An ultra-stable bio-inspired bacteriochlorin analogue for hypoxia-tolerant photodynamic therapy

Photodynamic therapy (PDT) greatly suffers from the weak NIR-absorption, oxygen dependence and poor stability of photosensitizers (PSs). Herein, inspired by natural bacteriochlorin, we develop a bacteriochlorin analogue, tetrafluorophenyl bacteriochlorin (FBC), by one-step reduction of tetrafluorophenyl porphyrin (TFPP). FBC can realize deep tissue penetration, benefitting from the strong NIR absorption. The reactive oxygen species (ROS) generation capacity of FBC can retain around 60% with a 1.0 cm-thick pork skin as the barrier. Besides, FBC could not only produce oxygen-dependent ¹O₂, but also generate less oxygen-dependent O₂⁻˙ and ˙OH to achieve excellent PDT even in hypoxic tumors. Moreover, FBC exhibits an ultra-high stability and it is almost unchanged even under visible light at room temperature for 15 months. Interestingly, the high reactivity of the fluorophenyl group makes it easy for FBC to produce FBC derivatives. A biocompatible FBC nanogel could be directly formed by blending FBC with SH–PEG–SH. The FBC nanogel displays excellent photodynamic efficacy in vitro and in vivo. Thus, FBC would be a promising PS for the clinical PDT of deep tumors.

A hypoxia-tolerant photosensitizer FBC-based nanoplatform with strong NIR absorbance and ultra-high stability was facilely prepared for PDT of deep tumors.     

Exploiting radical-pair intersystem crossing for maximizing singlet oxygen quantum yields in pure organic fluorescent photosensitizers

Fluorescent photosensitizers (PSs) often encounter low singlet oxygen (¹O₂) quantum yields and fluorescence quenching in the aggregated state, mainly involving the intersystem crossing process. Herein, we successfully realize maximizing ¹O₂ quantum yields of fluorescent PSs through promoting radical-pair intersystem crossing (RP-ISC), which serves as a molecular symmetry-controlling strategy of donor–acceptor (D–A) motifs. The symmetric quadrupolar A–D–A molecule PTP exhibits an excellent ¹O₂ quantum yield of 97.0% with bright near-infrared fluorescence in the aggregated state. Theoretical and ultrafast spectroscopic studies suggested that the RP-ISC mechanism dominated the formation of the triplet for PTP, where effective charge separation and an ultralow singlet–triplet energy gap (0.01 eV) enhanced the ISC process to maximize ¹O₂ generation. Furthermore, in vitro and in vivo experiments demonstrated the dual function of PTP as a fluorescent imaging agent and an anti-cancer therapeutic, with promising potential applications in both diagnosis and theranostics.

Maximizing singlet oxygen quantum yields of a fluorescent photosensitizer for realizing approximately 100% utilization of excitons by precisely controlling the molecular symmetry.     

A singlet oxygen self-reporting photosensitizer for cancer phototherapy

Photodynamic cancer therapy has attracted great attention with the increasing threat of tumors, and improving its therapeutic efficacy is highly desirable. However, due to the highly efficient intersystem crossing potency to generate singlet oxygen (¹O₂), high-efficiency photosensitizers often suffer from weak fluorescence and excess injury to normal tissue. To overcome these obstacles, here we show a reliable self-reporting strategy for real-time monitoring of therapeutic progression. As a proof of concept, a molecular dyad is designed by connecting benzo[a]phenoselenazinium (NBSe) to rhodamine (Rh), namely Rh-NBSe, where the fluorescence of the Rh unit is initially suppressed by the fluorescence resonance energy transfer mechanism, but enabled to recover as feedback signal once the reaction with photosensitized ¹O₂ takes place. The observed fluorescence increases by irradiation in vitro and in vivo successfully reflect the real-time ¹O₂ generation speed in photodynamic therapy. In addition, the favorable therapeutic advantages of Rh-NBSe are also verified, for example, the high Φ_Δ (0.8) and the low IC₅₀ (0.2 μM, 6 J cm⁻²). Based on the therapeutic ability and real-time ¹O₂ self-reporting ability, Rh-NBSe demonstrates significant potential for self-regulating phototherapy.

Photodynamic cancer therapy has attracted great attention with the increasing threat of tumors, and improving its therapeutic efficacy is highly desirable.     

A BODIPY-modified polymeric micelle for sustaining enhanced photodynamic therapy

Photodynamic therapy（PDT） has been gaining popularity in both scientific research and clinic applications due to its non-invasiveness and spatiotemporal targeting properties. Nevertheless, the local hypoxic microenvironment in tumor tissue impedes PDT universality. To overcome this drawback, a 2-pyridonebearing BODIPY photosensitizer was synthesized rationally and introduced to polyethyleneglycol-bpoly（aspartic acid） to form a photosensitizer-¹O₂ generation, storage/release...     

Rational design of a “dual lock-and-key” supramolecular photosensitizer based on aromatic nucleophilic substitution for specific and enhanced photodynamic therapy

Photosensitizing agents are essential for precise and efficient photodynamic therapy (PDT). However, most of the conventional photosensitizers still suffer from limitations such as aggregation-caused quenching (ACQ) in physiological environments and toxic side-effects on normal tissues during treatment, leading to reduced therapeutic efficacy. Thus, integrating excellent photophysical properties and accurate carcinoma selectivity in a photosensitizer system remains highly desired. Herein, a “dual lock-and-key” supramolecular photosensitizer BIBCl–PAE NPs for specific and enhanced cancer therapy is reported. BIBCl–PAE NPs are constructed by encapsulating a rationally designed glutathione (GSH)-activatable photosensitizer BIBCl in a pH-responsive diblock copolymer. In normal tissues, BIBCl is “locked” in the hydrophobic core of the polymeric micelles due to ACQ. Under the “dual key” activation of low pH and high levels of GSH in a tumor microenvironment, the disassembly of micelles facilitates the reaction of BIBCl with GSH to release water-soluble BIBSG with ideal biocompatibility, enabling the highly efficient PDT. Moreover, benefiting from the Förster resonance energy transfer effect of BIBSG, improved light harvesting ability and ¹O₂ production are achieved. In vitro and vivo experiments have demonstrated that BIBCl–PAE NPs are effective in targeting and inhibiting carcinoma. BIBCl–PAE NPs show superior anticancer efficiency relative to non-activatable controls.

The “dual lock-and-key” supramolecular photosensitizers enable specific and enhanced photodynamic therapy (PDT).     

An intramolecular photoswitch can significantly promote photoactivation of Pt(iv) prodrugs

Selective activation of prodrugs at diseased tissue through bioorthogonal catalysis represents an attractive strategy for precision cancer treatment. Achieving efficient prodrug photoactivation in cancer cells, however, remains challenging. Herein, we report two Pt(iv) complexes, designated as rhodaplatins {rhodaplatin 1, [Pt(CBDCA-O,O)(NH₃)₂(RhB)OH]; rhodaplatin 2, [Pt(DACH)ox(RhB)(OH)], where CBDCA is cyclobutane-1,1-dicarboxylate, RhB is rhodamine B, DACH is (1R,2R)-1,2-diaminocyclohexane, and ox is oxalate}, that bear an internal photoswitch to realize efficient accumulation, significant co-localization, and subsequent effective photoactivation in cancer cells. Compared with the conventional platform of external photocatalyst plus substrate, rhodaplatins presented up to 4.8 10⁴-fold increased photoconversion efficiency in converting inert Pt(iv) prodrugs to active Pt(ii) species under physiological conditions, due to the increased proximity and covalent bond between the photoswitch and Pt(iv) substrate. As a result, rhodaplatins displayed increased photocytotoxicity compared with a mixture of RhB and conventional Pt(iv) compound in cancer cells including Pt-resistant ones. Intriguingly, rhodaplatin 2 efficiently accumulated in the mitochondria and induced apoptosis without causing genomic DNA damage to overcome drug resistance. This work presents a new approach to develop highly effective prodrugs containing intramolecular photoswitches for potential medical applications.

The newly developed Pt(iv) prodrugs, rhodaplatins, contain an internal photoswitch and present up to 4.8 10⁴-fold increased photoconversion efficiency compared to the conventional photocatalyst plus Pt(iv) prodrug photocatalysis platform.     

Breaking the barrier: an osmium photosensitizer with unprecedented hypoxic phototoxicity for real world photodynamic therapy

Hypoxia presents a two-fold challenge in the treatment of cancer, as low oxygen conditions induce biological changes that make malignant tissues simultaneously more aggressive and less susceptible to standard chemotherapy. This paper reports the first metal-based photosensitizer that approaches the ideal properties for a phototherapy agent. The Os(phen)₂-based scaffold was combined with a series of IP-nT ligands, where phen = 1,10-phenanthroline and IP-nT = imidazo[4,5-f][1,10]phenanthroline tethered to n = 0–4 thiophene rings. Os-4T (n = 4) emerged as the most promising complex in the series, with picomolar activity and a phototherapeutic index (PI) exceeding 10⁶ in normoxia. The photosensitizer exhibited an unprecedented PI > 90 (EC₅₀ = 0.651 μM) in hypoxia (1% O₂) with visible and green light, and a PI > 70 with red light. Os-4T was also active with 733 nm near-infrared light (EC₅₀ = 0.803 μM, PI = 77) under normoxia. Both computation and spectroscopic studies confirmed a switch in the nature of the lowest-lying triplet excited state from triplet metal-to-ligand charge transfer (³MLCT) to intraligand charge transfer (³ILCT) at n = 3, with a lower energy and longer lifetime for n = 4. All compounds in the series were relatively nontoxic in the dark but became increasingly phototoxic with additional thiophenes. These normoxic and hypoxic activities are the largest reported to date, demonstrating the utility of osmium for phototherapy applications. Moreover, Os-4T had a maximum tolerated dose (MTD) in mice that was >200 mg kg^–1, which positions this photosensitizer as an excellent candidate for in vivo applications.     

Reversible carbon–boron bond formation at platinum centers through σ-BH complexes

A reversible carbon–boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(ii) complex [Pt(I^tBuⁱPr′)(I^tBuⁱPr)][BAr^F], 1, with tricoordinated boranes HBR₂. X-ray diffraction studies provided structural snapshots of the sequence of reactions involved in the process. At low temperature, we observed the initial formation of the unprecedented σ-BH complexes [Pt(HBR₂)(I^tBuⁱPr′)(I^tBuⁱPr)][BAr^F], one of which has been isolated. From −15 to +10 °C, the σ-BH species undergo a carbon–boron coupling process leading to the platinum hydride derivative [Pt(H)(I^tBuⁱPr–BR₂)(I^tBuⁱPr)][BAr^F], 4. Surprisingly, these compounds are thermally unstable undergoing carbon–boron bond cleavage at room temperature that results in the 14-electron Pt(ii) boryl species [Pt(BR₂)(I^tBuⁱPr)₂][BAr^F], 2. This unusual reaction process has been corroborated by computational methods, which indicate that the carbon–boron coupling products 4 are formed under kinetic control whereas the platinum boryl species 2, arising from competitive C–H bond coupling, are thermodynamically more stable. These findings provide valuable information about the factors governing productive carbon–boron coupling reactions at transition metal centers.

A reversible carbon–boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(ii) complex [Pt(I^tBuⁱPr′)(I^tBuⁱPr)][BAr^F], 1, with tricoordinated boranes HBR₂.     

Understanding and controlling the efficiency of Au24M(SR)18 nanoclusters as singlet-oxygen photosensitizers

Singlet oxygen, ¹O₂, can be generated by molecules that upon photoexcitation enable the ³O₂ → ¹O₂ transition. We used a series of atomically precise Au₂₄M(SR)₁₈ clusters, with different R groups and doping metal atoms M. Upon nanosecond photoexcitation of the cluster, ¹O₂ was efficiently generated. Detection was carried out by time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The resulting TREPR transient yielded the ¹O₂ lifetime as a function of the nature of the cluster. We found that: these clusters indeed generate ¹O₂ by forming a triplet state; a more positive oxidation potential of the molecular cluster corresponds to a longer ¹O₂ lifetime; proper design of the cluster yields results analogous to those of a well-known reference photosensitizer, although more effectively. Comprehensive kinetic analysis provided important insights into the mechanism and driving-force dependence of the quenching of ¹O₂ by gold nanoclusters. Understanding on a molecular basis why these molecules may perform so well in ¹O₂ photosensitization is instrumental to controlling their performance.

Atomically precise Au₂₄M(SR)₁₈ clusters were used as singlet-oxygen photosensitizers. Comprehensive kinetic analysis provided insights into the mechanism and driving-force dependence of the quenching of ¹O₂ by gold nanoclusters.     

A dynamic DNA nanosponge for triggered amplification of gene-photodynamic modulation

Nucleic acid therapeutics has reached clinical utility through modulating gene expression. As a potential oligonucleotide drug, DNAzyme has RNA-cleaving activity for gene silencing, but faces challenges due to the lack of a safe and effective delivery vehicle and low in vivo catalytic activity. Here we describe DNAzyme-mediated gene regulation using dynamic DNA nanomaterials with intrinsic biocompatibility, stability, tumor-targeted delivery and uptake, and self-enhanced efficacy. We assemble programmable DNA nanosponges to package and deliver diverse nucleic acid drugs and therapeutic agents such as aptamer, DNAzyme and its cofactor precursor, and photosensitizer in one pot through the rolling circle amplification reaction, formulating a controllable nanomedicine using encoded instructions. Upon environmental stimuli, DNAzyme activity increases and RNA cleavage accelerates by a supplementary catalytic cofactor. In addition, this approach induces elevated O₂ and ¹O₂ generation as auxiliary treatment, achieving simultaneously self-enhanced gene-photodynamic cancer therapy. These findings may advance the clinical trial of oligonucleotide drugs as tools for gene modulation.

Oligonucleotide drug delivery approach is provided with a biomimetic, dynamic DNA nanomaterial, which enables disease gene regulation and auxiliary therapy in a controllable and self-boosting manner.     

A plasmon-enhanced theranostic nanoplatform for synergistic chemo-phototherapy of hypoxic tumors in the NIR-II window

Development of simple and effective synergistic therapy by combination of different therapeutic modalities within one single nanostructure is of great importance for cancer treatment. In this study, by integrating the anticancer drug DOX and plasmonic bimetal heterostructures into zeolitic imidazolate framework-8 (ZIF-8), a stimuli-responsive multifunctional nanoplatform, DOX-Pt-tipped Au@ZIF-8, has been successfully fabricated. Pt nanocrystals with catalase-like activity were selectively grown on the ends of the Au nanorods to form Pt-tipped Au NR heterostructures. Under single 1064 nm laser irradiation, compared with Au NRs and Pt-covered Au NRs, the Pt-tipped Au nanorods exhibit outstanding photothermal and photodynamic properties owing to more efficient plasmon-induced electron–hole separation. The heat generated by laser irradiation can enhance the catalytic activity of Pt and improve the O₂ level to relieve tumor hypoxia. Meanwhile, the strong absorption in the NIR-II region and high-Z elements (Au, Pt) of the DOX-Pt-tipped Au@ZIF-8 provide the possibility for photothermal (PT) and computed tomography (CT) imaging. Both in vitro and in vivo experimental results illustrated that the DOX-Pt-tipped Au@ZIF-8 exhibits remarkably synergistic plasmon-enhanced chemo-phototherapy (PTT/PDT) and successfully inhibited tumor growth. Taken together, this work contributes to designing a rational theranostic nanoplatform for PT/CT imaging-guided synergistic chemo-phototherapy under single laser activation.

A plasmon-enhanced theranostic nanoplatform for synergistic chemo-phototherapy (PTT/PDT) of hypoxic tumors in the NIR-II window.     

Synthesis of Sn nanocluster@carbon dots for photodynamic therapy application

Recently, photodynamic therapy (PDT) has been extensively applied in clinical and coadjuvant treatment of various kinds of tumors. However, the photosensitizer (PS) of PDT still lack of high production of singlet oxygen (¹O₂), low cytotoxicity and high biocompatibility. Herein, we propose a facile method for establishing a new core-shell structured Sn nanocluster@carbon dots (CDs) PS. Firstly, Sn⁴⁺@S-CDs complex is synthesized using the sulfur-doped CDs (S-CDs) and SnCl₄ as raw materials, and subsequently the new PS (Sn nanocluster@CDs) is obtained after vaporization of Sn⁴⁺@S-CDs solution. Remarkably, the obtained Sn nanocluster@CDs show an enhanced fluorescence as well as a higher ¹O₂ quantum yield (QY) than S-CDs. The high ¹O₂ QY (58.3%) irradiated by the LED light (400–700 nm, 40 mW/cm²), induce the reduction of 4T1 cancer cells viability by 25%. More intriguingly, no visible damage happens to healthy cells, with little impact on liver tissue due to renal excretion, both in vitro and in vivo experiments demonstrate that Sn nanocluster@CDs may become a promising PS, owning a high potential for application in PDT.     

Protein nanoparticles containing Cu(II) and DOX for efficient chemodynamic therapy via self-generation of H2O2

Chemodynamic therapy (CDT) refers to generating hydroxyl radical (OH) in tumor sites via hydrogen peroxide (H₂O₂) catalyzed by transition metal ions in cancer cells under acidic environment. However, H₂O₂ content is not enough for effective CDT, although H₂O₂ content in cancer cells is higher than that of normal cells. Herein, we synthesized DOX@BSA-Cu NPs (nanoparticles) for effective CDT by providing enhanced content of H₂O₂ in cancer cells. The results proved Cu²⁺ in NPs could be reduced to Cu⁺ by glutathione (GSH) and effectively converted H₂O₂ to OH. Moreover, the loaded low-dose doxorubicin (DOX) in the NPs could improve the content of H₂O₂ and resulted in more efficient generation of OH in cancer cells. Thus DOX@BSA-Cu NPs exhibited higher cytotoxicity to cancer cells. This research may provide new ideas for the further studies on more effective Cu(II)-based CDT nanoagents.     

Visible light induced efficient activation of persulfate by a carbon quantum dots (CQDs) modified γ-Fe2O3 catalyst

In this study, a carbon quantum dots modified maghemite catalyst (CQDs@γ-Fe₂O₃) has been synthesized by a one-step solvothermal method for efficient persulfate (PDS) activation under visible light irradiation. Transmission electron microscopy (TEM), scanning electron microscopy (SEM) and UV–vis diffuse reflectance spectroscopy (UV–vis DRS) characterization indicated that the formation of heterojunction structure between CQDs and γ-Fe₂O₃ effectively reduced the catalyst band gap (E_g), favoring the separation rate of electrons and holes, leading to remarkable efficient sulfamethoxazole (SMX) degradation as compared to the dark-CQDs@γ-Fe₂O₃/PDS and vis-γ-Fe₂O₃/PDS systems. The evolution of dissolved irons also demonstrated that CQDs could accelerate the in-situ reduction of surface-bounded Fe³⁺. Electron paramagnetic resonance (EPR) and radical scavenging experiments demonstrated that both OH and SO₄⁻ were generated in the reaction system, while OH was relatively more dominant than SO₄⁻ for SMX degradation. Finally, the reaction mechanism in the vis-CQDs@γ-Fe₂O₃/PDS system was proposed involving an effective and accelerated heterogeneous-homogeneous iron cycle. CQDs would enrich the photo-generated electrons from γ-Fe₂O₃, causing efficient interfacial generation of surface-bond Fe²⁺ and reduction of adsorbed Fe³⁺. This visible light induced iron cycle would eventually lead to effective activation of PDS as well as the efficient degradation of SMX.     

Electro-catazone treatment of an ozone-resistant drug: Effect of sintering temperature on TiO2 nanoflower catalyst on porous Ti gas diffuser anodes

Electrochemical heterogeneous catalytic ozonation (E-catazone) is a promising and advanced oxidation technology that uses a titanium dioxide nanoflower (TiO_2-NF)-coated porous Ti gas diffuser as an anode material. Our previous study has highlighted that the importance of the TiO_2-NF coating layer in enhancing OH production and rapidly degrading O₃-resistant drugs. It is well known that the properties of TiO_2-NF are closely related to its sintering temperature. However, to date, related research has not been conducted in E-catazone systems. Thus, this study evaluated the effect of the sintering temperature on the degradation of the O₃-resistant drug para-chlorobenzoic acid (p-CBA) using both experimental and kinetic modeling and revealed its influence mechanism. The results indicated that the TiO_2-NF sintering temperature could influence p-CBA degradation and OH production. TiO_2-NF prepared at 450 °C showcased the highest p-CBA removal efficiency (98.5% in 5 min) at a rate of 0.82 min⁻¹, and an OH exposure of 8.41 × 10⁻¹⁰ mol L⁻¹ s. Kinetic modeling results and interface characterization data revealed that the sintering temperature could alter the TiO₂ crystallized phase and the content of surface-adsorbed oxygen, thus affecting the two key limiting reactions in the E-catazone process. That is, ≡TiO₂ surface reacted with H₂O to form TiO₂-(OH)₂, which then heterogeneously catalyzed O₃ to form OH. Consequently, E-catazone with a TiO_2-NF anode prepared at 450 °C generated the highest surface reaction rate (5.00 × 10⁻¹ s⁻¹ and 4.00 × 10^-3 L mol^-1 s⁻¹, respectively), owing to its higher anatase content and adsorbed oxygen. Thus, a rapid O₃-TiO₂ reaction was achieved, resulting in an enhanced OH formation and a highly effective p-CBA degradation. Overall, this study provides novel baseline data to improve the application of E-catazone technology.     

Promotional effect of nitrogen-doped and pore structure for the direct synthesis of hydrogen peroxide from hydrogen and oxygen by Pd/C catalyst at ambient pressure

Nitrogen-doped porous carbon is potential support for directly synthesizing H₂O₂ from H₂ and O₂. Here, density functional theory (DFT) was used to study the effect of N-doped porous carbon on H₂O₂ directly synthesized. The theoretical calculation results showed that N-doped improved H₂O₂ productivity and H₂ conversion by increasing the dispersion of Pd nanoparticles and the Pd⁰/Pd²⁺ ratio. However, N-doped decreased H₂O₂ selectivity by reducing oxygen's dissociation energies. The experimental results showed that adjusting the pore structure of N-doped porous carbon could improve the adverse effects of N-doping for H₂O₂ selectivity. The H₂O₂ productivity and selectivity of Pd/C catalyst with a macropore-mesoporous-microporous hierarchical porous structure were up to 328.4 mol_H2O2·kg_cat^-1·h^?1 and 71.9 %, respectively, at ambient pressure. The macropore structure enhances the transfer and diffusion performance of the catalyst and effectively inhibits the effect of N-doping on OO bond dissociation, which improves H₂O₂ productivity and selectivity. This research provides a possible solution for designing a high-performance Pd/C catalyst to directly synthesize H₂O₂ from H₂ and O₂ at ambient pressure.     

Enhanced visible light photocatalytic activity of CeO2@Zn0.5Cd0.5S by facile Ce(IV)/Ce(III) cycle

In this study, CeO₂@Zn_0.5Cd_0.5S heterostructure (Ce@ZCS) is synthesized via a simple two-step hydrothermal method. The effect of CeO₂ loading on the visible-light photoactivity of Zn_0.5Cd_0.5S is mainly investigated. It is found that Ce@ZCS shows a 1.9 times activity as high as ZCS for the MB degradation. The improved activity mainly results from the significant enhanced charge separation by CeO₂, in which the electron transfer is obviously promoted by the facile Ce(IV)/Ce(III) cycle. The excited electrons of ZCS is easy to transfer to CeO₂, thus obviously increasing the charge separation of ZCS. The accepted electrons by CeO₂ may easily be captured by the adsorbed O₂ to form O₂⁻, and then O₂⁻ could combine with H⁺/H₂O to form HO₂, and OH. Finally, O₂⁻, h⁺ and OH are confirmed as the major oxidative species in photocatalytic reaction for Ce@ZCS, and a possible photocatalytic mechanism is proposed. The cheap, efficient Ce@ZCS photocatalyst could be applied for practical waste water treatment.     

CsAlB3O6F: a beryllium-free deep-ultraviolet nonlinear optical material with enhanced thermal stability

The design of new beryllium-free deep-ultraviolet nonlinear optical materials is important but challenging. Here, we describe a new strategy to search for such materials based on rational selection of fundamental structural units. By combining asymmetric AlO₃F tetrahedra and π-conjugated B₃O₆ rings, a new aluminum borate fluoride, CsAlB₃O₆F was obtained. It exhibits excellent linear and nonlinear optical properties including a high optical transmittance with a cut-off edge shorter than 190 nm, large second harmonic generation intensities (2.0× KH₂PO₄, KDP), and suitable birefringence for phase-matching under 200 nm. It also has good thermal stability and can be synthesized easily in an open system.

A new potential deep-ultraviolet nonlinear optical material CsAlB₃O₆F was designed by a rational selection of fundamental structural units. This material does not require toxic raw materials and can be grown in an open system.

The exploration of new deep-ultraviolet (DUV) nonlinear optical (NLO) materials is intriguing and of great importance because these materials are crucial for the development of all-solid-state DUV lasers.^1–3 For NLO materials, the main obstacles to DUV application are 3-fold:^4,5 (i) a wide DUV transparency window (wavelength cut-off edge < 200 nm), (ii) high NLO coefficients (>1× commercial KH₂PO₄, KDP), and (iii) sufficient birefringence to satisfy phase matching conditions in the DUV region. Until now, only KBe₂BO₃F₂ (KBBF) can certainly break through these barriers and generate lasers with wavelengths shorter than 200 nm by direct second harmonic generation (SHG).⁶ However, KBBF is limited in practical use because of its adverse layered crystal growth habit and use of the highly toxic beryllium component. To find a KBBF replacement, many new NLO crystals have been developed continuously, but have so far been unable to achieve desired NLO properties.^7–10Recently, it was shown that fluorooxoborates and fluorophosphates with mixed O/F anionic groups might be recognized as new sources for discovering DUV NLO materials. For example, Pan''s group proposed that the [BO_xF_4−x] (x = 1, 2, 3) tetrahedra are good units to balance the multiple criteria of DUV NLO materials.¹¹ Accordingly, monofluorophosphates with non-π-conjugated asymmetric [PO₃F] units were also paid attention, exhibiting superior optical properties.^12,13 Thereafter, numerous fluorooxoborates and fluorophosphates with an unprecedented crystal structure and high performance as potential DUV NLO materials have been reported.^14–17 Nevertheless, because these materials are relatively unstable at high temperature in air, one need to develop a suitable crystal growth method under sealed conditions and/or search for a suitable flux (solvent) system at relatively low temperature.^14,16 Alternatively, it is possible to achieve a beryllium-free, higher stability DUV NLO crystal by combining other anionic groups, such as [AlO₄], [PO₄], [SiO₄], and [ZnO₄].^18–21Enlightened by the successful synthesis of NLO-active fluorooxoborates and fluorophosphates, we proposed that aluminum borate fluorides with [AlO_mF_n] (m + n = 4, 5, 6, AlOF for short) units might be another choice for exploring new NLO materials. Four specific aspects were considered: (I) aluminum borates are preferred because of the chemical and coordination environment similarity between Al³⁺ and Be²⁺ cations.²² (II) similar to fluorooxoborates, the substitution of O²⁻ with larger electronegativity F⁻ can increase the bandgap and optical anisotropy due to the ionicity of the Al–F bond. (III) The rich coordination environment of AlOF groups provides more structural possibilities than those of other mixed-anionic groups (e.g. [BeO₃F], [BO₃F], [BO₂F₂], see Fig. S1^†). Different from the B or Be atom, the Al atom has empty d orbitals, and it can form sp³, sp³d, and sp³d² hybrid orbitals when bonding with O/F atoms. Consequently, diverse AlOF groups without anion-site disorder, such as [AlO₃F] tetrahedra, [AlO₃F₂] or [AlO₄F] trigonal bipyramids, and [AlO₅F], [AlO₄F₂], [AlO₂F₄], or [AlOF₅] octahedra, have been achieved (Fig. S1^†). Replacing oxygen atoms with fluorine in the Al–O polyhedra not only increases the degree of freedom (e.g. cis/trans conformation), but also causes a (local) symmetry breaking and results in increased microscopic susceptibility and optical anisotropy, which are beneficial to build a noncentrosymmetric (NCS) material. (IV) Aluminum borate fluorides without B–F bonds (e.g. BaAlBO₃F₂,²³ Rb₃Al₃B₃O₁₀F,²⁴ and K₃Ba₃Li₂Al₄B₆O₂₀F²⁰) show good thermal stability, and large crystals could be obtained in air.By applying the strategy described above, we tried to design a new DUV NLO material according to the blueprints shown in Fig. 1a. From KBBF to fluorooxoborates (e.g. NH₄B₄O₆F,²⁵ ABF), the nontoxic [BO₃F] units were selected to replace the [BeO₃F] tetrahedra of KBBF while the NLO properties were retained. Meanwhile, benzene-like [B₃O₆] rings (the same as that in β-BaB₂O₄, BBO) with a better conjugated π-orbital system were utilized to replace [BO₃] triangles (the case in CsB₄O₆F,²⁶ CBF), which could contribute to the increase of SHG responses compared to KBBF. In this work, more stable [AlO₃F] units combined with the [B₃O₆] rings were chosen as fundamental building units (FBUs) and a new potential DUV NLO material CsAlB₃O₆F (CABF) has been successfully synthesized. The material can be obtained easily in an open system and it exhibits a short UV cutoff edge below 190 nm with a powder SHG response of 2.0× KDP under 1064 nm incident radiation. The first-principles calculations reveal that CABF possesses moderate SHG coefficients and sufficient birefringence for DUV phase-matching. With the introduction of new AlO₃F units, CABF continues to maintain the excellent structural features of both KBBF and β-BBO, and thus exhibits a great potential to be a Be-free DUV material for nonlinear light–matter interactions.Open in a separate windowFig. 1(a) The structural evolution from KBe₂BO₃F₂ to CsAlB₃O₆F. (b) The 2D [AlB₃O₆F]_∞ layer of CABF. (c) Crystal structure of CABF.Single crystals of CABF were obtained by the conventional flux method in an open system (see the Experimental details in the ESI^†). CABF crystallizes in the NCS orthorhombic polar space group Pna2₁ (Tables S1–S3^†). Its crystal structure is built up from [AlB₃O₆F]_∞ 2D layers and the Cs⁺ cations reside in the interlayer space (Fig. 1b and c). The FBUs of CABF are the [AlB₃O₈F] groups composed of one [B₃O₆] ring and one [AlO₃F] tetrahedron. Three crystallographically independent boron atoms are all three-coordinated to oxygen atoms forming the BO₃ triangles, which further form a B₃O₆ ring by sharing their terminal O atoms. The B–O bond distances and the O–B–O angles are in the range of 1.342(10) to 1.395(11) Å and 117.2(7) to 121.9(8)°, respectively. The Al³⁺ cation is coordinated to three oxygen atoms (Al–O bond lengths: 1.719(6)–1.734(6) Å) and one fluorine atom (Al–F bond length equals 1.675(5) Å) to form a distorted AlO₃F tetrahedron. In the bc-plane, the [AlO₃F] tetrahedra bond with discrete [B₃O₆] rings to create [AlB₃O₆F]_∞ layers that contain 18-membered rings (Fig. 1b). In one layer, the apical F atoms of [AlO₃F] tetrahedra point upward and downward regularly. The Cs⁺ cations are twelve-coordinated, forming the [CsO₁₁F] polyhedra with a Cs–F distance of 3.292(7) Å and Cs–O distances ranging from 3.256(5) to 3.585(6) Å (Fig. S2^†). Because the Cs⁺ cations reside in the tunnels created by the 18-membered rings and adjacent [AlB₃O₆F]_∞ layers, the interlayer distance in CABF is 4.03 Å. Compared to the distance of two adjacent layers in KBBF (6.25 Å), CABF should exhibit stronger interlayer interactions. Theoretical calculation based on the density functional theory (DFT) also confirms that CABF shows a larger interlayer binding energy than KBBF (0.178 vs. 0.0314 eV Å⁻² per layer). These results indicate that CABF might possess a better crystal growth habit without layering. The bond valence sum calculation²⁷ (Table S2^†) and IR spectrum (Fig. S3^†) indicate that all atoms of CABF have the expected oxidation states and coordination environments.Polycrystalline CABF was synthesized by a stoichiometric solid-state reaction of CsF, Al₂O₃ and H₃BO₃ at 500 °C, and the phase purity was confirmed by powder X-ray diffraction (PXRD) Rietveld refinement (Fig. S4^†). To check the stability of CABF, thermal measurements and further PXRD analysis were performed on its polycrystalline samples. Based on the re-crystallization experiment, the CABF sample after melting was almost the same as the original one; however, owing to the loss of volatile fluorines, a small amount of Cs₂Al₂(B₃O₆)₂O²⁸ was obtained (Fig. S6a^†). Thermogravimetric (TG) analysis shows that CABF has nearly no weight loss until 900 °C, and the differential scanning calorimetry (DSC) data show two sharp endothermic peaks around 505 and 702 °C on the heating curve (Fig. 2a). In addition, variable temperature PXRD measurements were performed (Fig. S6b^†), demonstrating a possible phase transition of CABF near 500 °C (consistent with the first peak on the DSC curve). Therefore, an excessive amount of fluorides should be used as the flux for crystal growth of CABF. Different from many fluorooxoborates (e.g. CaB₅O₇F₃ and SrB₅O₇F₃ (ref. 29–31)), CABF can survive at relatively high temperature in an open system after replacing BO₃F with AlO₃F units, which is an important advantage for large crystal growth.Open in a separate windowFig. 2(a) Thermal behaviour of CABF. (b) The diffuse reflectance spectrum of CABF. (c) PSHG measurements at 1064 nm. (d) Calculated type I phase-matching condition of CABF. Dashed lines: refractive-indices of fundamental light. Solid lines: refractive-indices of second-harmonic light. The λ_SH of CABF is estimated by satisfying n_Z(ω) = n_X(2ω). The SHG-weighted electron density maps of the occupied (e) and unoccupied (f) states in the VE process.CABF exhibits a wide transparency window from 300 to 1100 nm, with a short UV cut-off edge below 190 nm (Fig. 2b). Even at 190 nm, the reflectance is nearly 40%. DFT calculations of the band gap using the HSE06 hybrid functional with high accuracy result in 7.49 eV (corresponding to 166 nm), further indicating that CABF could be an excellent candidate for optical materials operating in the DUV region. As described earlier,^26,28 the large band gap of CABF could be attributed to the elimination of dangling bonds in [B₃O₆] units and the introduction of fluorine.Powder SHG (PSHG) measurement using the Kurtz–Perry method³² reveals that CABF has SHG intensities of 2.0× KDP (particle size range: 200–250 μm) under 1064 nm fundamental wave laser radiation. It also suggests that CABF is phase matchable as the SHG intensities continue to rise until it attains the maximum (Fig. 2c). Under 532 nm fundamental wave laser radiation, CABF also shows phase matching behavior and has an SHG response about 1/6 times that of BBO in the particle size range of 200–250 μm (Fig. S7^†). The SHG response of CABF is larger than that of KBBF (∼1.2× KDP) and suitable for DUV NLO applications. Applying Kleinmann symmetry in point group mm2, there are three nonzero and independent SHG coefficients, and our calculated SHG coefficients for CABF are d₁₅ = −0.027 pm V⁻¹, d₂₄ = 0.941 pm V⁻¹, and d₃₃ = −0.955 pm V⁻¹, which are consistent with the PSHG results. The SHG ability of CABF is comparable to those of other DUV NLO materials, including CBF (1.9× KDP),²⁶ ABF (3× KDP),²⁵ MB₅O₇F₃ (M = Ca and Sr, 2.3–2.5× KDP),^29–31 (NH₄)₂PO₃F (1.0× KDP),¹² and NaNH₄PO₃F·H₂O (1.1× KDP).¹⁶ Compared with the CBF archetype, the increased SHG response of CABF can be understood by considering the geometry factor of NLO-active [B₃O₆] units. Structurally, CABF is pretty much like CBF; however, the substitution of [BO₃F] by [AlO₃F] results in structural modulation of the [B₃O₆] groups. As shown in Fig. S8,^† the rotation angle (φ) and deviation angle (θ) of the B₃O₆ groups decrease from 33 and 6.8° in CBF, to 25 and 4.4° in CABF, respectively. The smaller φ and θ angles in CABF result in more “coplanar and aligned” [B₃O₆] units, that is, a favorable arrangement for generating the SHG response according to the anionic group approach.⁶The phase-matching ability is a key factor that should never be ignored for any practical DUV NLO application, which relies on both birefringence (Δn) and its dispersion of the crystal.³³ The calculated Δn of CABF is 0.091 at 1064 nm, large enough to satisfy DUV phase-matching (Fig. S10^†). Based on the dispersion of the refractive indices, the shortest SHG phase-matching wavelength (λ_SH) of CABF can reach 182 nm (Fig. 2d), which is comparable to that of KBBF and other recent reported NLO materials (Table S4^†). To the best of our knowledge, the phase-matching wavelength of CABF is the shortest among the SHG-active aluminum borates and aluminum borate fluorides (Table S4^†).To correlate the observed optical properties and electronic structure of CABF, band structure calculations were performed. The partial density of states (PDOS) projected on the constitutional atoms (see Fig. S9^†) demonstrates that B-2p, Al-3p, O-2p, and F-2p states occupy the frontier orbitals (the top of the valence band and the bottom of the conduction band). The high overlap of these orbitals indicates that both the [B₃O₆] and [AlO₃F] groups determine the SHG response and optical birefringence in CABF, while the Cs⁺ cations show a very small contribution. This observation was also supported by the SHG-weighted electron density analysis.³⁴ The directly perceived images (Fig. 2e, f, and S11^†) indicate that the 2p orbitals of O/F atoms in the occupied states and the anti π-orbitals of the [BO₃] groups in the unoccupied states dominate the SHG contribution. In particular, the O or F atoms in [AlO₃F] groups reveal considerable SHG density values, which further suggests that the [AlO₃F] group could be a promising NLO-active unit.     

Biogenic fabrication of silver nanoparticles,oxidative dissolution and antimicrobial activities

Metallic silver nanoparticles (AgNPs) were prepared by using Foeniculum vulgare Mill seeds extract. The silver nitrate was used as silver precursor in an aqueous solution. The photooxidative dissolution of AgNPs with persulfate (K₂S₂O₈) under UV light was investigated. Effects of initial concentration of K₂S₂O₈, AgNPs, initial solution pH, and temperature were studied on dissolution of AgNPs. The 100% AgNPs dissolution was achieved in 60 min under typical conditions (pH = 4.0, 1.2 mM K₂S₂O₈, and 30 ⁰C). The experimental results showed higher temperature brought faster dissolution rate, and the activation energy was 65.2 kJ/mol. The effects of ethanol, tertiary butanol, and nitrobenzene were studied to establish the role of SO₄^? and HO radical species. AgNPs dissolution was inhibited by Cl^?, Br^?, I^?, and NO₃^? ions. Staphylococcus auerus (s. aureus), Escherichia coli (E. coli) and Candida albicans (C. albicans) were the effective human pathogens against the AgNPs. The lag phase, growth kinetics, minimum bactericidal concentration, death rate, and antimicrobial efficacy depend on the concentration of AgNPs.     

New Cy5 photosensitizers for cancer phototherapy: a low singlet–triplet gap provides high quantum yield of singlet oxygen

Highly efficient triplet photosensitizers (PSs) have attracted increasing attention in cancer photodynamic therapy where photo-induced reactive oxygen species (ROSs, such as singlet oxygen) are produced via singlet–triplet intersystem crossing (ISC) of the excited photosensitizer to kill cancer cells. However, most PSs exhibit the fatal defect of a generally less-than-1% efficiency of ISC and low yield of ROSs, and this defect strongly impedes their clinical application. In the current work, a new strategy to enhance the ISC and high phototherapy efficiency has been developed, based on the molecular design of a thio-pentamethine cyanine dye (TCy5) as a photosensitizer. The introduction of an electron-withdrawing group at the meso-position of TCy5 could dramatically reduce the singlet–triplet energy gap (ΔE_st) value (from 0.63 eV to as low as 0.14 eV), speed up the ISC process (τ_ISC = 1.7 ps), prolong the lifetime of the triplet state (τ_T = 319 μs) and improve singlet oxygen (¹O₂) quantum yield to as high as 99%, a value much higher than those of most reported triplet PSs. Further in vitro and in vivo experiments have shown that TCy5-CHO, with its efficient ¹O₂ generation and good biocompatibility, causes an intense tumor ablation in mice. This provides a new strategy for designing ideal PSs for cancer photo-therapy.

The electron-withdrawing group at the meso-position of Thio-Cy5 could dramatically reduce the singlet–triplet energy gap, and speed up the intersystem crossing process.