Emotion Regulation Can Effectively Improve Decision-Making Behaviors of Individuals Who Use Methamphetamine.

PURPOSE: Negative emotions can cause people to make irrational decisions, and decision-making disorders may lead individuals who use methamphetamine (meth) to relapse. Therefore, the current study was performed to investigate whether emotion regulation (ER) can improve negative emotions and thus improve decision-making behavior of individuals who use meth. METHOD: Based on the Iowa Gambling Task, a three-factor mixed experimental design was used to examine the effects of cognitive reappraisal and expressive suppression strategies on negative emotions and decision-making behaviors of 157 individuals who use meth. RESULTS: Cognitive reappraisal and expressive suppression were effective in reducing participants' negative emotions and improving decision-making behaviors. Specifically, two types of ER strategies were effective in improving decision-making abilities of participants with negative emotional distress, and cognitive reappraisal was more effective than expressive suppression. CONCLUSION: Regarding cognitive reappraisal, female participants showed better decision-making behavior than males, which predicts that females who use meth might be more adept at using cognitive reappraisal. This finding suggests that mental health providers should aid substance users in managing their negative emotions and also pay attention to gender differences during the nursing process. [Journal of Psychosocial Nursing and Mental Health Services, xx(xx), xx-xx.].

Carbamoylphosphinidene: A Phosphorus Analogue of Carbonyl Nitrene.

Carbonyl nitrenes are versatile intermediates that have been extensively characterized; however, their phosphorus analogues remain largely unknown. Herein, we report the observation of a rare example of carbonyl phosphinidene NH2C(O)P, which was generated through the photolytic (193 nm) dehydrogenation of phosphinecarboxamide (NH2C(O)PH2) in a solid N2-matrix at 12 K. The characterization of NH2C(O)P in the triplet ground state with matrix-isolation IR and ultraviolet-visible (UV-vis) spectroscopy is supported by comprehensive isotope labeling experiments (D and 15N) and quantum chemical calculations. Upon visible-light irradiation at 680 nm, NH2C(O)P inserts into dihydrogen by the reformation of NH2C(O)PH2 with concomitant isomerization to the more stable aminophosphaketene (NH2PCO). Additionally, the photoisomerization of NH2C(O)PH2 to NH2C(OH) = PH along with decomposition by yielding hydrogen-bonded complexes HNCO···PH3 and HPCO···NH3 has been observed in the matrix.

Spectroscopy and Photochemistry of [Al, N, C, O, H]: Connectivity to Aluminium-Bearing Species in the Universe.

Aluminium is one of the most abundant metals in the universe and impacts the evolution of various astrophysical environments. Currently detected Al-bearing molecules represent only a small fraction of the aluminium budget, suggesting that aluminium may reside in other species. AlO and AlOH molecules are abundant in the oxygen-rich supergiant stars such as VY Canis Majoris, a stellar molecular factory with 60+ molecules including the prebiotic NC-bearing species. Additional Al-bearing molecules with N, C, O, and H may form in O-rich environments with radiation-accelerated chemistry. Here, we present spectroscopic identification of novel aluminium-bearing molecules composed of [Al, N, C, O, H] and [Al, N, C, O] from the reactions of Al atoms and HNCO in solid argon matrix, which are potential Al-bearing molecules in space. Photoinduced transformations among six [Al, N, C, O, H] isomers and three [Al, N, C, O] isomers, along with their dissociation reactions forming the known interstellar species, have been disclosed. These results provide new insight into the chemical network of astronomically detected Al-bearing species in space.

A rotational spectroscopy study of microsolvation effects on intramolecular proton transfer in trifluoroacetylacetone-(H2O)1-3.

Trifluoroacetylacetone (TFAA) has two enol forms, which can switch to each other via proton transfer. While much attention has been paid to their conformational preferences, the influence of microsolvation on regulating the proton position remains unexplored. Herein, we report the rotational spectra of trifluoroacetylacetone-(water)n (n = 1-3) investigated by chirped pulse Fourier transform microwave spectroscopy in the 2-8 GHz frequency range. Two conformers were identified for both TFAA-H2O and TFAA-(H2O)2, while only one conformer was characterized for TFAA-(H2O)3. The results indicate that water binding on the CH3 side stabilizes the enolF form, whereas water binding on the CF3 side stabilizes the enolH form. The enolF form predominates over the enolH form in these hydrated complexes, which contrasts with the fact that only enolH exists in isolated TFAA. EnolH becomes preferred only when water inserts itself into the intramolecular hydrogen bond. Instanton theory calculations reveal that the proton transfer reaction is dominated by quantum tunneling at low temperatures, leading to the stable existence of only one enol form in each configuration of the hydrated clusters.

Spectroscopic Study of [Mg, H, N, C, O] Species: Implications for the Astrochemical Magnesium Chemistry.

Magnesium is an abundant metal element in space, and magnesium chemistry has vital importance in the evolution of interstellar medium (ISM) and circumstellar regions, such as the asymptotic giant branch star IRC+10216 where a variety of Mg compounds bearing H, C, N, and O have been detected and proposed as the important components in the gas-phase molecular clouds and solid-state dust grains. Herein, we report the formation and infrared spectroscopic characterization of the Mg-bearing molecules HMg, [Mg, N, C], [Mg, H, N, C], [Mg, N, C, O], and [Mg, H, N, C, O] from the reactions of Mg/Mg+ and the prebiotic isocyanic acid (HNCO) in the solid neon matrix. Based on their thermal diffusion and photochemical behavior, a complex reactivity landscape involving association, decomposition, and isomerization reactions of these Mg-bearing molecules is developed, which can not only help understand the chemical processes of the magnesium (iso)cyanides in astrochemistry but also provide implications on the presence of magnesium (iso)cyanates in the ISM and the chemical model for the dust grain surface reactions. It also provides a new paradigm of the key intermediate nature of the cationic complexes in the formation of neutral interstellar species.

Hydrogen-Bonded Complex of the Parent Phosphinidene.

The diatomic molecule PH is very reactive, and it serves as the parent compound for phosphinidenes featuring a monovalent phosphorus atom. Herein, we report the characterization and reactivity of a rare hydrogen-bonded complex of PH. Specifically, the molecular complex between PH and HCl has been generated by photolysis of chlorophosphine (H2PCl) at 254 nm in a solid Ar-matrix at 10 K. The IR spectrum of the complex HP⋅⋅⋅HCl and quantum chemical calculations at the UCCSD(T)-F12a/haTZ level consistently prove that the phosphorus atom acts as a hydrogen bond acceptor with a binding energy (D0) of -0.6 kcal mol-1. In line with the observed absorption at 341 nm for the binary complex, the triplet phosphinidene PH undergoes prototype H-Cl bond insertion by reformation of H2PCl upon photoexcitation at 365 nm. However, this hydrogen-bonded complex is unstable in the presence of N2 and HCl, as both molecules prefers stronger interactions with HCl than PH in the observed complexes HP⋅⋅⋅HCl⋅⋅⋅N2 and HP⋅⋅⋅2HCl.

Observation of the Water-HNSO2 Complex.

Sulfamic acid (NH2SO3H, SFA) is supposed to play an important role in aerosol new particle formation (NPF) in the atmosphere, and its formation mainly arises from the SO3-NH3 reaction system in which weakly bonded donor-acceptor complexes such as SO3···NH3 and isomeric HNSO2···H2O have been proposed as the key intermediates. In this study, we reveal the first spectroscopic observation of HNSO2···H2O in two forms in a solid Ar matrix at 10 K. The major form consists of two intermolecular H bonds by forming a six-membered ring structure with a calculated dissociation energy of 7.6 kcal mol-1 at the CCSD(T)-F12a/aug-cc-pVTZ level of theory. The less stable form resembles SO3···H2O in containing a pure chalcogen bond (S···O) with a dissociation energy of 7.2 kcal mol-1. The characterization of HNSO2···H2O with matrix-isolation IR spectroscopy is supported by D- and 18O-isotope labeling and quantum chemical calculations.

Discovery of Pyroptosis-inducing Drugs and Antineoplastic Activity Based on the ROS/ER Stress/Pyroptosis Axis.

BACKGROUND: Pyroptosis, a cell death process triggered by chemotherapy drugs, has emerged as a highly promising mechanism for combating tumors in recent years. As the lead of new drugs, natural products play an important role in the discovery of anticancer drugs. Compared to other natural products, the medicine food homologous natural products (MFHNP) exhibit a superior safety profile. Among a series of MFHNP molecular skeletons, this study found that only benzylideneacetophenone (1) could induce cancer cell pyroptosis. However, the anti-cancer activity of 1 remains to be improved. AIMS: This study aimed to find a pyroptosis inducer with highly effective antitumor activity by modifying the chalcone structure. METHODS: To examine the effect of the Michael receptor in compound 1 on the induction of pyroptosis, several analogs were synthesized by modifying the Michael acceptor. Subsequently, the anticancer activity was tested by MTT assay, and morphological indications of pyroptosis were observed in human lung carcinoma NCI-H460 and human ovarian cancer CP-70 cell lines. Furthermore, to improve the activity of the chalcone skeleton, the anticancer group 3,4,5- trimethoxyphenyl was incorporated into the phenyl ring. Subsequently, compounds 2-22 were designed, synthesized, and screened in human lung cancer cells (NCI-H460, H1975, and A549). Additionally, a quantitative structure-activity relationship (QSAR) model was established using the eXtreme Gradient Boosting (XGBoost) machine learning library to identify the pharmacophore. Furthermore, both in vitro and in vivo experiments were conducted to investigate the molecular mechanisms of pyroptosis induced by the active compound. RESULTS: α, ß-unsaturated ketone was the functional group of the chalcone skeleton and played a pivotal role in inducing cancer cell pyroptosis. QSAR models showed that the regression coefficients (R2) were 0.992 (A549 cells), 0.990 (NCI-H460 cells), and 0.998 (H1975 cells). Among these compounds, compound 7 was selected to be the active compound. Moreover, compound 7 was found to induce pyroptosis in lung cancer cells by upregulating the expression of CHOP by increasing the ROS level. Furthermore, it effectively suppressed the growth of lung cancer xenograft tumors. CONCLUSION: Compound 7 exhibits antineoplastic activity by regulating the ROS/ER stress/pyroptosis axis and is a kind of promising pyroptosis inducer.

Comparative effectiveness of warfarin in cirrhotic patients with non-symptomatic portal vein thrombosis: a multicenter, randomized controlled trial.

The effectiveness and risks of anticoagulant therapy in cirrhotic patients with non-symptomatic portal vein thrombosis (PVT) remain unclear. We conducted a multicenter, Zelen-designed randomized controlled trial to determine the effectiveness of warfarin in cirrhotic patients with non-symptomatic PVT during a one-year follow-up. In brief, 64 patients were 1:1 randomly divided into the anticoagulation group or the untreated group. The probability of recanalization was significantly higher in the anticoagulation group than those untreated in both ITT analysis (71.9% vs 34.4%, p = 0.004) and PP analysis (76.7% vs 32.4%, p < 0.001). Anticoagulation treatment was the independent predictor of recanalization (HR 2.776, 95%CI 1.307-5.893, p = 0.008). The risk of bleeding events and mortality were not significantly different. A significantly higher incidence of ascites aggravation was observed in the untreated group (3.3% vs 26.5%, p = 0.015). In conclusion, warfarin was proved to be an effective and safe as an anticoagulation therapy for treating non-symptomatic PVT in cirrhotic patients.

Unveiling the Role of Water on π-π Stacking Through Microwave Spectroscopy of (Thiophene)2-(Water)1-2 Clusters.

There has been an ongoing debate about whether water enhances or hinders π-π stacking, a phenomenon crucial in various biological and chemical systems. In this study, the influence of water on π-π stacking is investigated by microwave spectroscopic observation of gas-phase hydrated clusters of thiophene dimers. Two isomers of (C4H4S)2-H2O and two isomers of (C4H4S)2-(H2O)2 have been unambiguously identified. These identifications are supported by quantum chemistry calculations and isotopic measurements. In each of these conformations, water molecules are situated between aromatic pairs, forming distinctive interactions. Water molecules engage with thiophene molecules either as hydrogen bond donors through OH···π interactions or as hydrogen bond acceptors through CH···O interactions. The energy decomposition analysis indicates that the bonding pattern of water molecules significantly affects the π···π interactions between aromatic rings. These findings offer valuable structural insights into the role of water in shaping π-π stacking.

Phosphinidenes: Fundamental Properties and Reactivity.

Phosphinidenes are heavy congeners of nitrenes that have been broadly used as in situ reagents in synthetic phosphorus chemistry and also serve as versatile ligands in coordination with transition metals. However, the detection of free phosphinidenes is largely challenged by their high reactivity and also the lack of suitable synthetic methods, rendering the knowledge about the fundamental properties of this class of low-valent phosphorus compounds limited. Recently, an increasing number of free phosphinidenes bearing prototype structural and bonding properties have been prepared for the first time, thus enabling the exploration of their distinct reactivity from the nitrene analogues. This Concept article will discuss the experimental approaches for the generation of the highly unstable phosphinidenes and highlight their distinct reactivity from the nitrogen analogues so as to stimuate future studies about their potential applications in phosphorus chemistry.

3-Fluoro-2H-azirine: Generation, Characterization, and Photochemistry.

The elusive 3-fluoro-2H-azirine, cyclic NCH2CF, has been generated through the stepwise decomposition of the acryloyl azide CH2CFC(O)N3 in an N2-matrix at 10 K. The characterization of cyclic NCH2CF with matrix-isolation IR spectroscopy is supported by 15N isotope labeling and the calculations with density functional theory (DFT) at the B3LYP/6-311++G(3df,3pd) level of theory. Upon irradiation at 193 nm, cyclic NCH2CF undergoes ring opening by forming the more stable nitrile isomer CH2FCN. In contrast to the photodecomposition reactions, the high-vacuum flash pyrolysis of CH2CFC(O)N3 in the gas phase at 500 °C yields the Curtius rearrangement product CH2CFNCO along with secondary fragmentation to the atmospherically relevant fluorocarbonyl radical (FCO) and cyanomethyl radical (CH2CN). Calculations on the potential energy profile for the decomposition reactions of CH2CFC(O)N3 demonstrate that the excessive energy, arising from the highly exothermic Curtius rearrangement of the azide, plays a key role in driving further dissociation reactions of CH2CFNCO by overcoming the formidable barriers (>50 kcal mol-1) under the pyrolysis conditions.

Identification and Photochemistry of the Mercaptomethyl Radical.

The mercaptomethyl radical (·CH2SH) is a higher-energy isomer of the methylthio radical (CH3S·) that has been proposed as an important intermediate in atmospheric and interstellar sulfur chemistry. Herein, we report the spectroscopic identification of ·CH2SH during the UV (365 nm) photolysis of CH3S· in a solid Ar-matrix at 10 K. Upon subsequent irradiation at 266 nm, the dehydrogenation of ·CH2SH to yield CS via the intermediacy of the elusive thioformyl radical (HCS·) has also been observed. The characterization of ·CH2SH and HCS· with matrix-isolation IR and UV-vis spectroscopy is supported by 13C-isotope labeling and quantum chemical calculations at the CCSD(T)-F12a/cc-pVTZ-F12 level using configuration-selective vibrational configuration interaction theory (VCI). The disclosed photochemistry of ·CH2SH provides new insight into understanding the chemical evolution of organosulfur molecules in the interstellar medium (ISM).

Recent advances in understanding T cell activation and exhaustion during HBV infection.

Chronic hepatitis B virus (HBV) infection remains a major public health concern globally, and T cell responses are widely believed to play a pivotal role in mediating HBV clearance. Accordingly, research on the characteristics of HBV-specific T cell responses, from activation to exhaustion, has advanced rapidly. Here, we summarize recent developments in characterizing T cell immunity in HBV infection by reviewing basic and clinical research published in the last five years. We provide a comprehensive summary of the mechanisms that induce effective anti-HBV T cell immunity, as well as the latest developments in understanding T cell dysfunction in chronic HBV infection. Furthermore, we briefly discuss current novel treatment strategies aimed at restoring anti-HBV T cell responses.

Spectroscopic identification of the ammonia-mercapto radical complex.

The elusive hydrogen-bonded radical complex (˙SH⋯NH3) consisting of ammonia (NH3) and a mercapto radical (˙SH) has been generated through the 193 nm laser photolysis of the molecular complex between NH3 and hydrogen sulfide (H2S) in solid Ar- and N2-matrixes at 10 K. The identification of ˙SH⋯NH3 with matrix-isolation IR spectroscopy and UV-vis spectroscopy is supported by 15N- and D-isotope labeling experiments and quantum chemical calculations at the B3LYP-D3(BJ)/6-311++G(3df,3pd) level of theory. In line with a large red shift of -172.2 cm-1 for the frequency of the S-H stretching mode observed in ˙SH⋯NH3 (cf. free ˙SH), the radical ˙SH acts as a hydrogen donor, and NH3 acts as an acceptor. According to the calculations at the CCSD(T)/aug-cc-pVTZ level, the SH⋯N bonded structure ˙SH⋯NH3 (binding energy De = 3.9 kcal mol-1) is more stable than the isomeric amidogen radical complex HSH⋯˙NH2 (De = 2.8 kcal mol-1) by 16.6 kcal mol-1. This is in sharp contrast to the photochemistry of the closely related HOH⋯NH3 complex, since the water-amidogen radical complex HOH⋯˙NH2 (De = 5.1 kcal mol-1) was generated under similar photolysis conditions, whereas the ammonia-hydroxyl radical complex ˙OH⋯NH3 (De = 7.9 kcal mol-1) is higher in energy by 9.3 kcal mol-1.

FP(µ-N)2 S: A Sulfur-Pnictogen Four-Membered Ring with 6π Electrons.

The new 6π-electron four-membered ring compound 3-fluoro-1λ2 ,2,4,3λ3 -thiadiazaphosphetidine, FP(µ-N)2 S, has been generated in the gas phase through high-vacuum flash pyrolysis (HVFP) of thiophosphoryl diazide, FP(S)(N3 )2 , at 1000 K. Subsequent isolation of FP(µ-N)2 S in cryogenic matrices (Ar, Ne, and N2 ) allows its characterization with matrix-isolation IR and UV-vis spectroscopy by combination with 15 N-isotope labeling and computations at the CCSD(T)-F12a/VTZ-F12 level of theory. Upon visible-light irradiation at 550 nm, this cyclic compound undergoes ring-opening to the thiazyl isomer FPNSN, followed by dissociation to FP and SN2 under subsequent UV-irradiation at 365 nm. In sharp contrast to the square planar structure for the isolobal four-membered ring S2 N2 , a puckered structure with significant biradical character has been found for FP(µ-N)2 S.

Generate Greater Gratitude When Being Help? A Study of the Psychological Mechanism of Gratitude for Chinese Poor College Students.

The Chinese government has invested much money to help poor college students complete their studies, but the gratitude of the recipients remains to be further studied. This study proposed a parallel mediation model and used questionnaires to investigate 260 thousand college students of China to examine the impact of the level of social support on poor college students' gratitude and the mediating role played by social responsibility and relative deprivation. The results showed that social support positively predicted the gratitude level of poor college students; social responsibility and relative deprivation mediated the relationship between social support and gratitude; gender, school type and difficulty level had a significant influence on gratitude level. In short, education to improve the sense of gratitude of poor college students can be summarized as "two increases and one decrease": increase social support, enhance social responsibility, and reduce relative deprivation.

A study on the social contract conditional reasoning of male substance abusers during detoxification.

Previous studies on social contract reasoning of male substance abusers only examined individuals who are using drugs, and most of them compared social contract and nonsocial contract reasoning, and paid less attention to the characteristics of social contract reasoning of substance abusers during withdrawal. In addition, there is little research on the difference between the standard social contract rules and the switched social contract rules. To further explore this issue, experiment 1 examined the differences between 110 male substance abusers' conditional reasoning for descriptive and social contract rules; Experiment 2 examined the differences between 110 other male substance abusers' conditional reasoning for standard and switched social contracts. Results: (1) for male substance abusers, the performance of social contract conditional reasoning is significantly better than descriptive conditional reasoning; (2) the performance of standard social contract rules is significantly better than that of switched social contract rules.

Hydrogen-Bonded π Complexes between Phosphaethyne and Hydrogen Chloride.

The highly labile complexes between phosphaethyne (HCP) and hydrogen chloride (HCl) with 1:1 and 1:2 stoichiometries have been generated in Ar and N2 matrices at 10 K through laser photolysis of the molecular precursors 1-chlorophosphaethene (CH2PCl) and dichloromethylphosphine (CH3PCl2), respectively. The IR spectrum of the 1:1 complex suggests the preference of a single "T-shaped" structure in which HCl acts as the hydrogen donor that interacts with the electron-rich C≡P triple bond. In contrast, three isomeric structures for the 1:2 complex bearing a core structure of the "T-shaped" 1:1 complex are present in the matrix. The spectroscopic identification of these rare HCP π-electron complexes is supported by D-isotope labeling and the quantum chemical calculations at the CCSD(T)-F12a/cc-pVTZ-F12 level of theory.

Quantum Tunneling in Peroxide O-O Bond Breaking Reaction.

The importance of quantum-mechanical tunneling becomes increasingly recognized in chemical reactions involving hydrogen as well as heavier atoms. Here we report concerted heavy-atom tunneling in an oxygen-oxygen bond breaking reaction from cyclic beryllium peroxide to linear dioxide in cryogenic Ne matrix, as evidenced by subtle temperature-dependent reaction kinetics and unusually large kinetic isotope effects. Furthermore, we demonstrate that the tunneling rate can be tuned through noble gas atom coordination on the electrophilic beryllium center of Be(O2), as the half-life dramatically increased from 0.1 h for NeBe(O2) at 3 K to 12.8 h for ArBe(O2). Quantum chemistry and instanton theory calculations reveal that noble gas coordination notably stabilizes the reactants and transition states, increases the barrier heights and widths, and consequently reduces the reaction rate drastically. The calculated rates and in particular kinetic isotope effects are in good agreement with experiment.