Effects of land clearing for agriculture on soil organic carbon stocks in drylands: A meta-analysis.

Agricultural activities have been expanding globally with the pressure to provide food security to the earth's growing population. These agricultural activities have profoundly impacted soil organic carbon (SOC) stocks in global drylands. However, the effects of clearing natural ecosystems for cropland (CNEC) on SOC are uncertain. To improve our understanding of carbon emissions and sequestration under different land uses, it is necessary to characterize the response patterns of SOC stocks to different types of CNEC. We conducted a meta-analysis with mixed-effect model based on 873 paired observations of SOC in croplands and adjacent natural ecosystems from 159 individual studies in global drylands. Our results indicate that CNEC significantly (p < .05) affects SOC stocks, resulting from a combination of natural land clearing, cropland management practices (fertilizer application, crop species, cultivation duration) and the significant negative effects of initial SOC stocks. Increases in SOC stocks (in 1 m depth) were found in croplands which previously natural land (deserts and shrublands) had low SOC stocks, and the increases were 278.86% (95% confidence interval, 196.43%-361.29%) and 45.38% (26.53%-62.23%), respectively. In contrast, SOC stocks (in 1 m depth) decreased by 24.11% (18.38%-29.85%) and 10.70% (1.80%-19.59%) in clearing forests and grasslands for cropland, respectively. We also established the general response curves of SOC stocks change to increasing cultivation duration, which is crucial for accurately estimating regional carbon dynamics following CNEC. SOC stocks increased significantly (p < .05) with high long-term fertilizer consumption in cleared grasslands with low initial SOC stocks (about 27.2 Mg ha-1 ). The results derived from our meta-analysis could be used for refining the estimation of dryland carbon dynamics and developing SOC sequestration strategies to achieve the removal of CO2 from the atmosphere.

Net carbon flux from cropland changes in the Central Asian Aral Sea Basin.

The transboundary Aral Sea Basin (ASB) covers parts of the former Union of Soviet Socialist Republics (USSR), the central Asian portion of Kazakhstan (KAZ), Uzbekistan (UZB), Turkmenistan (TUK), Kyrgyzstan (KGZ), and Tajikistan (TAJ). During recent decades, the region has experienced widespread cropland changes and has therefore attracted attention. However, carbon flux caused by these changes, which is critical to understand the carbon cycle in the region and to develop strategies for carbon sequestration, has not been quantified. We applied the Bookkeeping Model to analyze carbon flux caused by cropland changes. We found that the cropland area expanded from 1975 to 2019. Prior to 1990, the net increment in cropland area was 64.47 kha yr-1; this decreased to 11.02-18.69 kha yr-1 after the collapse of the USSR (1991). Grasslands and bare lands with low carbon density were the main types of land that were converted to cropland, accounting for approximately 70.3-99.29% of the land cleared for cropland. In terms of cropland loss, grassland accounted for more than 40.69% of the cropland converted to other land cover types, followed by artificial surfaces, which accounted for 25.84-45.16%. The expansion of cropland served as a carbon sink owing to the increase in irrigation and fertilization. The overall potential carbon emission was -89.38 ± 35.34 Tg C, and contributions of the five countries were as follows: TUR (-33.65 ± 6.30 Tg C), UZB (-29.23 ± 25.35 Tg C), KAZ (-12.76 ± 12.16 Tg C), TAJ (-11.11 ± 5.47 Tg C), KGZ (-2.63 ± 7.83 Tg C). The net carbon flux was -2.04 ± 0.23 Tg C yr-1 before 1990, and it decreased to -1.87 ± 1.03 Tg C yr-1 during the post-Soviet era. Finally, we state sustainable agricultural management is urgently needed to deal with the environmental problems of the Aral Sea, which have been primarily caused by cropland expansion.

Monitoring of carbon-water fluxes at Eurasian meteorological stations using random forest and remote sensing.

Simulating the carbon-water fluxes at more widely distributed meteorological stations based on the sparsely and unevenly distributed eddy covariance flux stations is needed to accurately understand the carbon-water cycle of terrestrial ecosystems. We established a new framework consisting of machine learning, determination coefficient (R2), Euclidean distance, and remote sensing (RS), to simulate the daily net ecosystem carbon dioxide exchange (NEE) and water flux (WF) of the Eurasian meteorological stations using a random forest model or/and RS. The daily NEE and WF datasets with RS-based information (NEE-RS and WF-RS) for 3774 and 4427 meteorological stations during 2002-2020 were produced, respectively. And the daily NEE and WF datasets without RS-based information (NEE-WRS and WF-WRS) for 4667 and 6763 meteorological stations during 1983-2018 were generated, respectively. For each meteorological station, the carbon-water fluxes meet accuracy requirements and have quasi-observational properties. These four carbon-water flux datasets have great potential to improve the assessments of the ecosystem carbon-water dynamics.

Rational design of type I photosensitizers based on Ru(ii) complexes for effective photodynamic therapy under hypoxia.

Photodynamic therapy (PDT) has been widely used in conjunction with molecular oxygen to cause cancer cell death. Hypoxia, the inherent property in solid tumors, is the obstacle during the process of PDT. It is urgent to develop PDT photosensitizers independent of the oxygen concentration. Herein, triphenylamine-modified Ru(ii) complexes have been used as photosensitizers to produce superoxide anions (O2-˙) and hydroxyl radicals (˙OH) through a type I photochemical process. Ru(ii) complexes with triphenylamine can provide a possibility to drive the reactive oxygen species production through low oxidation potential and good light-harvesting abilities. The investigation on light-mediated radical production showed that Ru4 could produce abundant ˙OH and O2-˙ compared to Ru1-Ru3 under hypoxic environments owing to the strong absorption. These radicals exhibit potent toxicity, which can damage the neighbouring biomolecules and cause the apoptosis of cancer cells. The PDT effect was evaluated in vitro under hypoxia, suggesting that Ru4 could maintain excellent performance in inducing a sharp decrease in the activity of cancer cells.

De Novo Design of Polymeric Carrier to Photothermally Release Singlet Oxygen for Hypoxic Tumor Treatment.

Intratumoral hypoxia extremely limits the clinic applications of photodynamic therapy (PDT). Endoperoxides allow thermally releasing singlet oxygen (1O2) in a defined quantity and offer promising opportunities for oxygen-independent PDT treatment of hypoxic tumors. However, previous composite systems by combining endoperoxides with photothermal reagents may result in unpredicted side effects and potential harmful impacts during therapy in vivo. Herein, we de novo design an all-in-one polymer carrier, which can photothermally release 1O2. The strategy has been demonstrated to effectively enhance the production of 1O2 and realize the photodamage in vitro, especially in hypoxic environment. Additionally, the polymer carrier accumulates into tumor after intravenous injection via the enhanced permeation and retention effects and accelerates the oxygen-independent generation of 1O2 in tumors. The oxidative damage results in good inhibitory effect on tumor growth. Realization of the strategy in vivo paves a new way to construct photothermal-triggered oxygen-independent therapeutic platform for clinical applications.

Oxygen self-sufficient NIR-activatable liposomes for tumor hypoxia regulation and photodynamic therapy.

The inherent hypoxic environment in tumors severely resists the efficacy of photodynamic therapy. To address this problem, herein, the strategy of using oxygen self-sufficient liposomes (denoted as CaO2/B1/NH4HCO3 lipo), which contained aza-BODIPY dye (B1) and CaO2 nanoparticles in the hydrophobic layer and NH4HCO3 in the hydrophilic cavity, was presented to overcome hypoxia-associated photodynamic resistance. Under near-infrared (NIR) irradiation, NIR-absorbable B1 was activated to induce hyperthermia and further triggered the decomposition of NH4HCO3. Subsequently, with the aid of NH4HCO3 and CaO2 nanoparticles, oxygen was rapidly and self-sufficiently generated, during which clean by-products were produced. Furthermore, the increased amount of oxygen promoted the singlet oxygen production in the presence of B1, which served as a photosensitizer because of the heavy atom effect. The oxygen self-sufficient system improved the anticancer efficiency and alleviated the hypoxic environment in vivo, which demonstrated a valuable attempt to regulate intratumoral hypoxia and overcome the limitation of current photodynamic therapy systems. To our knowledge, this highlights the first example of using NIR light to activate CaO2 nanoparticle-containing liposomes for the modulation of the hypoxic environment in tumors.

Facile Phototherapeutic Nanoplatform by Integrating a Multifunctional Polymer and MnO2 for Enhancing Tumor Synergistic Therapy.

Recent studies indicate that the synergistic phototherapy (SPT) process can simultaneously generate heat for photothermal therapy (PTT) and singlet oxygen (1 O2 ) for photodynamic therapy (PDT) to overcome the recurrence of tumors. However, the hypoxic environment in tumors seriously limits the therapeutic effect of the oxygen-dependent PDT, leading to the domination of PTT in the SPT process. Therefore, it is urgent to develop a novel SPT platform for overcoming hypoxia in tumors and improving the therapeutic effect of both PTT and PDT. In this work, a novel phototherapeutic platform based on a nanocomposite of aza-BODIPY/manganese dioxide (MnO2 ) is developed via simple electrostatic self-assembly. In this design, MnO2 nanosheets, which could produce heat and catalyze endogenous hydrogen peroxide (H2 O2 ) to generate oxygen, are prepared as a nanocarrier. After being coated with the as-prepared water-soluble aza-BODIPY-based polymer (PPAIB), the obtained MnO2 @PPAIB performs as a smart phototherapeutic agent for enhancing the efficiency of both PTT and PDT. More importantly, compared to PPAIB, MnO2 @PPAIB generates more heat and reactive oxygen species to realize the enhanced therapy effects of PTT and PDT. Hence, this work provides a new method to enhance the therapeutic efficacy of SPT by using a polymer/MnO2 nanoplatform to improve the oxygen concentration and produce more heat.

Enhancing singlet oxygen generation in semiconducting polymer nanoparticles through fluorescence resonance energy transfer for tumor treatment.

Photosensitizers (PSs) are of particular importance for efficient photodynamic therapy (PDT). Challenges for PSs simultaneously possessing strong light-absorbing ability, high 1O2 generation by effective intersystem crossing from the singlet to the triplet state, good water-solubility and excellent photostability still exist. Reported here are a new kind of dual-emissive semiconducting polymer nanoparticles (SPNs) containing fluorescent BODIPY derivatives and near-infrared (NIR) phosphorescent iridium(iii) complexes. In the SPNs, the BODIPY units serve as the energy donors in the fluorescence resonance energy transfer (FRET) process for enhancing the light absorption of the SPNs. The NIR emissive iridium(iii) complexes are chosen as the energy acceptors and efficient photosensitizers. The ionized semiconducting polymers can easily self-assemble to form hydrophilic nanoparticles and homogeneously disperse in aqueous solution. Meanwhile, the conjugated backbone of SPNs provides effective shielding for the two luminophores from photobleaching. Thus, an excellent overall performance of the SPN-based PSs has been realized and the high 1O2 yield (0.97) resulting from the synergistic effect of BODIPY units and iridium(iii) complexes through the FRET process is among the best reported for PSs. In addition, owing to the phosphorescence quenching of iridium(iii) complexes caused by 3O2, the SPNs can also be utilized for O2 mapping in vitro and in vivo, which assists in the evaluation of the PDT process and provides important instructions in early-stage cancer diagnosis.

Rational Design of Efficient Organic Phototherapeutic Agents via Perturbation Theory for Enhancing Anticancer Therapeutics.

The development of efficient phototherapeutic agents (PTA) through rational and specific principles exhibits great potential to the biomedical field. In this study, a facile and rational strategy was used to design PTA through perturbation theory. According to the theory, both the intersystem crossing rate for singlet oxygen generation and nonradiative transition for photothermal conversion efficiency can be simultaneously enhanced by the rational optimization of donor-acceptor groups, heavy atom number, and their functional positions, which can effectively decrease the energy gap between the singlet and triplet states and increase the spin-orbit coupling constant. Finally, efficient PTA were obtained that showed excellent performance in multimode-imaging-guided synergetic photodynamic/photothermal therapy. This study therefore expands the intrinsic mechanism of organic PTA and should help guide the rational design of future organic PTA via perturbation theory.

Highly Stable and Multifunctional Aza-BODIPY-Based Phototherapeutic Agent for Anticancer Treatment.

Phototherapy, as an important class of noninvasive tumor treatment methods, has attracted extensive research interest. Although a large amount of the near-infrared (NIR) phototherapeutic agents have been reported, the low efficiency, complicated structures, tedious synthetic procedures, and poor photostability limit their practical applications. To solve these problems, herein, a donor-acceptor-donor (D-A-D) type organic phototherapeutic agent (B-3) based on NIR aza-boron-dipyrromethene (aza-BODIPY) dye has been constructed, which shows the enhanced photothermal conversion efficiency and high singlet oxygen generation ability by simultaneously utilizing intramolecular photoinduced electron transfer (IPET) mechanism and heavy atom effects. After facile encapsulation of B-3 by amphiphilic DSPE-mPEG5000 and F108, the formed nanoparticles (B-3 NPs) exhibit the excellent photothermal stabilities and reactive oxygen and nitrogen species (RONS) resistance compared with indocyanine green (ICG) proved for theranostic application. Noteworthily, the B-3 NPs can remain outstanding photothermal conversion efficiency (η = 43.0%) as well as continuous singlet oxygen generation ability upon irradiation under a single-wavelength light. Importantly, B-3 NPs can effectively eliminate the tumors with no recurrence via synergistic photothermal/photodynamic therapy under mild condition. The exploration elaborates the photothermal conversion mechanism of small organic compounds and provides a guidance to develop excellent multifunctional NIR phototherapeutic agents for the promising clinical applications.

Halogenated Aza-BODIPY for Imaging-Guided Synergistic Photodynamic and Photothermal Tumor Therapy.

It is always a huge challenge to develop novel near-infrared (NIR) phototherapeutic agents suitable for imaging-guided cancer therapy. In order to clarify the positive heavy atom effects on the photodynamic and photothermal efficiencies of phototherapeutic agents, a series of chlorine-, bromide-, or iodine-substituted aza-BODIPYs (B2, B3, and B4, respectively) are designed and synthesized. Among them, B4 exhibits both excellent photodynamic and photothermal effects (singlet oxygen yield of B4 is 1.57 times more than that of B3) and excellent photothermal effects (1.3 °C higher than that of B3). Then, nanoparticles of B4 (IABNs) with excellent biocompatibility are prepared by coating hydrophobic B4 with hydrophilic polymer DSPE-mPEG5000 . IABN exhibits high photostability, excellent biocompatibility, and low dark toxicity both in vivo and in vitro. Furthermore, IABN shows the enhanced photodynamic effect and high photothermal conversion efficiency (34.8%). In addition, the strong fluorescence emission of IABN makes it suitable for fluorescence imaging-guided tumor therapy in vivo. Finally, IABN has successfully healed the Hela tumor-bearing mice under NIR fluorescence imaging- and photothermal imaging-guided synergistic photothermal and photodynamic therapy with low side effects, demonstrating that it is promising for future clinical applications.

Organic emitter integrating aggregation-induced delayed fluorescence and room-temperature phosphorescence characteristics, and its application in time-resolved luminescence imaging.

Thermally activated delayed fluorescence (TADF) with a substantially long lifetime furnishes a new paradigm in developing probes for time-resolved imaging. Herein, a novel TADF fluorophore, namely, PXZT, with terpyridine as the acceptor and phenoxazine (PXZ) as the donor, was rationally designed and synthesized. The new compound shows typical thermally activated delayed fluorescence, aggregation-induced emission and crystallization-induced room-temperature phosphorescence (RTP). The coordination of PXZT with a zinc ion causes the quenching of the fluorescence of PXZT due to the enhanced intramolecular charge transfer of the resulting complex ZnPXZT1. With the dissociation of the ZnPXZT1 to release PXZT and the subsequent in situ hydrophobic aggregation of the free PXZT to resist the influence of oxygen, the TADF emission of PXZT is recovered. This zinc-assisted process is successfully used for time-resolved imaging of HeLa and 3T3 cells. This work presents a simple and effective strategy for time-resolved imaging by in situ forming TADF aggregates to turn on the TADF emission.