth of this strategy was demonstrated by the synthesis of densely substituted indoles, oxindoles and novel tetrahydrobenzoazepinoindolones, as well as the application towards the formal syntheses of bioactive compounds.

A novel platinum dichloride complex supported by an ambiphilic bisphosphinodichlorogermane ligand photo-isomerizes into a tetravalent platinum trichloride germyl complex. Further irradiation of this new complex triggers the elimination of chlorine and the formation of a covalent Pt–Ge bond. Transient absorption spectroscopy points to the intermediacy of a charge-transfer complex involving the nascent chlorine atom and the aromatic ligand.

3D single-particle-tracking microscopy combined with a lock-in filtering algorithm for the quantitative observation of individual protein–nanoparticle (NP) interactions without surface immobilization is presented. This highly sensitive method, which can be applied in various protein–NP systems, gives insight into in situ protein corona on a per-particle basis and provides the possibility to study transient protein–NP interactions.

The performance of discrete heteropolynuclear Yb/Er salts is switched from a Yb/Er doublet to competitive upconversion luminescence exploiting fluoride association. A more than 20-fold enhancement of the relative quantum yield ϕ_UC under low power densities in non-deuterated solvents at room temperature was recorded.

A NIR-II absorbing BF₂ complex with high photothermal performance was designed. The complex achieves a high photothermal conversion efficiency value of 80 % under 1064 nm laser irradiation. In vivo studies reveal the great potential of the complex in photoacoustic imaging-guided photothermal therapy in the NIR-II window.

Fusion of benzofuran to either s-indacene or dicyclopenta[b,g]naphthalene results in two dramatically different outcomes depending upon heterocycle orientation. Whereas the „anti“ isomers are unstable and hydrolyze readily to ring-opened products, the „syn“ isomers are quite stable and afford molecules that either possess a high degree of antiaromaticity or exhibit pronounced diradical character.

A catalytic carbonylative cleavage of carbon–carbon triple bonds is achieved. This allows for a general and direct synthesis of α,β-unsaturated piperidones by palladium-catalyzed cascade carbonylation of alkynols.

Powerful combination of experimental methods and calculations highlights the distinct molecular mechanisms underlying stereoselective [4+2] cycloadditions catalyzed by a pair of decalin synthases, Fsa2 and Phm7, that catalyze intramolecular cycloadditions to form enantiomeric decalin scaffolds. Our proposed mechanism would open a new window on the enzymatic [4+2] cycloadditions.

Tertiary chiral nanostructures have been created by assembling chiroptical superatoms of [Au₇Ag₆Cu₂(S- or R-BINAP)₃(SCH₂Ph)₆]⁺ (BINAP=2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl). Both metal framework (primary structure) and surface ligands (secondary) of the nanocluster display perfect mirror symmetry. C−H⋅⋅⋅F hydrogen bonding between the clusters and SbF₆⁻ counterions direct formation of left- or right-handed helices.

Butterfly-like oxacalix[2]arene[2]pyrazine molecules exhibit typical aggregation-induced emission (AIE) characteristics through restriction of intramolecular vibrations. When used as ligands for the construction of MOFs, AIE luminogens (AIEgens) with multiple luminescence properties are produced.

Self-bending organic single crystals of coronene with controlled width, length, and curvature are constructed for customized electronic micro-devices. The bending crystal device presents a huge improvement beyond seven orders of magnitude in the conductivity over the straight one, which benefited from both π electron level changing and carrier mobility enhancement caused by the structural deformation in the bent regions.

Multivariate covalent organic frameworks provide an ideal platform for ionic functionalization, enabling the integration of large surface areas, high pore volumes, and abundant binding sites, thereby leading to unprecedented levels of I₂-capture performance under both static and dynamic adsorption conditions.

An engineered aptamer with a Cy7-based photocleavable linker can be used as anticoagulant. With tissue-penetrating red light, the aptamer is cleaved, and blood clotting is restored in human whole blood.

Access to the elusive mid-infrared by direct second-harmonic generation (SHG) enabled by a vanadate crystal is reported. Cs₄V₈O₂₂ exhibits a wide transparent range, a strong SHG response, a large laser damage threshold and congruent-melting behavior. Quantum mechanical calculations demonstrate the key role played by its quasi-rigid layered structure in the improvement in linear and second-order nonlinear optical performance.

A cobalt-catalyzed regio-controllable sequential hydrosilylation/hydroboration of alkynes has been developed with complete control of all the possible regioselectivities for the double addition processes (up to >20/1 rr for all the cases). Various silylboronate regioisomers can be efficiently obtained from the same materials, with good functional group tolerance, regioselectivities as well as atom and pot economy.

Next-generation, base-activated latent sulfinate reagents have been successfully developed for use in the construction of heteroaromatic frameworks, such as 2-arylpyridines. Under Pd-catalyzed conditions, these species unmask to give the sulfinate in situ, which then undergoes efficient desulfinative cross-coupling with an array of (hetero)aryl halides.

A series of new alkyl-substituted dienyltriphenylarsonium ylides was synthesized and used as monomers in the borane-initiated polymerization, achieving almost pure C5-polymer (95.8 %), with photoluminescent properties.

Nitrogen-doped ordered porous carbon was synthesized by microwave heating using Fe₃O₄ nanoparticles as hard templates. The microwave-assisted method reduces the reaction time and provides highly ordered structure with large surface area and nitrogen doping. NaAlH₄ was confined into the pores of the carbon scaffold and the hydrogen sorption kinetics is improved by the synergistic effects of nanoconfinement and nitrogen doping.

The trifluoroacyl radical is generated by C−O bond fragmentation of trifluoroacetic anhydride under photoredox conditions and undergoes olefinic C−H bond trifluoroacetylation in a mechanistically unique fashion. The protocol is operationally simple, scalable, and enables the late-stage diversification of complex biorelevant molecules delivering the corresponding α,β-unsaturated trifluoromethyl ketones in one step.

An expanded, 18-ring coronoid molecule, inspired by the structures of Chichibabin and Schlenk hydrocarbons, features a cross-over of Kekulé and non-Kekulé conjugation, resulting in a distinct hexaradicaloid character, easy accessibility of high-spin states, and redox amphoterism.

Dynamic constitutional frameworks are expressed in the presence of bacteria templating from dynamic covalent libraries made of aromatic cores, PEGylated connectors, and ionic heads. This templated DCFs further translate into the multivalent presentation of cationic heads, subsequently promoting antibacterial and antibiofilm activities.

A series of carbon-supported atomic metal-N-C catalysts with similar structural and physicochemical properties were synthesized to uncover the activity trends and mechanisms in peroxymonosulfate-assisted reactive oxygen species production. Fe-SAC displays the best single-site kinetic value (1.65×10⁵ min⁻¹ mol⁻¹), and the PMS→OH*→O*→¹O₂ is the most reasonable ¹O₂ reaction pathway.

Highly selective acetylene semi-hydrogenation is realized using a polyoxometalate-based metal–organic framework supported single Pd atom catalyst by creating dynamic confinement regions which preferentially adsorb acetylene from acetylene/ethylene gas mixtures and release the produced ethylene. This catalyst combines the advantages of MOFs for gas separation and single atomic sites for catalysis.

Synthetic polypeptide vesicles can regulate their membrane permeability via ordered transition of secondary conformations. Particularly, a transformation from extended β-strands to compact α-helices in response to reactive oxygen species reduces the vesicular wall thickness and remodels the membrane structure, thereby enhancing the membrane permeability for efficient nanoreaction, glucose-triggered insulin secretion and effective therapy of diabetes mellitus.

pH fronts are generated from feedback-controlled reaction networks encapsulated in hydrogel spheres. The pH front/reaction diffusion chemistry is utilized to understand the systems such as membrane activity and inter-sphere communication. Further, its potential to develop smart self-growing materials as 2D and 3D hydrogel structures is showcased as an alternative to 3D printing tool.

Dithiolactone monomers derived from abundant feedstocks show appealing chemical properties, including accelerated ring closure and polymerizability, high depolymerizability and selectivity. The derived polymers constitute a unique class of polythioester materials exhibiting controlled molecular weight, atactic yet high crystallinity, structural diversity, and chemical recyclability.

A robust hole transporting layer based on cobalt(II) acetate was developed by aqueous solution processing technology, low temperature thermal annealing and UV-ozone treatment, which enabled a record high-power conversion efficiency of 18.77 % of binary blend organic solar cells.

Ausgehend von einfachen Bausteinen wurden sechs heterobimetallische Würfel durch einfache Subkomponenten Selbstorganisation hergestellt. Drei der Käfige auf Basis von Eisen(II)ionen zeigten Spin-Crossover-Verhalten in Lösung. Dabei hing die Übergangstemperatur stark von der verwendeten Aldehydkomponenten ab, wodurch eine effiziente Strategie zur Beeinflussung des magnetischen Verhaltens der Komplexe etabliert werden konnte.

Die unerwartete Reduktion von Selen(IV)- und Tellur(IV)-Oxiden zu Chalkogeniden wurde unter ultraalkalischen Bedingungen durch die Verwendung von As₂O₃ als Reduktionsmittel ermöglicht. Durch Optimierung der Reaktionsbedingungen konnten innerhalb von zwei Tagen große Kristalle von K₂Se₃, K₂Te₃ und K₂Se₂Te gezüchtet werden. In der letztgenannten Verbindung wurde das neue gemischte Chalkogenid-Anion (SeTe)²⁻ entdeckt.

Die physiologische Rolle der Abbauprodukte von Chlorophyll und Häm, der exogenen Phyllobiline bzw. endogenen Biline, blieb jahrzehntelang ein ungelöstes Rätsel. Wir beschreiben den Einfluss dieser Tetrapyrrole auf das Aktin-Zytoskelett und stellen G-Aktin als erstes menschliches Zielprotein für Phyllobiline und als neue Zielstruktur für Biline vor. Diese Studie eröffnet eine völlig neue Perspektive auf die Bedeutung dieser ubiquitären Naturstoffe.