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Core–shell and multivariant metal–organic frameworks (MOFs) of the PCN-224 type were prepared using metal-free and metalated porphyrin building blocks. Probing these MOFs with luminescence quenching upon exposure to oxygen reveals efficient gas transport and oxygen quenching in the core of the MOF. Undesirable energy transfer results in diminished contribution of the phosphorescent component in all mixed MOFs except for the physical mixture of individual crystals used as a reference. [ABSTRACT FROM AUTHOR]

The optical oxygen sensing capabilities of the porphyrin-based metal–organic frameworks, PCN-224, Pt(II)PCN-224 and Pd(II)PCN-224 were investigated. The bimolecular quenching constants (kq) of 37 000 (PCN-224), 6700 (Pd(II)PCN-224) and 3900 Pa−1 s−1 (Pt(II)PCN-224) were found and reveal an exceptionally high oxygen-permeability for these materials. Fast gas transport within the network, large pore sizes, and electronic and spatial isolation of the porphyrin indicator in the framework are held responsible for the unprecedentedly high kq values. PCN-224 shows 6.7 ns fluorescence lifetime and the fluorescence in air is quenched 4.2-fold. The metal–organic frameworks based on phosphorescent Pt(II) and Pd(II) porphyrins possess significantly longer decay times of 18.6 and 390 μs, respectively, and are suited to detect oxygen in trace and ultra-trace ranges with limits of detection of 1 and 0.015 Pa, respectively. Apart from free-standing crystals, also metal–organic frameworks supported on different fibrous substrates (poly(acrylonitrile) nanofibers, glass fibres), and flat substrates (TLC silica-gel, poly(amide) filter) were prepared in order to provide oxygen sensor materials of practical use. Electrospun and thermally treated poly(acrylonitrile) nanofibers were found to be particularly favourable and the resulting composite material exhibited the same sensitivity as the free crystals. All sensing materials show reversible cross-talk to humidity at levels up to 53% relative humidity but demonstrate a drastic decrease of oxygen sensitivity at high humidity levels and when exposed to water. A decrease of the quenching constant with rising temperature indicates an important role of surface-adsorbed oxygen in the quenching process. [ABSTRACT FROM AUTHOR]

Luminescent metal–organic frameworks (MOFs) are known to spontaneously self-assemble on human fingerprints. Here, we investigate the different chemical components of fingerprints and determine that MOF growth is predominantly induced by insoluble fatty acids. This finding shows that these simple biomolecules can be employed for the precise positioning of luminescent MOFs. [ABSTRACT FROM AUTHOR]

A series of electron-deficient platinum(ii) and palladium(ii) meso-(diethoxyphosphoryl)porphyrins, namely [10-(diethoxyphosphoryl)-5,15-bis(p-tolyl)porphyrinato]palladium(ii) (PdDTolPP), {10-(diethoxyphosphoryl)-5,15-bis[p-(methoxycarbonyl)phenyl]porphyrinato}palladium(ii) [PdD(CMP)PP], [10-(diethoxyphosphoryl)-5,15-dimesitylporphyrinato]palladium(ii) (PdDMesPP), [5-(diethoxyphosphoryl)-10,15,20-trimesitylporphyrinato]palladium(ii) (PdTMesPP) and the corresponding platinum(ii) compounds, were synthesized and structurally characterized in solution by means of 1H, 13C, 31P NMR spectroscopies and in the solid state by single crystal X-ray diffraction [PdDTolPP, PdD(CMP)PP and PtD(CMP)PP]. Their optical and photophysical properties (UV-vis absorption, luminescence and excitation spectra, phosphorescence quantum yields and lifetimes) were also determined. The complexes under investigation emit at room temperature in the near-infrared region (670–770 nm). Phosphorescence quantum yields of the palladium(ii) meso-phosphorylated porphyrins lie in the range of 3.4 to 5.8%, with lifetimes of 633 to 858 μs in deoxygenated toluene solutions at room temperature. The corresponding platinum(ii) complexes exhibit phosphorescence quantum yields in the range of 9.2 to 11%, with luminescence decay times of 56 to 69 μs. Moreover, effective homogeneous oxygen quenching and good sensitivity in toluene (∼155 Pa−1 s−1) were observed for the platinum(ii) complexes with phosphorylporphyrins in solution. Investigations of the photostability of porphyrinylposphonates and related complexes lacking a phosphoryl group in DMF under irradiation in air using a 400 W vis–NIR lamp demonstrated that photobleaching is strongly dependent on the substituents at the periphery of the macrocycle. Platinum and palladium trimesitylphosphorylporphyrins PdTMesPP and PtTMesPP exhibit high photostability in DMF solution and seem to be the most potentially interesting derivatives of the series for oxygen sensing in biological samples and the covalent immobilization on solid supports to prepare sensing devices including optic fibers. [ABSTRACT FROM AUTHOR]

New aza-BODIPY pH indicators with spectral properties modulated solely by photoinduced electron transfer (PET) are presented. The pH sensitive hydroxyl group is located in the meta-position of a phenyl substituent with respect to the aza-BODIPY core, which eliminates the conjugation to the chromophore. The new dyes show reversible “on”–“off” fluorescence response upon deprotonation of the receptor but no changes in the absorption spectrum, which is in contrast to state-of-the-art indicators of the aza-BODIPY family. This eliminates potential changes in the efficiency of the inner filter effect and Förster resonance energy transfer (FRET) and makes the new dyes suitable acceptors in light harvesting systems used for ratiometric pH imaging. The introduction of electron-withdrawing or electron-donating groups into the receptor results in a set of indicators suitable for measurements from physiological (pH 7) to very alkaline (pH 13) conditions. The new sensors are particularly promising for monitoring of pH changes in concrete, as was recently shown elsewhere. [ABSTRACT FROM AUTHOR]

New complexes of Zn(ii), Pd(ii) and Pt(ii) with Schiff bases are prepared in a one-step condensation of 4-(dibutylamino)-2-hydroxybenzaldehyde and 4,5-diaminophthalonitrile in the presence of a metal salt. The complexes possess efficient absorption in the blue-green part of the spectrum with molar absorption coefficients up to 98 000 M−1 cm−1. The Pt(ii) complex shows very strong red phosphorescence in anoxic solutions at room temperature with a quantum yield of 65% in toluene which places it among the brightest emitters available for this spectral range. The phosphorescence of the Pd(ii) complex under the same conditions is very weak (Φ ＜ 1%) but is enhanced to Φ ＞ 10% upon immobilization into polymers. Optical thermometers based on self-referenced lifetime read-out are prepared upon immobilization of the dyes into gas-blocking poly(vinylidene chloride-co-acrylonitrile). At 25 °C, the materials based on Pd(ii) and Pt(ii) complexes show sensitivities of −2.1 and −0.52%τ/K, respectively. Application of the sensors for imaging of temperature on surfaces (planar optode) and for monitoring of fast temperature fluctuations (fiber-optic microsensor) is demonstrated. Immobilized into a gas-permeable matrix, the Pt(ii) complex also performs as a promising oxygen-sensing material. The new systems are also attractive for imaging of oxygen or temperature with the help of multi-photon microscopy, due to a good match with the biological optical window and much better brightness under two photon excitation compared to that of the conventional Pt(ii) meso-tetra-(pentafluorophenyl)porphyrin. [ABSTRACT FROM AUTHOR]

An electron donor–acceptor dyad based on BODIPY (acceptor) and anthracene (donor) plays either the role of sensitizer or emitter in triplet–triplet annihilation photon up-conversion (TTA-UC). This Janus-like behavior was achieved via altering the relative ordering of charge-transfer and local excited state energies in the dyad through the polarity of TTA-UC media. [ABSTRACT FROM AUTHOR]

The photophysical properties of nitridoosmium(vi) corroles have been investigated. The complexes exhibit room temperature NIR phosphorescence (λmax 779–795 nm). Long decay times (110–150 μs in solution and 136–183 μs in polystyrene) are responsible for efficient quenching of the emission by oxygen. All the complexes act as efficient sensitizers of singlet oxygen (quantum yields of 1O2 0.76–0.95). Optical oxygen sensors prepared on the basis of nitridoosmium(vi) corroles exhibit high photostability and excellent sensitivity in the physiologically relevant range. The complexes have also been found to be promising sensitizers in triplet–triplet annihilation-based upconversion systems. Finally and not least, simple synthetic accessibility makes these dyes particularly attractive for application as optical materials. [ABSTRACT FROM AUTHOR]

We present a microfluidic platform that contains a micro flow reactor for on-chip biomolecule labelling that is directly followed by a separation bed for continuous free-flow electrophoresis and has an integrated hydrogel-based near-infrared fluorescent pH sensor layer. Using this assembly, labelling of protein and peptide mixtures, their separation via free-flow isoelectric focusing and the determination of the isoelectric point (pI) of the separated products via the integrated sensor layer could be carried out within typically around 5 minutes. Spatially-resolved immobilization of fluidic and sensing structures was carried out via multistep photolithography. The assembly was characterized and optimized with respect to their fluidic and pH sensing properties and applied in the IEF of model proteins, peptides and a tryptic digest from physalaemine. We have therefore realized continuous sample preparation and preparative separation, analyte detection, process observation and analyte assignment capability based on pI on a single platform the size of a microscope slide. [ABSTRACT FROM AUTHOR]

New aza-BODIPY indicators which cover the pH scale from 1.5 to 13 are presented. The new indicators feature absorption/emission bands in the red/near-infrared (NIR) spectral region, exhibit high molar absorption coefficients (∼ 80 000 M−1 cm−1) and show good quantum yields (∼20%). All dyes represent promising building blocks for the development of a broad-range sensor for various pH ranges. Combination of four of these pH indicators yields a pH sensor with an extended dynamic range from pH 2 to 9. [ABSTRACT FROM AUTHOR]

A new class of pH-sensitive indicator dyes for optical carbon dioxide sensors based on di-OH-aza-BODIPYs is presented. These colorimetric indicators show absorption maxima in the near infrared range (λmax 670–700 nm for the neutral form, λmax 725–760 nm for the mono-anionic form, λmax 785–830 nm for the di-anionic form), high molar absorption coefficients of up to 77 000 M−1 cm−1 and unmatched photostability. Depending on the electron-withdrawing or electron-donating effect of the substituents the pKa values are tunable (8.7–10.7). Therefore, optical carbon dioxide sensors based on the presented dyes cover diverse dynamic ranges (0.007–2 kPa; 0.18–20 kPa and 0.2–100 kPa), which enables different applications varying from marine science and environmental monitoring to food packaging. The sensors are outstandingly photostable in the absence and presence of carbon dioxide and can be read out via absorption or via the luminescence-based ratiometric scheme using the absorption-modulated inner-filter effect. Monitoring of the carbon dioxide production/consumption of a Hebe plant is demonstrated. [ABSTRACT FROM AUTHOR]

This study highlights possible errors in luminescence lifetime measurements when using bright optical oxygen sensors with high excitation light intensities. An analysis of the sensor with a mathematical model shows that high light intensities will cause a depopulation of the ground state of the luminophore, which results in a non-linear behaviour of the luminescence emission light with respect to the excitation light. The effect of this non-linear behaviour on different lifetime determination methods, including phase-fluorometry, is investigated and in good agreement with the output of the model. Furthermore, the consequences of increasingly high light intensities on phase fluorometric lifetime measurements are illustrated for different oxygen sensors based on benzoporphyrin indicators. For the specific case of PdTPTBPF-based sensors an error as high as 50% is possible under high light conditions (0.25 mol m−2 s−1≈ 50 mW mm−2). A threshold of applied excitation light intensity is derived, thus enabling the point at which errors become significant to be estimated. Strategies to further avoid such errors are presented. The model also predicts a similar depopulation of the ground state of the quencher; however, the effect of this process was not seen in lab measurements. Possible explanations for this deviation are discussed. [ABSTRACT FROM AUTHOR]

A low cost imaging set-up for optical chemical sensors based on NIR-emitting dyes is presented. It is based on a commercially available 2-CCD colour near infrared camera, LEDs and tailor-made optical sensing materials for oxygen and pH. The set-up extends common ratiometric RGB imaging based on the red, green and blue channels of colour cameras by an additional NIR channel. The hardware and software of the camera were adapted to perform ratiometric imaging. A series of new planar sensing foils were introduced to image oxygen, pH and both parameters simultaneously. The used NIR-emitting indicators are based on benzoporphyrins and aza-BODIPYs for oxygen and pH, respectively. Moreover, a wide dynamic range oxygen sensor is presented. It allows accurate imaging of oxygen from trace levels up to ambient air concentrations. The imaging set-up in combination with the normal range ratiometric oxygen sensor showed a resolution of 4–5 hPa at low oxygen concentrations (<50 hPa) and 10–15 hPa at ambient air oxygen concentrations; the trace range oxygen sensor (<20 hPa) revealed a resolution of about 0.5–1.8 hPa. The working range of the pH-sensor was in the physiological region from pH 6.0 up to pH 8.0 and showed an apparent pKa-value of 7.3 with a resolution of about 0.1 pH units. The performance of the dual parameter oxygen/pH sensor was comparable to the single analyte pH and normal range oxygen sensors. [ABSTRACT FROM AUTHOR]

New optical pH-sensors relying on 1,4-diketopyrrolo-[3,4-c]pyrroles (DPPs) as fluorescent pH-indicators are presented. Different polymer hydrogels are useful as immobilization matrices, achieving excellent sensitivity and good brightness in the resulting sensor. The operational pH can be tuned over a wide range (pH 5–12) by selecting the fine structure of the indicator and the matrix. A ratiometric sensor in the form of nanoparticles is also presented. It is suitable for RGB camera readout, and its practical applicability for fluorescence imaging in microfluidic systems is demonstrated. The indicators are synthesized starting from the commercially available DPP pigments by a straightforward concept employing chlorosulfonation and subsequent reaction with amines. Their sensitivity derives from two distinct mechanisms. At high pH (＞9), they exhibit a remarkable alteration of both absorption and fluorescence spectra due to deprotonation of the lactam nitrogen atoms. If a phenolic group is introduced, highly effective fluorescence quenching at near-neutral pH occurs due to photoinduced electron transfer (PET) involving the phenolate form. [ABSTRACT FROM AUTHOR]

Novel pH sensors relying on 1-aminoperylene bisimide dyes covalently grafted onto cross-linked poly(acryloylmorpholine) are presented. They feature fluorescence in the near infra-red range and a large Stokes shift (＞90 nm). [ABSTRACT FROM AUTHOR]

New optical pH-sensors relying on 1,4-diketopyrrolo-[3,4- c ]pyrroles (DPPs) as fluorescent pH-indicators are presented. Different polymer hydrogels are useful as immobilization matrices, achieving excellent sensitivity and good brightness in the resulting sensor. The operational pH can be tuned over a wide range (pH 5-12) by selecting the fine structure of the indicator and the matrix. A ratiometric sensor in the form of nanoparticles is also presented. It is suitable for RGB camera readout, and its practical applicability for fluorescence imaging in microfluidic systems is demonstrated. The indicators are synthesized starting from the commercially available DPP pigments by a straightforward concept employing chlorosulfonation and subsequent reaction with amines. Their sensitivity derives from two distinct mechanisms. At high pH (>9), they exhibit a remarkable alteration of both absorption and fluorescence spectra due to deprotonation of the lactam nitrogen atoms. If a phenolic group is introduced, highly effective fluorescence quenching at near-neutral pH occurs due to photoinduced electron transfer (PET) involving the phenolate form.

Red light-excitable pH sensing materials are manufactured which rely on the use of a fluorescent seminaphthorhodafluor indicator and a luminescent inorganic phosphor as a reference. The phosphors, chromium(III)-activated lanthanide aluminium borates, benefit from chemical and photochemical robustness and are not affected by oxygen. Particularly, a dual lifetime referenced sensing material relies on Cr(III)-activated gadolinium aluminium borate which has low temperature dependence of the decay time. The second material is based on highly temperature-sensitive Cr(III)-doped yttrium aluminium borate and enables dual sensing of pH and temperature. Here, the phosphor simultaneously acts as a temperature probe and as a reference for the pH indicator. The adverse effects of temperature on the properties of the pH indicator are compensated for. The dynamic range of the sensors is optimized by varying the ratio of the components which makes the materials suitable for physiological measurements and for marine applications. The rather poor chemical and photochemical stability of the pH indicator at room temperature should be considered if prolonged measurements are performed.

Core-shell particles (CSPs) composed of a polystyrene core and a poly(vinyl pyrrolidone) shell were dyed with a luminescent platinum(ii) porphyrin probe for oxygen. In parallel, microparticles were dyed with a luminescent iridium(ii) complex acting as a probe for temperature. The particles were deposited (by spraying) on a surface to enable continuous imaging of the distribution of oxygen (and thus of barometric pressure) and temperature. Unlike most previous paints of this kind, a binder polymer is not needed and water can be used as a dispersant. This makes the paint environmentally friendly and reduces costs in terms of occupational health, clean-up, and disposal. Both indicator probes in the sensor paint can be excited at 405 nm using LEDs or diode lasers, whilst their emission maxima are spectrally separated by about 130 nm. Thus, two independent optical signals are obtained that allow for fluorescent imaging of barometric pressure (in fact oxygen partial pressure) and of temperature, and also to correct the oxygen signal for effects of temperature. The paint was calibrated at air pressures ranging from 50 mbar to 2000 mbar and at temperatures between 1 degrees C and 50 degrees C.

Optical nanosensors are advanced analytical tools that combine advantages of conventional sensor technology with flexibility in use of dissolved indicators. Introduced a decade ago, optical nanosensors attract increasingly more attention each year. In fact, the number of reports on the topic has doubled in the last 2-3 years. In this contribution, we aim to highlight recent developments of optical nanosensors and give an overview on strategies to design these nanosensors with different levels of complexity. Applications of this smart technology, advantages, challenges, and risks will be discussed.