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Here we report on carbon monoxide-photoreleasable compounds (photoCORMs) that combine heptamethine cyanine and flavonol chromophores and are activated upon irradiation with near-infrared light. Excellent CO-release yields and uncaging cross sections in aqueous solutions, enhanced water solubilities thanks to polar substituents or a host-guest approach using cucurbit[7]uril are demonstrated. The hybrids display outstanding biocompatibility and diverse, structure-dependent cell penetrability and internalization.

We report a method of glycosylated enzymes' surface immobilisation and stabilisation. The enzyme is immobilised at the surface of silica nanoparticles through the reversible covalent binding of vicinal diols of the enzyme glycans with a surface-attached boronate derivative. A soft organosilica layer of controlled thickness is grown at the silica surface, entrapping the enzyme and thus avoiding enzyme leaching. We demonstrate that this approach results not only in high and durable activity retention but also enzyme stabilisation.

Field-effect transistor (FET) sensors are attractive potentiometric (bio)chemical measurement devices because of their fast response, low output impedance, and potential for miniaturization in standard integrated circuit manufacturing technologies. Yet the wide adoption of these sensors for real-world applications is still limited, mainly due to temporal drift and cross-sensitivities that introduce considerable error in the measurements. In this paper, we demonstrate that such non-idealities can be corrected by joint use of an array of FET sensors – selective to target and major interfering ions – with machine learning (ML) methods in order to accurately predict ion concentrations continuously and in the field. We studied the predictive performance of linear regression (LR), support vector regression (SVR), and state-of-art deep neural networks (DNNs) when monitoring pH from combinatorial H+, Na+, and K+ion-sensitive FET (ISFET) sequences of readings collected over a period of 90 consecutive days in real water quality assessment conditions. The proposed ML algorithms were trained against reference online measurements obtained from a commercial pH sensor. Results show a greater capability of DNNs to provide precise pH monitoring for longer than a week, achieving a relative root-mean-square error reduction of 73% over standard two-point sensor calibration methods., The authors acknowledge funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie grant agreement No 747848 and the SNSF-Sinergia WeCare project (No.CRSII5_177255).

Triangulene is the smallest non-Kekulé graphene fragment known as Clar's hydrocarbon. Due to its open-shell electronic structure, triangulene is a promising molecular building block of carbon-based organic materials for spintronics and quantum molecular science. It comprises six benzenoid rings arranged in a triangular shape with two unpaired electrons delocalized over the entire conjugated core, making this molecule highly reactive. A triplet ground state is predicted for this hydrocarbon by Ovchinnikov's rule, or Lieb's theorem, in accord with Hund's rule. The pioneering work on triangulene was performed almost 70 years ago by Erich Clar, who attempted to prepare the pristine compound. Since then, several synthetic approaches to prepare this molecule have been exploited. The extreme reactivity of triangulene can be circumvented using on-surface techniques or by installation of sterically demanding substituents, which kinetically stabilize the diradical core against oligomerization in solution. The first two examples of a persistent derivative of triangulene were simultaneously and independently developed last year. This article presents a historical development in the synthesis of triangulene and its derivatives and outlines possible future applications in ferromagnetic materials, electrically conductive polymers or quantum computing.

Triangulene, known as Clar's hydrocarbon, is a prototypical non-Kekul�� diradical comprised of six benzenoid rings fused in a triangular shape. We synthesized and characterized its trimesityl derivative, illustrating that three bulky substituents installed in the centers of the zigzag edges suffice to protect all reactive positions. This work brings prospects to use triangulene and its open-shell analogs in spintronic materials via solution-phase synthesis.

Iron is important for bacterial growth and survival, as it is a common co-factor in essential enzymes. Although iron is very abundant in the earth crust, its bioavailability is low in most habitats because ferric iron is largely insoluble under aerobic conditions and at neutral pH. Consequently, bacteria have evolved a plethora of mechanisms to solubilize and acquire iron from environmental and host stocks. In this review, I focus on Pseudomonas spp. and first present the main iron uptake mechanisms of this taxa, which involve the direct uptake of ferrous iron via importers, the production of iron-chelating siderophores, the exploitation of siderophores produced by other microbial species, and the use of iron-chelating compounds produced by plants and animals. In the second part of this review, I elaborate on how these mechanisms affect interactions between bacteria in microbial communities, and between bacteria and their hosts. This is important because Pseudomonas spp. live in diverse communities and certain iron-uptake strategies might have evolved not only to acquire this essential nutrient, but also to gain relative advantages over competitors in the race for iron. Thus, an integrative understanding of the mechanisms of iron acquisition and the eco-evolutionary dynamics they drive at the community level might prove most useful to understand why Pseudomonas spp., in particular, and many other bacterial species, in general, have evolved such diverse iron uptake repertoires.

Ni/CoOx sites were supported on an around 2 nm-TiOx modified hematite photoanode for water oxidation. TiOx demonstrates insignificant hole accumulation and a catalytically inactive surface that serves as an ideal platform. We reveal that the NiOx favors the extraction of holes from the TiOx surface, which are efficiently transferred to active CoOx for water oxidation.

This communication presents a novel truncated NiII-containing metbalamin and describes its reversible one electron reduction to a catalytically active NiI species, that features cofactor F430 model character. Our results strikingly demonstrate that stabilization of NiI is not restricted to the related hydroporhyrinoid ligands and is of relevance to the application of metallocorrins in (biomimetic) catalysis., Chemical Communications, 57 (59), ISSN:1359-7345, ISSN:1364-548X

Acid bone lysates (ABLs) represent the growth factors and other molecules released during autologous graft resorption. However, the impact of these bone-derived growth factors on the healing of bone defects has not yet been investigated. The aim of the present study was, therefore, to examine the impact of ABLs adsorbed to collagen membranes on bone regeneration. To this end, in 16 female Sprague Dawley rats, a standardized 5-mm-diameter critical size defect on the calvarial bone was created. The defects were covered with collagen membranes that had been soaked either in serum-free media or ABLs followed by lyophilization. After a healing period of 4���weeks, micro-computed tomography (��CT) and histological analyses by means of undecalcified thin ground sections were performed. ��CT analysis of the inner 4���mm of the calvaria defect showed a greater bone defect coverage in the control group when compared to ABL group, 29.8% (confidence interval [CI]: 17.7-50.3) versus 5.6% (CI: 1.0-29.8, p =���.03), respectively. Moreover, we found significantly more absolute bone volume (BV) in the control group when compared to ABL group, 0.59���mm3 (CI: 0.27-1.25) versus 0.07���mm3 (CI: 0.06-0.59, p =���.04), respectively. Histomorphometry confirmed these findings with a relative BV in the central compartment of 14.1% (CI: 8.4-20.6) versus 5.6% (CI: 3.4-7.9, p =���.004), respectively. These findings indicate that bone-derived growth factors contained in ABLs are able to attenuate bone regeneration within collagen membranes.

We report the synthesis of novel tetraplatinated metalloporphyrin-based photosensitizers (PSs) for photodynamic therapy (PDT), their characterization, cellular uptake and localization, as well as the determination of their in vitro light-induced anticancer properties. The PSs show excellent phototoxic indexes up to 5800 against HeLa cells, which is, to the best of our knowledge, the highest value reported for any porphyrin so far. Furthermore, isotopic labelling of the porphyrin with a highly enriched 67Zn isotope was performed in order to determine the distribution ratio of zinc to platinum by ICP-MS, allowing to differentiate between naturally occurring zinc and 67Zn that was introduced into the cells by the PS. We conclude that the platinum units within the platinum-PS conjugates help to solubilize the PS and, at the same time, act as cell-penetrating vectors, enhancing the efficiency of the PS without causing a significant dark toxicity.

Cycloruthenation is a well known process in organometallic ruthenium chemistry. In this work, we report unprecedented cycloruthenated rhenium bis-arene compounds with planar chirality. In a two-step process, the reaction of acetyl-pyridine with [Re(η6-C6H6)2]+ introduced a pyridinyl-methanol ligand at one of the arene rings. Coordination of [Ru(CO)2Cl2] led to cycloruthenation, and the products were obtained as two diastereomeric pairs of enantiomers. Under basic pH conditions, the two pairs of enantiomers undergo spontaneous and reversible dimerization. The cycloruthenated monomers were fully characterized, and the dimerization process was studied by NMR, IR spectroscopy, and DFT calculations., Chemical Communications, 56 (73), ISSN:1359-7345, ISSN:1364-548X

Upon solidification, most metallic alloys form dendritic structures that grow along directions corresponding to low index crystal axes, e.g., $$\langle100\rangle$$ 〈 100 〉 directions in fcc aluminum. However, recent findings[1,2] have shown that an increase in the zinc content in Al-Zn alloys continuously changes the dendrite growth direction from $$\langle100\rangle$$ 〈 100 〉 to $$\langle110\rangle$$ 〈 110 〉 in {100} planes. At intermediate compositions, between 25 wt pct and 55 wt pct Zn, $$\langle320\rangle$$ 〈 320 〉 dendrites and textured seaweeds were reported. The reason for this dendrite orientation transition is that this system exhibits a large solubility of zinc, a hexagonal metal, in the primary fcc aluminum phase, thus modifying its weak solid-liquid interfacial energy anisotropy. Owing to the complexity of the phenomenology, there is still no satisfactory theory that predicts all the observed microstructures. The current study is thus aimed at better understanding the formation of these structures. This is provided by the access to their 3D morphologies via synchrotron-based X-ray tomographic microscopy of quenched Bridgman solidified specimens in combination with the determination of the crystal orientation of the dendrites by electron-backscattered diffraction. Most interestingly, all alloys with intermediate compositions were shown to grow as seaweeds, constrained to grow mostly in a (001) symmetry plane, by an alternating growth direction mechanism. Thus, these structures are far from random and are considered less hierarchically ordered than common dendrites

The Kirkendall effect, usually associated with the formation of undesirable fields of micron-size pores, can be used to fabricate hollow nano- and microstructures, where all pores have coalesced into a single cavity. Here, this concept is used with the goal of converting 50 μm diameter Ni-20wt.%Cr wires into Ni–Cr–Al tubes by diffusion of a surface-deposited aluminide coating. The formation and evolution of Kirkendall pores, created by imbalanced diffusion fluxes of Al, Ni and/or Cr, are investigated using both in situ X-ray tomographic microscopy and ex situ annealing studies. The tomography results indicate that the pores nucleate near the interface between the Ni–Cr core and β-NiAl(Cr) reaction layer that develops upon homogenization. They then grow and coalesce near the center of the radial cross-section of the wire. This is followed by a stagnation period until the pores migrate longitudinally due to the influence of a temperature gradient imposed by the laser heating used for annealing. The ex situ experiments are in qualitative agreement with the tomography study with the exception of the secondary pore migration along the wire length, as expected because the ex situ study is conducted under isothermal conditions. Detailed features of the microstructure were discernable only upon metallographic preparation and include Cr-rich precipitates and an α-Cr(Al,Ni) rejection region that formed during coating and homogenization, respectively. In situ X-ray tomographic microscopy is thus demonstrated to be a viable technique to use in conjunction with more conventional ex situ metallographic techniques to conduct interdiffusion and Kirkendall pore studies.

Post-translational modification (PTM) of proteins plays essential regulatory roles in a variety of pathological conditions. Reliable and practical assays are required to accelerate the discovery of inhibitors and activators for PTM related diseases. Today, methodologies are based on specific or group-specific PTM recognition of e.g. phosphate for kinase activity without extending to other type of PTMs. Here we have established a universal time-resolved luminescence assay on a peptide-break platform for the direct detection of wide variety of PTMs. The developed assay is based on the leucine zipper concept wherein a europium-chelate labeled detection peptide and a non-labeled peptide substrate form a highly luminescent dimer. As an active PTM enzyme at sub or low nanomolar concentration modifies the substrate peptide, the luminescent signal of the detached detection peptide is quenched in the presence of soluble quenchers. The functionality of this universal assay technique has been demonstrated for the monitoring of phosphorylation, dephosphorylation, deacetylation, and citrullination with high applicability also to other PTMs in a high throughput format.

Magnetic properties of endohedral metallofullerenes with nitride clusters DySc(2)N and Dy(2)ScN and different carbon cages are studied by SQUID magnetometry. All molecules behave as single molecule magnets (SMMs) and exhibit magnetic hysteresis. It is found that the blocking temperature of magnetization and relaxation times strongly depend on the fullerene cage, with the C(80)-I(h) isomer offering the best SMM properties.

This communication describes a disassembly based approach for the detection of biologically relevant di- and tri-phosphates in water using locked fluorescent salicylaldehyde probes.

To better understand the influence of Fe-rich intermetallics on solidification defect formation, fast in situ synchrotron X-ray tomographic microscopy experiments were performed on a commercial A319 alloy (Al–7.5Si–3.5Cu, wt.%) with 0.2 and 0.6 wt.% Fe. Real-time observations during solidification and semi-solid deformation experiments reveal that β-intermetallics contribute via several different mechanisms to porosity formation and hot tearing susceptibility. While β-intermetallics were not observed to nucleate porosity directly, they do block interdendritic channels, thereby reducing the shrinkage feeding, and increasing pore tortuosity. Pores also grow preferentially along the surface of the β-intermetallics, suggesting that the β-phase has a lower gas–solid interfacial energy than α-Al, thus assisting in increasing pore volume. During uniaxial tension experiments, the ductile failure of the semi-solid, intermetallic-poor, base alloy transitions to a brittle-like failure when a large amount of β-intermetallics are present. In all post-failure microstructures, internal damage was preferentially orientated perpendicular to the loading direction, agreeing with prior experimental and numerical studies., Acta Materialia, 68, ISSN:1359-6454

Many studies and personalized medicine in general require frequent measurements and/or rapid results of biomarker levels. Here we show that 20 low volatility metabolites of the tryptophan pathway can be detected in exhaled human breath. This real-time and non-invasive method offers an attractive alternative to blood analysis.

Bi 2 O 2 CO 3 nanosheets with exposed {0 0 1} facets were obtained from the straightforward and economic room temperature conversion of commercial Bi 2 O 3 with CO 2 as atmospheric carbon source. The growth process of Bi 2 O 2 CO 3 was investigated with a variety of analytical methods including X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). (BiO) 4 CO 3 (OH) 2 was identified as an intermediate during the transformation of bulk Bi 2 O 3 into Bi 2 O 2 CO 3 nanosheets. The humidity sensing tests indicated high sensitivities with impedance changes of 4 orders and capacitance changes of 3 orders of magnitude over a relative humidity (RH) range from 11 to 95%. Moreover, the humidity sensor based on Bi 2 O 2 CO 3 nanosheets revealed a narrow humidity hysteresis, rapid response and recovery time with good reproducibility. These results demonstrated that Bi 2 O 2 CO 3 is a promising humidity sensing material for environmental monitoring and humidity control.

The time-of-day of drug application is an important factor in maximizing efficacy and minimizing toxicity. Real-time in vivo mass spectrometric breath analysis of mice was deployed to investigate time-of-day variation in ketamine metabolism. Different production rates of ketamine metabolites, including the recently described anti-depressant hydroxynorketamine, were found in opposite circadian phases. Thus, breath analysis has potential as a rapid and 3Rs (Replacement, Reduction and Refinement) conforming screening method to estimate the time-dependence of drug metabolism.\ud \ud

This communication describes the anti-platelet effects of a new class of cis-rhenium(II)- dicarbonyl-vitamin B12 complexes (B12-ReCORMs) with tuneable CO releasing properties.

The β-phase of the industrially important Pigment Red 170 (β-P.R. 170) has a structure with severe layer stacking disorder. The single-crystal X-ray diffraction pattern consists of a difficult-to-disentangle mix of Bragg diffraction superimposed on rods of diffuse scattering which impede the estimation of accurate Bragg intensities. Two average monoclinic structure models with the same unit-cell dimensions, but different extents of disorder in the layers and different space groups seem plausible, one with the non-conventional space group settingB21/g(No. 14,Z′ = 2) and one inP21/a(No. 14,Z′ = 4). Disordered molecules related by a translation of 0.158bare present in all layers of theB21/gmodel and in every second layer of theP21/amodel. Layer-to-layer contacts are practically the same in both models. According to order–disorder theory, both models are valid superposition structures. Structure-factor calculations show that the pattern of strong and weak Bragg reflections is very similar for the two models.Rfactors indicate that theB21/gmodel is the most economic representation of the average structure. However, given the limitations in data processing, theP21/amodel should not be discarded and further insight sought from a detailed analysis of the experimental diffuse scattering. The difficulties encountered in this analysis raise the question of whether or not the concept of an average structure is applicable in practice to β-P.R. 170.

Silicene–the silicon-based counterpart of graphene–has a two dimensional structure that is responsible for the variety of potentially useful chemical and physical properties. The existence of silicene has been achieved recently owing to experiments involving epitaxial growth of silicon as stripes on Ag(001), ribbons on Ag(110), and sheets on Ag(111). The nano-ribbons observed on Ag(110) were found–by both high definition experimental scanning tunneling microscopy images and density functional theory calculations–to consist of an arched honeycomb structure. Angle resolved photo-emission experiments on these silicene nano-ribbons on Ag(110), along the direction of the ribbons, showed a band structure which is analogous to the Dirac cones of graphene. Unlike silicon surfaces, which are highly reactive to oxygen, the silicene nano-ribbons were found to be resistant to oxygen reactivity. On the theoretical side, recent extensive efforts have been deployed to understand the properties of standalone silicene sheets and nano-ribbons using both tight-binding and density functional theory calculations. Unlike graphene it is demonstrated that silicene sheets are stable only if a small buckling (0.44 A) is present. The electronic properties of silicene nano-ribbons and silicene sheets were found to resemble those of graphene. Although this is a fairly new avenue, the already obtained outcome from these important first steps in understanding silicene showed promising features that could give a new future to silicon in the electronics industry, thus opening a promising route toward wide-range applications. In this review, we plan to introduce silicene by presenting the available experimental and theoretical studies performed to date, and suggest future directions to be explored to make the synthesis of silicene a viable one.

Highly aligned arrays of ZnO/TiO2 core/shell nanorods were fabricated on glass substrates by hydrothermal growth of ZnO nanorods cores followed by the deposition of anatase TiO2 shells in a sol–gel process. The characterization of these composite materials with scanning electron microscopy (SEM), Raman spectroscopy, X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX) and transmission emission microscopy (TEM) points to the formation of crystalline ZnO nanorod cores that are coated with anatase TiO2 shells. Humidity sensors based on these core/shell nanorod arrays exhibit outstanding sensitivities with capacitances varying from 101 to 106 pF over a relative humidity (RH) range of 11%–95% at room temperature, which is 1.5 and 3 orders of magnitude higher than that of pristine TiO2 films and ZnO nanorods, respectively. Complex impedance analysis indicated that the enhanced humidity sensitivity is probably due to the high surface/volume ratio of this core/shell material in combination with the remarkable hydrophilicity of the TiO2 shell.

The purpose of this study was to determine whether macrophage depletion using clodronate liposomes diminishes wear-debris-induced inflammatory osteolysis in a murine osteolysis model. Ultra high molecular weight polyethylene (UHMWPE) particles were introduced into established air pouches on BALB/c mice, followed by implantation of calvaria bone from syngeneic littermates. Macrophages were depleted by the intraperitoneal injection of clodronate liposome (2 mg) 2 days before bone implantation and re-injection every 3 days (1 mg) until the sacrifice of the mice. Mice without clodronate liposome therapy or treated with empty liposome as well as mice injected with saline alone were included in this study as controls. Pouch tissues were collected 14 days after bone implantation for molecular and histology analysis. Our findings indicated that (1) macrophage depletion in clodronate-liposome-treated mice was achieved, as illustrated by F4/80 immunostaining in both pouch and spleen tissues; (2) clodronate-liposome treatment significantly reduced UHMWPE-induced tissue inflammation, with diminished pouch membrane thickness, reduced inflammatory cellular infiltration, and lowered interleukin 1beta (IL-1beta) and tumor necrosis factor alpha (TNFalpha) expression; (3) clodronate-liposome treatment markedly reduced the number of TRAP(+) cells in pouch tissues and protected against bone collagen depletion. In conclusion, this study demonstrates that macrophage depletion using clodronate-liposome reduces UHMWPE particle-induced inflammatory osteolysis. This observation supports the hypothesis that macrophages contribute to the severity of UHMWPE particles induced inflammatory osteolysis, and suggest that macrophage depletion represents a viable therapeutic approach to the prevention and treatment of patients with aseptic loosening.

This paper presents the first use of Digital Volume Correlation (DVC) on Carbon Fibre Reinforced Plastics (CFRPs) to quantify the strain fields ahead of a Mode I delamination. DVC is a relatively novel tool that can be used to measure displacements and strains occurring inside materials under load. In conjunction with Computed Tomography (CT), the technique has been applied to porous materials, with results providing strain data for validation of Finite Element (FE) models. However, the application of the technique to laminated materials has been limited, with studies often requiring fiducial markings required for volume correlation. In this work, crack propagation steps were captured at a 325 nm voxel resolution using Synchrotron Radiation Computed Tomography (SRCT). The material systems investigated featured different crack bridging mechanisms such as; particle-bridges, resin ligaments, and fibre-bridges. An assessment of noise and sub-volume size on the strain measurement determined that the optimal sub-volume size was 150 voxels with 50% overlap. This provided a spatial resolution of 48.8 μm for strain and a corresponding strain resolution ranging between 220 and 690 μe for the repeated reference scans. A rigid body translation study confirmed that specimen movements perpendicular to the fibre orientation support the ‘real’ physical displacements. However, along the fibre direction, the correlation was poor, with correct displacements being detected only within the particle-toughened interlayers. The study demonstrates that strain measurements can be made perpendicular to the fibre direction across the interlayer, which could be used to validate future FE models of these poorly understood particle-toughened interlayers.

An in situ method to study the behavior of alloys during rapid heating and cooling combining laser heating with synchrotron micro X-ray diffraction and high-speed imaging is presented. Near-spherical Ti-48Al specimens were melted using a laser-based heating system consisting of two diode lasers and subsequently rapidly solidified using a Cu support structure. The Al-rich Ti-48Al forms a fine grained dual phase alpha(2) + gamma microstructure. Upon solidification, the formation of the beta-phase is fully suppressed. Time-resolved peak evolution and temperature-corrected micro X-ray diffraction data provides clear observations of solidification and solid state phase transformations under non-equilibrium conditions similar to beam-based additive manufacturing. (C) 2015 Elsevier Ltd. All rights reserved.

DMAT is a new fluorescent thymidine mimic composed of 2′-deoxyuridine fused to dimethylaniline. DMAT exhibits the same pKa and base pairing characteristics as native thymidine residues, and its fluorescence properties are highly sensitive to nucleobase ionization, base pairing and metal binding.

Cellular uptake of vitamin B12-cisplatin conjugates was estimated via detection of their metal constituents (Co, Pt, and Re) by inductively coupled plasma mass spectrometry (ICP-MS). Vitamin B12 (cyano-cob(iii)alamin) and aquo-cob(iii)alamin [Cbl-OH2](+), which differ in the β-axial ligands (CN(-) and H2O, respectively), were included as control samples. The results indicated that B12 derivatives delivered cisplatin to both cellular cytosol and nuclei with an efficiency of one third compared to the uptake of free cisplatin cis-[Pt(II)Cl2(NH3)2]. In addition, uptake of charged B12 derivatives including [Cbl-OH2](+), [{Co}-CN-{cis-PtCl(NH3)2}](+), [{Re}-{Co}-CN-{cis-PtCl(NH3)2}](+), and [{Co}-CN-{trans-Pt(Cyt)(NH3)2}](2+) (Cyt = cytarabin) was high compared to neutral B12, which implied the existence of an additional internalization pathway for charged B12 vitamin analogs. The affinities of the charged B12 derivatives to the B12 transporters HC, IF and TC were similar to that of native vitamin B12.

The presented label-free optical biosensor system relies on a MEMS micro-mirror to interrogate waveguide grating regions at a high repetition rate in the kHz range by scanning the angle of the incident coherent light. The angle-tunable MEMS mirror permits an extended scanning range and offers the flexibility to measure at various wavelengths and optical powers – an interesting feature for an enhanced surface-to-bulk sensitivity ratio and extended, multiplexed sensor arrays. An excellent refractometric sensitivity with a limit of detection towards effective refractive index changes of Δneff 150 kDa) and small (

4-4'-Disubstituted biphenyl boronic acids (BBAs) are push-pull fluorophores with "turn-on" fluorescence properties. Upon carbohydrate triol binding, BBA boronate esters can participate in photon-induced electron transfer, giving a twisted intramolecular charge transfer (TICT) complex. The resulting TICT emissions distinguish between carbohydrates that bind to boron as a diol versus triol unit, thereby revealing stereochemical information about the carbohydrate.

Palladium-catalyzed hydrogenation of an octahedral zinc trans-ditriflate hemiporphyrazine "HpH2Zn(OTf)2" furnishes a new macrocycle "HpH6Zn(OTf)2". This reaction is fully reversible upon heating in nitrobenzene, and the conversion is easily monitored by changes in color and fluorescence properties. The reversible cycling between these molecules may find future applications in hemiporphyrazine-based catalysts and/or hydrogen storage devices.

Triphenylamine-based fluorophores containing pyrene or corannulene show variable fluorescence quenching sensitivity toward nitro explosives. The most sensitive fluorophore is capable of detecting TNT on the ng cm(-2) scale; the array is useful for identifying nitro aromatics.

The caging of small molecules has revolutionized biological research by providing a means to regulate a wide range of processes. Here we report on a generic pharmacological method to cage proteins in a similar fashion. The present approach is of value in both fundamental and applied research, e.g. in tissue engineering., Chemical Communications, 49 (53), ISSN:1359-7345, ISSN:1364-548X