Reactive Uptake of Gaseous Sesquiterpenes on Aqueous Surfaces Matsuoka, Kohei; Sakamoto, Yosuke; Hama, Tetsuya ...
The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory,
02/2017, Volume:
121, Issue:
4
Journal Article
Peer reviewed
Sesquiterpenes emitted from biogenic sources play important roles in atmospheric HOx cycles and new particle formation. Current atmospheric models, however, fail to account for their fates, possibly ...due to missing heterogeneous sinks. Here we apply interface-specific mass spectrometry to detect carbocation products of the reactive uptake of gaseous sesquiterpenes C15H24 (β-caryophyllene (β-C), α-humulene (α-H), and alloaromadendrene (a-d)) on the surface of aqueous microjets as functions of water acidity and gas concentration. We find that these gases are effectively protonated to C15H25 + upon colliding with the surface of pH < 5 water microjets. We determine inflection points from plots of product yields vs bulk pH: pH1/2 = 4.17 ± 0.05, 4.28 ± 0.06, and 4.36 ± 0.19, and kinetic isotope effects (KIEs) from H2O/D2O (1:1 = vol/vol) experiments: KIE = 2.31 ± 0.08, 1.95 ± 0.05, and 2.71 ± 0.11, for β-C, α-H, and a-d, respectively. These results are analyzed vis-a-vis previous reports on isoprene and monoterpenes experiments. We estimate 6.2 × 10–5 ≤ γ ≤ 3.1 × 10–4 for the reactive uptake of gaseous sesquiterpenes on acidic (1 < pH < 3) water surfaces. The atmospheric implications of present findings are discussed.
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Current immunotherapies aim to modulate the balance among different immune cell populations, thereby controlling immune reactions. However, they often cause immune overactivation or over-suppression, ...which makes them difficult to control. Thus, it would be ideal to manipulate immune cells at a local site without disturbing homeostasis elsewhere in the body. Recent technological developments have enabled the selective targeting of cells and tissues in the body. Photo-targeted specific cell therapy has recently emerged among these. Near-infrared photoimmunotherapy (NIR-PIT) has surfaced as a new modality for cancer treatment, which combines antibodies and a photoabsorber, IR700DX. NIR-PIT is in testing as an international phase III clinical trial for locoregional recurrent head and neck squamous cell carcinoma (HNSCC) patients (LUZERA-301, NCT03769506), with a fast-track designation by the United States Food and Drug Administration (US-FDA). In Japan, NIR-PIT for patients with recurrent head and neck cancer was conditionally approved in 2020. Although NIR-PIT is commonly used for cancer therapy, it could also be exploited to locally eliminate certain immune cells with antibodies for a specific immune cell marker. This strategy can be utilized for anti-allergic therapy. Herein, we discuss the recent technological advances in local immunomodulation technology. We introduce immunomodulation technology with NIR-PIT and demonstrate an example of the knockdown of regulatory T cells (Tregs) to enhance local anti-tumor immune reactions.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Molybdenum and tungsten are redox-sensitive elements, and their stable isotope ratios have attracted attention as paleoceanographic proxies. However, our knowledge of the distribution of stable Mo ...and W isotopes in the modern hydrosphere remains limited. In this study, we provided the concentrations and isotope ratios of dissolved Mo and W in the oceans (the North Pacific and Indian Oceans), marginal seas (the East China Sea and Sea of Japan), and a river-estuary system in Japan (from the Uji-Yodo rivers to Osaka Bay). In the North Pacific and Indian Oceans, the W concentration was 48.2 ± 6.2 pmol/kg (ave ± 2sd,
n
= 109),
δ
186/184
W was 0.52 ± 0.06 ‰, the Mo concentration was 105.1 ± 8.0 nmol/kg, and
δ
98/95
Mo was 2.40 ± 0.06 ‰. The results indicate that W has the constant concentration and isotopic composition in the modern ocean as well as Mo. In the East China Sea and the Sea of Japan, the W concentration and
δ
186/184
W in the upper water (< 1000 m depth) were different from those in the ocean (W = 56 ± 18 pmol/kg,
δ
186/184
W = 0.45 ± 0.06 ‰,
n
= 24). However, the concentrations in deeper water were congruent with those in the oceans (W = 49.9 ± 7.6 pmol/kg,
δ
186/184
W = 0.50 ± 0.02 ‰,
n
= 7). The Mo concentration was 105.4 ± 3.1 nmol/kg and
δ
98/95
Mo was 2.36 ± 0.03 ‰ (
n
= 31) throughout the water column, congruent with those in the ocean. In the Uji River-Yodo River-Osaka Bay system, the W concentration reached 1074 pmol/kg and
δ
186/184
W reached 0.20 ‰. We propose that the enrichment of W with a low
δ
186/184
W in the river-estuary system and marginal seas is caused by anthropogenic pollution. Anthropogenic Mo pollution was not detected in marginal seas. However, the Mo concentration and
δ
98/95
Mo showed high anomalies above the mixing line of river water and seawater in the lower Yodo River and Osaka Bay, implying possible anthropogenic pollution of Mo in the metropolitan area.
The conventional treatment of thoracic tumors includes surgery, anticancer drugs, radiation, and cancer immunotherapy. Light therapy for thoracic tumors has long been used as an alternative; ...conventional light therapy also called photodynamic therapy (PDT) has been used mainly for early-stage lung cancer. Recently, near-infrared photoimmunotherapy (NIR-PIT), which is a completely different concept from conventional PDT, has been developed and approved in Japan for the treatment of recurrent and previously treated head and neck cancer because of its specificity and effectiveness. NIR-PIT can apply to any target by changing to different antigens. In recent years, it has become clear that various specific and promising targets are highly expressed in thoracic tumors. In combination with these various specific targets, NIR-PIT is expected to be an ideal therapeutic approach for thoracic tumors. Additionally, techniques are being developed to further develop NIR-PIT for clinical practice. In this review, NIR-PIT is introduced, and its potential therapeutic applications for thoracic cancers are described.
BackgroundNear-infrared photoimmunotherapy (NIR-PIT) is a new modality for treating cancer, which uses antibody-photoabsorber (IRDye700DX) conjugates that specifically bind to target tumor cells. ...This conjugate is then photoactivated by NIR light, inducing rapid necrotic cell death. NIR-PIT needs a highly expressed targeting antigen on the cells because of its reliance on antibodies. However, using antibodies limits this useful technology to only those patients whose tumors express high levels of a specific antigen. Thus, to propose an alternative strategy, we modified this phototechnology to augment the anticancer immune system by targeting the almost low-expressed immune checkpoint molecules on tumor cells.MethodsWe used programmed death-ligand 1 (PD-L1), an immune checkpoint molecule, as the target for NIR-PIT. Although the expression of PD-L1 on tumor cells is usually low, PD-L1 is almost expressed on tumor cells. Intratumoral depletion with PD-L1-targeted NIR-PIT was tested in mouse syngeneic tumor models.ResultsAlthough PD-L1-targeted NIR-PIT showed limited effect on tumor cells in vitro, the therapy induced sufficient antitumor effects in vivo, which were thought to be mediated by the ‘photoimmuno’ effect and antitumor immunity augmentation. Moreover, PD-L1-targeted NIR-PIT induced antitumor effect on non-NIR light-irradiated tumors.ConclusionsLocal PD-L1-targeted NIR-PIT enhanced the antitumor immune reaction through a direct photonecrotic effect, thereby providing an alternative approach to targeted cancer immunotherapy and expanding the scope of cancer therapeutics.
Detecting molecular targets in specimens from patients with lung cancer is essential for targeted therapy. Recently, we developed a highly sensitive, rapid-detection device (an immuno-wall device) ...that utilizes photoreactive polyvinyl alcohol immobilized with antibodies against a target protein via a streptavidin-biotin interaction. To evaluate its performance, we assayed epidermal growth factor receptor (EGFR) mutations, such as E746_A750 deletion in exon 19 or L858R substitution in exon 21, both of which are common in non-small cell lung cancer and important predictors of the treatment efficacy of EGFR tyrosine kinase inhibitors. The results showed that in 20-min assays, the devices detected as few as 1% (E746_A750 deletion) and 0.1% (L858R substitution) of mutant cells. Subsequent evaluation of detection of the mutations in surgically resected lung cancer specimens from patients with or without EGFR mutations and previously diagnosed using commercially available, clinically approved genotyping assays revealed diagnostic sensitivities of the immuno-wall device for E746_A750 deletion and L858R substitution of 85.7% and 87.5%, respectively, with specificities of 100% for both mutations. These results suggest that the immuno-wall device represents a good candidate next-generation diagnostic tool, especially for screening of EGFR mutations.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
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