Reactive Magnesium Nanoparticles to Perform Reactions in Suspension.

Zerovalent magnesium (Mg(0)) nanoparticles are prepared in the liquid phase (THF) by reduction of MgBr2 either with lithium naphthalenide ([LiNaph]) or lithium biphenyl ([LiBP]). [LiBP]-driven reduction results in smaller Mg(0) nanoparticles (10.3±1.7 nm) than [LiNaph]-driven reduction (28.5±4 nm). The as-prepared Mg(0) nanoparticles are monocrystalline (d101=245±5 pm) for both types of reduction. Their reactivity is probed by liquid-phase reaction (THF, toluene) in suspension near room temperature (20-120 °C) with 1-bromoadamantane (AdBr), chlortriphenylsilane (Ph3SiCl), trichlorphenylsilane (PhSiCl3), 9H-carbazole (Hcbz), 7-azaindole (Hai), 1,8-diaminonaphthalene (H4nda) and N,N'-bis(α-pyridyl)-2,6-diaminopyridine (H2tpda) as exemplary starting materials. The reactions result in the formation of 1,1'-biadamantane (1), [MgCl2(thf)2]×Ph6Si2 (2), [Mg9(thf)14Cl18] (3), [Mg(cbz)2(thf)3] (4), [Mg4O(ai)6]×1.5 C7H8 (5), [Mg4(H2nda)4(thf)4] (6) and [Mg3(tpda)3] (7) with 40-80 % yield. 1 and 2 show the reactivity of Mg(0) nanoparticles for C-C and Si-Si coupling reactions with sterically demanding starting materials. 3-7 represent new coordination compounds using sterically demanding N-H-acidic amines as starting materials. The formation of multinuclear Mg2+ complexes with multidentate ligands illustrates the potential of the oxidative approach to obtain novel compounds with Mg(0) nanoparticles in the liquid phase.

Correction: (TeCl)4(TiCl4) with isolated Te4Cl16 and TiCl4 molecules and second-harmonic-generation.

Correction for '(TeCl)4(TiCl4) with isolated Te4Cl16 and TiCl4 molecules and second-harmonic-generation' by Maxime A. Bonnin et al., Dalton Trans., 2024, 53, 4962-4967, https://doi.org/10.1039/D4DT00284A.

[GeRu6(CO)18HI]: A Germanium-Centered Ruthenium Carbonyl Cluster with Aromatic Ring Current.

The carbonyl cluster compound [GeRu6(CO)18HI] is unique in regard to its structure and bonding with a GeRu6 cluster core, a planar GeRu4HI unit, extensive multi-center bonding, and an aromatic ring current similar to benzene (9-10 nA T-1). The open-shell cluster core is a Ge-centered five-membered Ru4(Ru2) ring with CO ligands and an additional H and I atom, each bridging two Ru atoms on opposite sides of the cluster core. The compound is prepared at 130 °C in a weakly-coordinating ionic liquid.

Cocktail of lipophilic and hydrophilic chemotherapeutics in high-load core@shell nanocarriers to treat pancreatic tumours.

ITC/Toc@Gd2(FLP)3 core@shell nanocarriers with a chemotherapeutic cocktail of lipophilic irinotecan (ITC) as the particle core and hydrophilic fludarabine phosphate (FLP) in the particle shell are realized. They are prepared via a microemulsion approach with ITC dissolved in tocopherol (Toc) as droplet phase and stabilized by water-insoluble Gd2(FLP)3. The synthesis can be followed by zeta-potential analysis. X-ray powder diffraction, infrared spectroscopy, elemental analysis, thermogravimetry, and photometry show a drug load of 49 µg per mL ITC and 317 µg per mL FLP at a nanocarrier concentration of 1.5 mg mL-1. Size and structure are evidenced by electron microscopy, resulting in a total diameter of 45 ± 16 nm, an inner core of 40 ± 17 nm, and a shell of 3-8 nm. In vitro studies with different cancer cell lines (i.e., human melanoma/SK-Mel-28, cervical cancer/HeLa, mouse pancreatic cancer/Panc02 and KPC as well as human pancreatic cancer/Capan-1 cells) prove efficient nanocarrier uptake and promising cytostatic efficacy. Specifically for KPC cells, ITC/Toc@Gd2(FLP)3 nanocarriers show an increased efficacy, with half maximal inhibitory concentration (IC50: 4.2 µM) > 10 times lower than the free drugs (IC50: ITC: 47.7 µM, FLP: 143 µM). This points to the synergistic effect of the ITC/FLP drug cocktail in the nanocarriers and may result in a promising strategy to treat pancreatic ductal adenocarcinoma (PDAC).

(TeCl)4(TiCl4) with isolated Te4Cl16 and TiCl4 molecules and second-harmonic-generation.

(TeCl4)4(TiCl4) is obtained by reaction of TeCl4 and TiCl4 at 50 °C with quantitative yield. The compound is composed of isolated, molecular (TeCl4)4 heterocubane-type units as well as isolated, molecular TiCl4 tetrahedra. The (TeCl4)4 heterocubane is arranged like a body-centred cubic cell with TiCl4 tetrahedra occupying 4 of 6 octahedral sites. (TeCl4)4(TiCl4) crystallizes in the space group I4̄ with an unidirectional alignment of the tetrahedral building units. The structure of the compound is obtained from single crystal X-ray diffraction and confirmed by Rietveld refinement of powder diffraction data. Thermogravimetry, optical spectroscopy, infrared and Raman spectroscopy are employed to further characterize the title compound. Second harmonic generation (SHG) is observed with a strong intensity (1.6-times higher than potassium dihydrogen phosphate/KDP). The SHG effect is observed in the visible spectral regime as the band gap, derived from a Tauc plot, is 2.8 eV.

Sc, Zr, Hf, and Mn Metal Nanoparticles: Reactive Starting Materials for Synthesis Near Room Temperature.

Zerovalent scandium, zirconium, hafnium, and manganese nanoparticles are prepared by reduction of ScCl3, ZrCl4, HfCl4, and MnCl2 with lithium or sodium naphthalenide in a one-pot, liquid-phase synthesis. Small-sized monocrystalline nanoparticles are obtained with diameters of 2.4 ± 0.2 nm (Sc), 4.0 ± 0.9 nm (Zr), 8.0 ± 3.9 nm (Hf) and 2.4 ± 0.3 nm (Mn). Thereof, Zr(0) and Hf(0) nanoparticles with such size are shown for the first time. To probe the reactivity and reactions of the as-prepared Sc(0), Zr(0), Hf(0), and Mn(0) nanoparticles, they are exemplarily reacted in the liquid phase (e.g., THF, toluene, ionic liquids) with different sterically demanding, monodentate to multidentate ligands, mainly comprising O-H and N-H acidic alcohols and amines. These include isopropanol (HOiPr), 1,1'-bi-2-naphthol (H2binol), N,N'-bis(salicylidene)ethylenediamine (H2salen), 2-mercaptopyridine (2-Hmpy), 2,6-diisopropylaniline (H2dipa), carbazole (Hcz), triphenylphosphane (PPh3), N,N,N',N'-tetramethylethylenediamine (tmeda), 2,2'-bipyridine (bipy), N,N'-diphenylformamidine (Hdpfa), N,N'-(2,6-diisopropylphenyl)-2,4-pentanediimine ((dipp)2nacnacH), 2,2'-dipydridylamine (Hdpa), and 2,6-bis(2-benzimidazolyl)pyridine (H2bbp). As a result, 22 new compounds are obtained, which frequently exhibit a metal center coordinated only by the sterically demanding ligand. Options and restrictions for the liquid-phase syntheses of novel coordination compounds using the oxidation of base-metal nanoparticles near room temperature are evaluated.

Glucocorticoid Nanoparticles Show Full Therapeutic Efficacy in a Mouse Model of Acute Lung Injury and Concomitantly Reduce Adverse Effects.

Glucocorticoids (GCs) are widely used to treat inflammatory disorders such as acute lung injury (ALI). Here, we explored inorganic-organic hybrid nanoparticles (IOH-NPs) as a new delivery vehicle for GCs in a mouse model of ALI. Betamethasone (BMZ) encapsulated into IOH-NPs (BNPs) ameliorated the massive infiltration of neutrophils into the airways with a similar efficacy as the free drug. This was accompanied by a potent inhibition of pulmonary gene expression and secretion of pro-inflammatory mediators, whereas the alveolar-capillary barrier integrity was only restored by BMZ in its traditional form. Experiments with genetically engineered mice identified myeloid cells and alveolar type II (AT II) cells as essential targets of BNPs in ALI therapy, confirming their high cell-type specificity. Consequently, adverse effects were reduced when using IOH-NPs for GC delivery. BNPs did not alter T and B cell numbers in the blood and also prevented the induction of muscle atrophy after three days of treatment. Collectively, our data suggest that IOH-NPs target GCs to myeloid and AT II cells, resulting in full therapeutic efficacy in the treatment of ALI while being associated with reduced adverse effects.

Experimental and computational study of the exchange interaction between the V(III) centers in the vanadium-cyclal dimer.

[V2(HCyclal)2] is prepared by controlled oxidation of vanadium nanoparticles at 50 °C in toluene. The V(0) nanoparticles are synthesized in THF by reduction of VCl3 with lithium naphthalenide. They exhibit very small particle sizes of 1.2 ± 0.2 nm and a high reactivity (e.g. with air or water). By reaction of V(0) nanoparticles with the azacrown ether H4Cyclal, [V2(HCyclal)2] is obtained with deep green crystals and high yield. The title compound exhibits a V(III) dimer (V⋯V: 304.1(1) pm) with two deprotonated [HCyclal]3- ligands as anions. V(0) nanoparticles as well as the sole coordination of V(III) by a crown ether as the ligand and nitrogen as sole coordinating atom are shown for the first time. Magnetic measurements and computational results point to antiferromagnetic coupling within the V(III) couple, establishing an antiferromagnetic spin S = 1 dimer with the magnetic susceptibility determined by the thermal population of the total spin ranging from ST = 0 to ST = 2.

High-Load Gemcitabine Inorganic-Organic Hybrid Nanoparticles as an Image-Guided Tumor-Selective Drug-Delivery System to Treat Pancreatic Cancer.

Pancreatic ductal adenocarcinoma (PDAC) has a devastating prognosis without effective treatment options. Thus, there is an urgent need for more effective and safe therapies. Here, inorganic-organic hybrid nanoparticles (GMP-IOH-NPs) are presented as a novel drug-delivery system for the selective delivery of extraordinarily high concentrations of gemcitabine monophosphate (GMP), not only to the primary tumor but also to metastatic sites. GMP-IOH-NPs have a composition of [ZrO]2+ [GMP]2 - with GMP as drug anion (76% of total IOH-NP mass). Multiscale fluorescence imaging confirms an efficient uptake in tumor cells, independent of the activity of the human-equilibrative-nucleoside transporter (hENT1), being responsible for gemcitabine (GEM) transport into cells and a key factor for GEM resistance. Delivering already phosphorylated GMP via GMP-IOH-NPs into tumor cells also allows the cellular resistance induced by the downregulation of deoxycytidine kinase to be overcome. GMP-IOH-NPs show high accumulation in tumor lesions and only minor liver trapping when given intraperitoneally. GMP-IOH-NPs result in a higher antitumor efficacy compared to free GEM, which is further enhanced applying cetuximab-functionalized GMP-CTX-IOH-NPs. By maximizing the therapeutic benefits with high drug load, tumor-specific delivery, minimizing undesired side effects, overcoming mechanisms of chemoresistance, and preventing systemic GEM inactivation, GMP-IOH-NPs are anticipated to have a high chance to significantly improve current PDAC-patient outcome.

Excited State Dynamics of Alizarin Red S Nanoparticles in Solution.

Alizarin red S is a sulfonated, water-soluble derivative of alizarin. This work presents femtosecond studies of alizarin red S (ARS) nanoparticles in comparison to ARS in aqueous solution and to alizarin in DMSO. The femtosecond studies cover a probing spectral range of 350-750 nm using different excitation wavelengths, taking into account the variation of the absorption spectra with the pH values of the solvent. Stationary absorption spectra show slight differences between solution and nanoparticles. Excitation at 530 nm results in low and noisy responses, therefore, we additionally recorded transient spectra of the nanoparticles at λex = 267 nm. While the results in DMSO are comparable to previous studies in non-aqueous solvents, we report a relatively fast relaxation of 14 ps in [La(OH)2][ARS] nanoparticles in aqueous solution after excitation at 530 nm, which is similar to Na(ARS) solution (19 ps). The dynamics changed with lower pH, but still without significant differences between nanoparticles and solution. We propose [La(OH)2][ARS] nanoparticles as a suitable alternative to dissolved molecules with similar spectroscopic properties, for example, with regard to biomarker applications.

Solvent-free room-temperature synthesis of brightly luminescent [BMPyr]2[SnCl4].

The pseudo-ternary tin(II) halide [BMPyr]2[SnCl4] can be obtained just by mixing the starting materials [BMPyr]Cl and SnCl2 at room temperature without additional solvents. The compound shows bright Sn(II)-based emission of deep-red light (λmax: 740 nm) with a quantum yield of 88 ± 3% after optimised synthesis. Characterization is performed by X-ray structure analysis, infrared and fluorescence spectroscopy. Exemplary fluorescent thinfilms are realized by solvent processing.

Oxychloridoselenites(IV) with cubane-derived anions and stepwise chlorine-to-oxygen exchange.

The novel oxychloridoselenites(IV) [BMIm][Se3Cl13] (1), [BMIm][Se4Cl15O] (2), [BMIm]2[Se4Cl14O2] (3), [BMPyr]2[Se4Cl14O2] (4), [BMPyr]2[Se6Cl18O4] (5), [BMIm]2[SeCl4O] (6), [BMPyr]2[Se2Cl6O2] (7), and [BMPyr]2[Se6Cl14O6] (8) are prepared by ionic-liquid-based synthesis. Accordingly, SeCl4, SeO2 (1-6), and/or SeOCl2 (7,8) as the starting materials are reacted in [BMIm]Cl or [BMPyr]Cl as ionic liquid (BMIm: 1-butyl-3-methylimidazolium, BMPyr: 1-butyl-1-methylpyrrolidinium; partially with AlCl3 in addition). Generally, the composition and structure of title compounds can be derived from the tetrameric, heterocubane-type (SeCl4)4 as the initial building unit. Thus, chlorine is successively exchanged by oxygen from 1 to 8. Moreover, the four edge-sharing (SeCl6) octahedra in (SeCl4)4 are increasingly dismantled, ending with a [SeCl4O]2- anion as a single pseudo-octahedron in 6. Based on the weakly coordinating ionic liquid, it is possible to selectively obtain the different species via synthesis near room temperature (20-80 °C). The oxychloridoselenite anions [Se4Cl15O]-, [Se4Cl14O2]2-, [Se6Cl18O4]2-, and [Se6Cl14O6]2- are obtained for the first time. The title compounds are characterized by X-ray structure analysis based on single crystals and powders as well as by infrared spectroscopy and thermal analysis.

Amorphous Drug Nanoparticles for Inhalation Therapy of Multidrug-Resistant Tuberculosis.

Tuberculosis (TB) is one of the most prevalent infectious diseases. The global TB situation is further complicated by increasing patient numbers infected with Mycobacterium tuberculosis (M.tb.) strains resistant to either one or two of the first-line therapeutics, promoted by insufficient treatment length and/or drug levels due to adverse reactions and reduced patient compliance. An intriguing approach to improve anti-TB therapy relates to nanocarrier-based drug-delivery systems, which enhance local drug concentrations at infection sites without systemic toxicity. Recently developed anti-TB antibiotics, however, are lipophilic and difficult to transport in aqueous systems. Here, the very lipophilic TB-antibiotics bedaquiline (BDQ) and BTZ (1,3-benzothiazin-4-one 043) are prepared as high-dose, amorphous nanoparticles via a solvent-antisolvent technique. The nanoparticles exhibit mean diameters of 60 ± 13 nm (BDQ) and 62 ± 44 nm (BTZ) and have an extraordinarily high drug load with 69% BDQ and >99% BTZ of total nanoparticle mass plus a certain amount of surfactant (31% for BDQ, <1% for BTZ) to make the lipophilic drugs water-dispersible. Suspensions with high drug load (4.1 mg/mL BDQ, 4.2 mg/mL BTZ) are stable for several weeks. In vitro and in vivo studies employing M.tb.-infected macrophages and susceptible C3HeB/FeJ mice show promising activity, which outperforms conventional BDQ/BTZ solutions (in DMF or DMSO) with an up to 50% higher efficacy upon pulmonary delivery. In vitro, the BDQ/BTZ nanoparticles demonstrate their ability to cross the different biological barriers and to reach the site of the intracellular mycobacteria. In vivo, high amounts of the BDQ/BTZ nanoparticles are found in the lung and specifically inside granulomas, whereas only low BDQ/BTZ-nanoparticle levels are observed in spleen or liver. Thus, pulmonary delivered BDQ/BTZ nanoparticles are promising formulations to improve antituberculosis treatment.

Amikacin@SiO2 core@shell nanocarriers to treat pulmonal bacterial infections.

AMC@SiO2 core@shell nanocarriers (AMC: amikacin) are realized and contain an exceptionally high drug load of 0.8 mg mg-1 (i.e. 80% AMC of total nanocarrier mass). They are prepared via a solvent-antisolvent approach with AMC nanoparticles formed in a first step, which are then covered and stabilised by a thin silica shell in a one-pot synthesis. In total, the core@shell nanocarriers exhibit a mean diameter of 240 nm with an inner AMC core of 200 nm and an outer silica shell of 20 nm. Subsequent to synthesis, the nanocarriers can be stored in frozen dimethylsulfoxide (DMSO) and applied directly after warming to room temperature with particle contents of 5 mg mL-1. Size, structure, and composition of the AMC@SiO2 core@shell nanocarriers are evidenced by electron microscopy (SEM, TEM), spectroscopic methods (EDXS, FT-IR, UV-Vis), as well as X-ray powder diffraction and elemental analysis. As proof-of-concept, the AMC release and the activity of the novel nanocarriers are tested against two relevant, difficult-to-treat and notoriously multidrug resistant, bacterial pathogens: Mycobacterium tuberculosis (M.tb.) and Mycobacterium abscessus (M.abs.). Colloidal stability, storage stability, high drug load, and activity of the AMC@SiO2 core@shell nanocarriers are promising for, e.g., aerosol-type pulmonal application.

SMART RHESINs-Superparamagnetic Magnetite Architecture Made of Phenolic Resin Hollow Spheres Coated with Eu(III) Containing Silica Nanoparticles for Future Quantitative Magnetic Particle Imaging Applications.

Magnetic particle imaging (MPI) is a powerful and rapidly growing tomographic imaging technique that allows for the non-invasive visualization of superparamagnetic nanoparticles (NPs) in living matter. Despite its potential for a wide range of applications, the intrinsic quantitative nature of MPI has not been fully exploited in biological environments. In this study, a novel NP architecture that overcomes this limitation by maintaining a virtually unchanged effective relaxation (Brownian plus Néel) even when immobilized is presented. This superparamagnetic magnetite architecture made of phenolic resin hollow spheres coated with Eu(III) containing silica nanoparticles (SMART RHESINs) was synthesized and studied. Magnetic particle spectroscopy (MPS) measurements confirm their suitability for potential MPI applications. Photobleaching studies show an unexpected photodynamic due to the fluorescence emission peak of the europium ion in combination with the phenol formaldehyde resin (PFR). Cell metabolic activity and proliferation behavior are not affected. Colocalization experiments reveal the distinct accumulation of SMART RHESINs near the Golgi apparatus. Overall, SMART RHESINs show superparamagnetic behavior and special luminescent properties without acute cytotoxicity, making them suitable for bimodal imaging probes for medical use like cancer diagnosis and treatment. SMART RHESINs have the potential to enable quantitative MPS and MPI measurements both in mobile and immobilized environments.

Reactions of noble-metal oxides in ionic liquids near room temperature.

The reaction of Ag2O, Au2O3, and HgO with CuCl, CuI, AgCl, AgI, AuCl, and AuI in ionic liquids ([EMIm]Cl, [BMIm]Cl) near room temperature (20-80 °C) is evaluated and results in the new compounds (C8H14N2)CuCl, (C8H14N2)AgI, (C6H10N2)AuCl, [(C8H14N2)2Hg][CuCl3], [(C8H14N2)2Hg][AgCl3], and [EMIm][Ag2I2Cl]. Thereof, (C8H14N2)CuCl, (C8H14N2)AgI, (C6H10N2)AuCl, [(C8H14N2)2Hg][CuCl3], and [(C8H14N2)2Hg][AgCl3] are NHC complexes (NHC: N-heterocyclic carbene) with M-C bonds (M: Cu, Ag, Au, Hg). Whereas (C8H14N2)CuCl and (C8H14N2)AgI crystallize as single molecules, (C6H10N2)AuCl is dimerized via aurophilic interactions. [(C8H14N2)2Hg][CuCl3] and [(C8H14N2)2Hg][AgCl3] exhibit Hg atoms with two Hg-C bonds. Moreover, (C8H14N2)AgI shows intense green fluorescence at room temperature with a quantum yield of 44%, whereas all other compounds do not show any emission at room temperature. Finally, [EMIm][Ag2I2Cl] is not an NHC compound but contains ∞ 1[AgI1/2I2/4Cl1/2]- chains with infinite d10-d10 interaction of the silver atoms. The title compounds are characterized by single-crystal structure analysis, infrared spectroscopy, thermogravimetry, and fluorescence spectroscopy.

Theranostic inorganic-organic hybrid nanoparticles with a cocktail of chemotherapeutic and cytostatic drugs.

Theranostic inorganic-organic hybrid nanoparticles (IOH-NPs) with a cocktail of chemotherapeutic and cytostatic drugs and a composition Gd23+[(PMX)0.5(EMP)0.5]32-, [Gd(OH)]2+[(PMX)0.74(AlPCS4)0.13]2-, or [Gd(OH)]2+[(PMX)0.70(TPPS4)0.15]2- (PMX: pemetrexed, EMP: estramustine phosphate, AlPCS4: aluminum(III) chlorido phthalocyanine tetrasulfonate, TPPS4: tetraphenylporphine sulfonate) are presented for the first time. These IOH-NPs are prepared in water (40-60 nm in size) and have a non-complex composition with outstanding drug loading (71-82% of total nanoparticle mass) of at least two chemotherapeutic or a mixture of cytostatic and photosensitizing agents. All IOH-NPs show red to deep-red emission (650-800 nm) to enable optical imaging. The superior performance of the IOH-NPs with a chemotherapeutic/cytostatic cocktail is validated based on cell-viability assays and angiogenesis studies with human umbilical vein endothelial cells (HUVEC). The synergistic anti-cancer effect of the IOH-NPs with a chemotherapeutic cocktail is shown in a murine breast-cancer cell line (pH8N8) and a human pancreatic cancer cell line (AsPC1), whereas the synergistic cytotoxic and phototoxic efficacy is verified in response to illumination of HeLa-GFP cancer cells, MTT assays with human colon cancer cells (HCT116), and normal human dermal fibroblasts (NHDF). HepG2 spheroids as 3D cell cultures prove the effective uptake of the IOH-NPs with high uniform distribution and the release of the chemotherapeutic drugs with the strong synergistic effect of the cocktail of drugs.

Tin Bromido Aluminate Networks with Bright Luminescence.

The novel tin bromido aluminates [Sn3 (AlBr4 )6 ](Al2 Br6 ) (1), Sn(AlBr4 )2 (2), [EMIm][Sn(AlBr4 )3 ] (3) and [BMPyr][Sn(AlBr4 )3 ] (4) ([EMIm]: 1-ethyl-3-methylimidazolium, [BMPyr]: 1-butyl-1-methyl-pyrrolidinium), are obtained from a ionic-liquid-based reaction of AlBr3 and SnCl2 or SnBr2 , resulting in colorless and transparent crystals. 1 contains a neutral, inorganic ∞ 3 [Sn3 (AlBr4 )6 ] network filled with intercalated Al2 Br6 molecules. 2 represents a 3D structure isotypic to Pb(AlCl4 )2 or α-Sr[GaCl4 ]2 . 3 and 4 exhibit infinite ∞ 1 [Sn(AlBr4 )3 ]n- chains that are separated by the voluminous [EMIm]+ /[BMPyr]+ cations. All title compounds contain Sn2+ coordinated by AlBr4 tetrahedra, resulting in chains or 3D networks. Moreover, all title compounds show photoluminescence due to Br- →Al3+ ligand-to-metal charge-transfer excitation, followed by 5s2 p0 ←5s1 p1 emission on Sn2+ . Most surprisingly, the luminescence is highly efficient (quantum yield >50 %). Specifically, 3 and 4 exhibit outstanding quantum yields of 98 and 99 %, which are the highest values observed for Sn2+ -based luminescence so far. The title compounds have been characterized by single-crystal structure analysis, elemental analysis, energy-dispersive X-ray analysis, thermogravimetry, infrared and Raman spectroscopy, UV-Vis and photoluminescence spectroscopy.

Monitoring nanoparticle dissolution via fluorescence-colour shift.

[La(OH)]2+[ICG]-2 and [La(OH)]2+2[PTC]4- inorganic-organic hybrid nanoparticles (IOH-NPs) with indocyanine green (ICG) and perylene-3,4,9,10-tetracarboxylate (PTC) as fluorescent dye anions are used for emission-based monitoring of the dissolution of nanoparticles. Whereas ICG shows a deep red emission in the solid [La(OH)]2+[ICG]-2 IOH-NPs, the emission of PTC in the solid [La(OH)]2+2[PTC]4- IOH-NPs is completely quenched due to π-stacking. After nanoparticle dissolution, the emission of freely dissolved ICG is weak, whereas freely dissolved PTC shows intense green emission. We report on the synthesis of IOH-NPs and nanoparticle characterization as well as on the fluorescence properties and how to avoid undesirable energy transfer between different fluorescent dyes. The emission shift from red (intact solid nanoparticles) to green (freely dissolved dye anions), indicating nanoparticle dissolution, is shown for aqueous systems and verified in vitro. Based on this first proof-of-the-concept, the IOH-NP marker system can be interesting to monitor nanoparticle dissolution in cells and tissues of small animals and to evaluate cell processes and/or drug-delivery strategies.

pH-Dependent fluorescence of [La(OH)2]+[ARS]- hybrid nanoparticles for intracellular pH-sensing.

Saline inorganic-organic hybrid nanoparticles (IOH-NPs) [La(OH)2]+[ARS]- (ARS: alizarin red S) are prepared in water as a new compound (particle size: 47 ± 7 nm, ARS load: 65 wt%). The IOH-NPs not only show a pH-dependent absorption colour but also a pH-dependent fluorescence with green emission at pH 5.0-9.0 and red emission at pH < 4.5. According to first in vitro studies, the pH-dependend fluorescence can be used to monitor nanoparticle internalization in cells as well as the respective intracellular pH.