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1.
ACS Cent Sci ; 10(4): 890-898, 2024 Apr 24.
Artículo en Inglés | MEDLINE | ID: mdl-38680568

RESUMEN

Herein, we introduce a model of electronic spin isomers, the electronic counterpart of nuclear spin isomers, by using a stable organic diradical. The diradical, composed of two benzotriazinyl radicals connected by a rigid triptycene skeleton, exhibits a small singlet-triplet energy gap of -3.0 kJ/mol, indicating ca. 1:1 coexistence of the two spin states at room temperature. The diradical shows characteristic near-IR absorption bands, which are absent in the corresponding monoradical subunit. Variable temperature measurements revealed that the absorbance of the NIR band depends on the abundance of the singlet state, allowing us to identify the NIR band as the singlet-specific absorption band. It enables photoexcitation of one of the two spin states coexisting in thermal equilibrium. Transient absorption spectroscopy disclosed that the two spin states independently follow qualitatively different excited-state dynamics. These results demonstrate a novel approach to the design and study of electronic spin isomers based on organic diradicals.

2.
Am J Gastroenterol ; 2024 Mar 29.
Artículo en Inglés | MEDLINE | ID: mdl-38345215

RESUMEN

INTRODUCTION: To verify the value of the pathological criteria for additional treatment in locally resected pT1 colorectal carcinoma (CRC) which have been used in the Japanese Society for Cancer of the Colon and Rectum (JSCCR) guidelines since 2009. METHODS: We enrolled 4,719 patients with pT1 CRC treated at 27 institutions between July 2009 and December 2016 (1,259 patients with local resection alone [group A], 1,508 patients with additional surgery after local resection [group B], and 1,952 patients with surgery alone [group C]). All 5 factors of the JSCCR guidelines (submucosal resection margin, tumor histologic grade, submucosal invasion depth, lymphovascular invasion, and tumor budding) for lymph node metastasis (LNM) had been diagnosed prospectively. RESULTS: Any of the risk factors were present in 3,801 patients. The LNM incidence was 10.3% (95% confidence interval 9.3-11.4) in group B/C patients with risk factors, whereas it was 1.8% (95% confidence interval 0.4-5.2) in those without risk factors ( P < 0.01). In group A, the incidence of recurrence was 3.4% in patients with risk factors, but it was only 0.1% in patients without risk factors ( P < 0.01). The disease-free survival rate of group A patients classified as risk positive was significantly worse than those of groups B and C patients. However, the 5-year disease-free survival rate in group A patients with no risk was 99.2%. DISCUSSION: Our large-scale real-world multicenter study demonstrated the validity of the JSCCR criteria for pT1 CRC after local resection, especially regarding favorable outcomes in patients with low risk of LNM.

3.
Ann Surg Oncol ; 31(4): 2425-2438, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38253948

RESUMEN

BACKGROUND: Extramural venous invasion (EMVI) is a prognostic factor in rectal cancer. There are two types: EMVI detected by magnetic resonance imaging (MRI) (mr-EMVI) and EMVI detected by pathology (p-EMVI). They have been separately evaluated, but they have not yet been concurrently evaluated. We therefore evaluate both mr-EMVI and p-EMVI in rectal cancer at the same time and clarify their association with prognosis. PATIENTS AND METHODS: Included were the 186 consecutive patients who underwent complete radical resection of tumors ≤ stage III at Wakayama Medical University Hospital, Japan, between 2010 and 2018. All underwent preoperative MRI examination, and were reassessed for EMVI by a radiologist. Surgically resected specimens were then reassessed for EMVI by a pathologist. We assessed the correlation between positivity of mr-EMVI and p-EMVI and prognosis, and the clinicopathological background behind them. RESULTS: Patients with double negativity for mr-EMVI and p-EMVI had better prognosis than patients with mr-EMVI or p-EMVI positivity (p < 0.0001). Positivity for mr-EMVI or p-EMVI was a poor independent prognostic factor in multivariate analysis. CONCLUSIONS: Combined analysis of mr-EMVI and p-EMVI may enable prediction of postoperative prognosis of rectal cancer. Patients with double negativity of mr-EMVI and p-EMVI had better prognosis than patients with some form of positivity. Stated differently, patients with positivity of mr-EMVI, p-EMVI, or both had a poorer prognosis than those with double negativity. Postoperative adjuvant chemotherapy may improve poor prognosis. Combined evaluation of mr-EMVI and p-EMVI may be used to predict clinical outcomes and may be an effective prognostic predictor of rectal cancer.


Asunto(s)
Neoplasias del Recto , Humanos , Pronóstico , Invasividad Neoplásica/patología , Neoplasias del Recto/diagnóstico por imagen , Neoplasias del Recto/cirugía , Neoplasias del Recto/patología , Imagen por Resonancia Magnética/métodos , Quimioradioterapia , Estudios Retrospectivos
4.
Nanomaterials (Basel) ; 14(2)2024 Jan 12.
Artículo en Inglés | MEDLINE | ID: mdl-38251139

RESUMEN

This study investigates the nanostructural properties of pseudo-binary Al-1.0Mg2Si (mass%) alloys with and without 0.5Cu using transmission electron microscopy (TEM) and small-angle neutron scattering (SANS). The TEM results show that both alloys exhibit extra electron diffraction spots related to MgSiMg second clusters at peak-aged conditions. High-resolution TEM images have revealed that the second cluster exists as a needle-shaped precipitate that is shorter and thicker than the ß″ phase. We found that the second cluster, which we referred to as the R phase in this paper, is more likely to form partially along the longitudinal axis of a random-type precipitate. Thus, the atomic arrangement in the random-type precipitate is not completely random. SANS is used to quantify the size and volume fraction of the observed needle-shaped precipitates since the R phase is difficult to observe with TEM. The R phase forms even in the Cu-free alloy, but the volume fraction is low, and the growth and formation are retarded near the peak-aged conditions. Undoubtedly, the Cu addition has the effect of stabilizing the growth of the R phase and also promoting its formation. Therefore, the R phase also contributes to the increase in hardness at both under- and peak-aged conditions in the Cu-containing alloy in addition to the strengthening ß″ phases.

5.
Ann Surg ; 279(2): 290-296, 2024 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-37669045

RESUMEN

OBJECTIVE: To investigate how omitting additional surgery after local excision (LE) affects patient outcomes in high-risk T1 colorectal cancer (CRC). BACKGROUND: It is debatable whether additional surgery should be performed for all patients with high-risk T1 CRC regardless of the tolerability of invasive procedures. METHODS: Patients who had received LE for T1 CRC at the Japanese Society for Cancer of the Colon and Rectum institutions between 2009 and 2016 were analyzed. Those who had received additional surgical resection and those who did not were matched one-on-one by the propensity score-matching method. A total of 401 propensity score-matched pairs were extracted from 1975 patients at 27 Japanese Society for Cancer of the Colon and Rectum institutions and were compared. RESULTS: Regional lymph node metastasis was observed in 31 (7.7%) patients in the LE + surgery group. Comparatively, the incidence of oncologic adverse events was low in the LE-alone group, such as the 5-year cumulative risk of local recurrence (4.1%) or overall recurrence (5.5%). In addition, the difference in the 5-year cancer-specific survival between the LE + surgery and LE-alone groups was only 1.8% (99.7% and 97.9%, respectively), whereas the 5-year overall survival was significantly lower in the LE-alone group than in the LE + surgery group [88.5% vs 94.5%, respectively ( P = 0.002)]. CONCLUSIONS: Those who had decided to omit additional surgery at the dedicated center for CRC treatment presented a small number of oncologic events and a satisfactory cancer-specific survival, which may suggest an important role of risk assessment regarding nononcologic adverse events to achieve a best practice for each individual with high-risk T1 tumors.


Asunto(s)
Neoplasias del Colon , Neoplasias Colorrectales , Humanos , Pronóstico , Recurrencia Local de Neoplasia/epidemiología , Recurrencia Local de Neoplasia/patología , Estudios Retrospectivos , Neoplasias Colorrectales/cirugía , Neoplasias Colorrectales/patología , Neoplasias del Colon/patología , Resultado del Tratamiento , Estadificación de Neoplasias
6.
J Am Chem Soc ; 145(48): 26202-26212, 2023 12 06.
Artículo en Inglés | MEDLINE | ID: mdl-37987622

RESUMEN

The covalent inhibition of a target protein has gained widespread attention in the field of drug discovery. Most of the current covalent drugs utilize the high reactivity of cysteines toward modest electrophiles. However, there is a growing need for warheads that can target lysine residues to expand the range of covalently druggable proteins and to deal with emerging proteins with mutations resistant to cysteine-targeted covalent drugs. We have recently developed an N-acyl-N-alkyl sulfonamide (NASA) as a lysine-targeted electrophile. Despite its successful application, this NASA warhead suffered from instability in physiological environments, such as serum-containing medium, because of its high intrinsic reactivity. In this study, we sought to modify the structure of the NASA warhead and found that N-acyl-N-aryl sulfonamides (ArNASAs) are promising electrophiles for use in a lysine-targeted covalent inhibition strategy. We prepared a focused library of ArNASA derivatives with diverse structures and reactivity and identified several warhead candidates with suppressed hydrolysis-mediated inactivation and reduced nonspecific reactions with off-target proteins, without sacrificing the reactivity toward the target. These reaction properties enabled the improved covalent inhibition of intracellular heat shock protein 90 (HSP90) in the presence of serum and the development of the first irreversible inhibitor for ibrutinib-resistant Bruton's tyrosine kinase (BTK) bearing the C481S mutation. This study clearly demonstrated the use of a set of ArNASA warheads to create highly potent covalent drugs and highlighted the importance of enriching the current arsenal of lysine-reactive warheads.


Asunto(s)
Lisina , Piperidinas , Lisina/química , Agammaglobulinemia Tirosina Quinasa/metabolismo , Piperidinas/farmacología , Cisteína/química , Sulfanilamida , Sulfonamidas/farmacología , Inhibidores de Proteínas Quinasas/farmacología , Inhibidores de Proteínas Quinasas/química
7.
Langenbecks Arch Surg ; 408(1): 281, 2023 Jul 18.
Artículo en Inglés | MEDLINE | ID: mdl-37460849

RESUMEN

PURPOSE: A notable advantage of laparoscopic colorectal surgery is that only a small incision at the extraction site is necessary, which is considered to be cosmetically beneficial. Meanwhile, the optimal extraction site for the resected specimen in laparoscopic colectomy is controversial in terms of cosmetic benefit. This randomized controlled trial compares midline and off-midline extraction sites in laparoscopic colectomy in patients with colon cancer, with consideration of cosmetic benefits as the primary endpoint. METHODS: Included were patients that underwent elective laparoscopic colectomy at WMUH between October 2014 and February 2017. Patients were randomly assigned to either midline incision group or off-midline incision group. Prospectively collected data included cosmetic results (patients and observer assessment scale) and complications including incidence of incisional hernia, SSI, and pain. This trial was registered with UMIN Clinical Trials (UMIN000028943). RESULTS: Finally, 98 patients with colorectal cancer were analyzed. No significant differences were found between the two groups in patient and observer assessment scales of cosmetic results (midline 8 ± 1.1 vs off-midline 11 ± 5.9 p = 0.16, midline 13.5 ± 6.6 vs off-midline 15 ± 11 p = 0.58, respectively) or in postoperative pain. However, incisional hernia occurred in four cases in the midline group (8%), which was significantly higher than that in the off-midline group (no cases, 0%). CONCLUSION: There was no significant difference in terms of cosmetic benefit, the primary endpoint, between the two groups. In this study, only the extraction site location was compared; future studies will examine differences depending on the incisional direction, including the incidence of incisional hernia.


Asunto(s)
Hernia Incisional , Laparoscopía , Herida Quirúrgica , Humanos , Hernia Incisional/epidemiología , Hernia Incisional/cirugía , Colectomía/efectos adversos , Colectomía/métodos , Laparoscopía/efectos adversos , Laparoscopía/métodos , Infección de la Herida Quirúrgica , Dolor Postoperatorio/epidemiología , Herida Quirúrgica/complicaciones
8.
Chemistry ; 29(46): e202300126, 2023 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-37246241

RESUMEN

An asymmetric diarylethene dimer composed of 2- and 3-thienylethene units linked by m-phenylene developed various colors upon UV irradiation via an independent photochromic reaction on each unit. The change in contents and the other photoresponses of the photogenerated four isomers were analyzed using quantum yield for all the possible photochemical paths, i. e., photoisomerization, fluorescence, energy transfer, and the other non-radiative paths. Almost all the rate constants of photochemical paths were calculated using measurable quantum yields and lifetimes. It was found that a significant contribution on photoresponse was the competition between photoisomerization and intramolecular energy transfer. The clear difference was observed in the photoresponses of the dimer and the 1 : 1 mixture solution of the model compounds. The m-phenylene spacer appropriately regulated the rate of energy transfer in the asymmetric dimer, and the spacer enabled isolation of the excited state of the dimer, making the above quantitative analysis possible.

9.
Lancet Reg Health West Pac ; 33: 100680, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-37181532

RESUMEN

Background: There are no standardised criteria for the 'regional' pericolic node in colon cancer, which represents a major cause of the international uncertainty regarding the optimal bowel resection margin. This study aimed to determine 'regional' pericolic nodes based on prospective lymph node (LN) mapping. Methods: According to preplanned in vivo measurements of the bowel, the anatomical distributions of the feeding artery and LNs were determined in 2996 stages I-III colon cancer patients who underwent colectomy with resection margin >10 cm at 25 institutions in Japan. Findings: The mean number of retrieved pericolic nodes was 20.9 (standard deviation, 10.8) per patient. In all patients except seven (0.2%), the primary feeding artery was distributed within 10 cm of the primary tumour. The metastatic pericolic node most distant from the primary tumour was within 3 cm in 837 patients, 3-5 cm in 130 patients, 5-7 cm in 39 patients and 7-10 cm in 34 patients. Only four patients (0.1%) had pericolic lymphatic spread beyond 10 cm; all of whom had T3/4 tumours accompanying extensive mesenteric lymphatic spread. The location of metastatic pericolic node did not differ by the feeding artery's distribution. Postoperatively, none of the 2996 patients developed recurrence in the remaining pericolic nodes. Interpretation: The pericolic nodes designated as 'regional' were those located within 10 cm of the primary tumours, which should be fully considered when determining the bowel resection margin, even in the era of complete mesocolic excision. Funding: Japanese Society for Cancer of the Colon and Rectum.

10.
Materials (Basel) ; 16(5)2023 Mar 02.
Artículo en Inglés | MEDLINE | ID: mdl-36903169

RESUMEN

In this paper, the effects of compressive pre-deformation and successive pre-artificial aging on the compressive creep aging behavior and microstructure evolution of the Al-Cu-Li alloy have been studied. Severe hot deformation mainly occurs near the grain boundaries during the compressive creep initially, which steadily extends to the grain interior. After that, the T1 phases will obtain a low radius-thickness ratio. The secondary T1 phases in pre-deformed samples usually only nucleate on dislocation loops or Shockley incomplete dislocations induced by movable dislocations during creep, which are especially prevalent in low plastic pre-deformation. For all pre-deformed and pre-aged samples, two precipitation situations exist. When pre-deformation is low (3% and 6%), solute atoms (Cu and Li) can be consumed prematurely during pre-aging at 200 °C, with dispersed coherent Li-rich clusters in the matrix. Then, the pre-aged samples with low pre-deformation no longer have the ability to form secondary T1 phases in large quantities during subsequent creep. When dislocation entangles seriously to some extent, a large quantity of stacking faults, together with a "Suzuki atmosphere" containing Cu and Li, can provide the nucleation sites for the secondary T1 phase, even when pre-aged at 200 °C. The sample, pre-deformed by 9% and pre-aged at 200 °C, displays excellent dimensional stability during compressive creep because of the mutual reinforcement of entangled dislocations and pre-formed secondary T1 phases. In order to decrease the total creep strain, increasing the pre-deformation level is more effective than pre-aging.

11.
Updates Surg ; 75(4): 837-845, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-36997824

RESUMEN

OBJECTIVES: The population of very elderly patients is increasing, and nonagenarians have significantly higher mortality rates and poorer rates of survival than younger patients. Meanwhile, recent studies have shown colorectal cancer surgery in nonagenarian patients to be feasible regarding postoperative outcomes. This retrospective study aims to evaluate the postoperative outcomes of nonagenarians in the latest clinical settings. METHODS: Consecutive nonagenarian patients who underwent elective colorectal cancer surgery between 2018 and 2020 retrospectively enrolled (Trial registration number: UMIN000046296 on December 7th, 2021). Clinicopathological data and short-term postoperative outcomes were collected for statistical analysis. RESULTS: This study included 81 nonagenarian patients (31 males, 50 females). Postoperative complications occurred in 21 patients (25.9%), and 3 patients died within 90 days (3.7%). Multivariate analysis revealed prognostic nutritional index was a significant predictor of postoperative complications (OR 2.99, 95% CI 0.78-9.10, P = 0.048), and performance status ≥ 3 could be an independent risk factor of 90-day mortality (HR 32.30, 95% CI 3.20-326.10, P = 0.032). CONCLUSIONS: Short-term outcomes after surgical treatment for nonagenarian patients with colorectal cancer were acceptable. Low prognostic nutritional index was closely related to postoperative complications and poor performance status could also lead to 90-day mortality. In aging populations, risk stratification to prevent poorer postoperative outcomes in nonagenarian patients is needed.


Asunto(s)
Neoplasias Colorrectales , Procedimientos Quirúrgicos del Sistema Digestivo , Masculino , Anciano de 80 o más Años , Femenino , Humanos , Anciano , Estudios Retrospectivos , Nonagenarios , Complicaciones Posoperatorias/epidemiología , Factores de Riesgo
12.
Gastrointest Endosc ; 97(6): 1119-1128.e5, 2023 06.
Artículo en Inglés | MEDLINE | ID: mdl-36669574

RESUMEN

BACKGROUND AND AIMS: Since 2009, the Japanese Society for Cancer of the Colon and Rectum guidelines have recommended that tumor budding and submucosal invasion depth, in addition to lymphovascular invasion and tumor grade, be included as risk factors for lymph node metastasis (LNM) in patients with T1 colorectal cancer (CRC). In this study, a novel nomogram was developed and validated by usirge-scale, real-world data, including the Japanese Society for Cancer of the Colon and Rectum risk factors, to accurately evaluate the risk of LNM in T1 CRC. METHODS: Data from 4673 patients with T1 CRC treated at 27 high-volume institutions between 2009 and 2016 were analyzed for LNM risk. To prepare a nonrandom split sample, the total cohort was divided into development and validation cohorts. Pathologic findings were extracted from the medical records of each participating institution. The discrimination ability was measured by using the concordance index, and the variability in each prediction was evaluated by using calibration curves. RESULTS: Six independent risk factors for LNM, including submucosal invasion depth and tumor budding, were identified in the development cohort and entered into a nomogram. The concordance index was .784 for the clinical calculator in the development cohort and .790 in the validation cohort. The calibration curve approached the 45-degree diagonal in the validation cohort. CONCLUSIONS: This is the first nomogram to include submucosal invasion depth and tumor budding for use in routine pathologic diagnosis based on data from a nationwide multi-institutional study. This nomogram, developed with real-world data, should improve decision-making for an appropriate treatment strategy for T1 CRC.


Asunto(s)
Neoplasias del Colon , Neoplasias Colorrectales , Humanos , Nomogramas , Metástasis Linfática , Neoplasias Colorrectales/cirugía , Neoplasias Colorrectales/patología , Invasividad Neoplásica/patología
13.
J Microsc ; 288(1): 10-15, 2022 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-35916115

RESUMEN

Convergent beam electron diffraction (CBED) was used to profile the thickness of aluminium alloys foils prepared by using the twinjet electropolishing method. The two-beam CBED condition was obtained by exciting the { 200 } $\{ {200} \}$ and { 111 } $\{ {111} \}$ aluminium diffracted g-vector. The aluminium alloy foil thicknesses were calculated at different distances from the sample hole edge. In areas where only one Kossel-Möllenstedt (K-M) minima fringe was obtained, the thickness was determined by matching the experimental with simulated convergent beam diffraction patterns. In areas far away from the sample edge, the thickness of foils was high enough to generate at least two (K-M) minima fringes, required for linear regression fitting.

14.
J Phys Chem Lett ; 13(32): 7429-7436, 2022 Aug 18.
Artículo en Inglés | MEDLINE | ID: mdl-35929722

RESUMEN

Photoswitching molecules that reversibly switch upon visible-light irradiation are some of the most attractive targets for biological and imaging applications. In this study, we found a diarylethene (DAE) derivative having a covalently attached perylenebisimide (PBI) unit (DAE-PBI dyad) underwent an unexpected cyclization reaction upon irradiation with green (500-550 nm) light, where the DAE unit has no absorbance. The photoreactivity was enhanced in solvents containing heavy atoms and in the presence of oxygen. As inferred from the solvent dependence and the calculated excited-state energies of DAE and PBI units, it was suggested that the probable mechanism for this unique visible-light-induced cyclization reaction is multiplicity conversion based on intramolecular energy transfer from the excited singlet state of the PBI unit to the triplet state of DAE units (i.e., DAE-1[PBI]* → 3[DAE]*-PBI). Such a unique photoreaction mechanism with the assistance of oxygen will pave the way for new molecular design for the development of visible-light switching molecules.


Asunto(s)
Luz , Oxígeno , Ciclización , Transferencia de Energía , Solventes
15.
J Org Chem ; 87(14): 9034-9043, 2022 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-35749313

RESUMEN

Herein, we describe the synthesis and characterization of fully fused tetraphenylthieno[3,4-d]pyridazine 1 and N-methylpyrrolo[3,4-d]pyridazine 2 with two embedded seven-membered rings. Owing to the incorporated heptagon, 1 and 2 exhibited Cs-symmetric saddle conformations in the solid state with mean plane deviation around 0.38 Å. π-Expanded thienopyridazine 1 showed a one-dimensional (1-D) columnar packing along the b axis with net dipole moment aligning perpendicular to the b axis in the polar crystal system Pc. On the other hand, 2 formed a partially π-stacked brick-work structure. In addition to the Cs-symmetric saddle conformations found in the crystals, density functional theory (DFT) calculation found C2-symmetric twisted conformations of both 1 and 2 close in energy to the saddle conformations. The barrier of conformational interconversion was calculated to be 32 (1) and 31 kJ·mol-1 (2), and the interconversion occurs fast even at -60 °C as evidenced by variable-temperature (VT)-NMR studies. While 1 and 2 have moderately curved structures, optical and electrochemical studies revealed effective π-conjugation over the fused diphenylene units, which is also supported by DFT calculation. As the result of the intrinsic large dipole moment of thieno- and pyrrolo-pyridazines and the notably curved structure, 1 (2) has a substantial out-of-plane dipole moment of 2.0 (3.3) D in the saddle conformations.

16.
Org Lett ; 24(20): 3707-3711, 2022 May 27.
Artículo en Inglés | MEDLINE | ID: mdl-35561030

RESUMEN

Synthesis and characterization of doubly diphenylene-fused 2,3,6,7-tetraazanaphthalene 1 are described. Single-crystal X-ray diffraction analysis showed the highly twisted structure of 1 with a degree of twisting of 13.0°/Å, which is one of the largest values for a π-system. In the crystal, molecules of 1 formed an orthogonal one-dimensional column with π-stacking of diphenylene moieties and a short intermolecular C···N distance due to lone-pair/π* interaction, which is a rare example of lone-pair/π* interaction in a supramolecular assembly.

17.
Surg Endosc ; 36(12): 8843-8855, 2022 12.
Artículo en Inglés | MEDLINE | ID: mdl-35562509

RESUMEN

BACKGROUND: Accurate tumor stage diagnosis during laparoscopic surgery remains difficult. We clarify the impact of new diagnostic strategy using narrow-band imaging (NBI) during laparoscopic surgery for colorectal cancer compared with other strategies. METHODS: We defined angiogenesis (Ag) and fibrosis (Fib) grades using NBI laparoscopy (lap-NBI), and assessed the clinicopathological features associated with these grades for 67 patients with colorectal cancer who underwent surgery. We assessed vessel density and gray scale with computer software. RESULTS: NBI-Ag-grade and NBI-Fib-grade of the serosal surface of cancer lesions and peritoneal nodules correlated with vessel density and gray scale of those assessed by Image J computer software. NBI-Fib-grades of liver nodules also correlated with gray scale. NBI-Ag- grade and Fib-grade of the serosal surface of cancer lesions correlated with pathological depth of invasion. These NBI grades of pathological metastatic peritoneal nodules were higher than those of pathologically benign peritoneal nodules. NBI- Fib grades of pathological metastatic liver nodules were higher than those of pathologically benign liver nodules. In multivariate analysis, lap-NBI was associated with different diagnosis for T3, T4 and non-T3, and non-T4. Moreover, lap-NBI was associated with different diagnosis for T4 and non-T4. Predictive value for T4 by lap-NBI showed high sensitivity (85%) specificity (87%), positive predictive value (74%), negative predictive value (93%), and overall accuracy (87%). Sensitivity and overall accuracy of lap-NBI was superior to that of other diagnostic modalities. CONCLUSION: We clarified the usefulness of the new diagnostic strategy using lap-NBI during laparoscopic surgery for colorectal cancer in comparison with other strategies.


Asunto(s)
Neoplasias Colorrectales , Laparoscopía , Humanos , Imagen de Banda Estrecha/métodos , Laparoscopía/métodos , Valor Predictivo de las Pruebas , Neoplasias Colorrectales/diagnóstico por imagen , Neoplasias Colorrectales/cirugía , Sensibilidad y Especificidad
18.
Nat Commun ; 13(1): 1475, 2022 Apr 04.
Artículo en Inglés | MEDLINE | ID: mdl-35379795

RESUMEN

Helically twisted conductive nanocarbon materials are applicable to optoelectronic and electromagnetic molecular devices working on the nanometer scale. Herein, we report the synthesis of per-peri-perbenzo[5]- and [9]helicenes in addition to previously reported π-extended [7]helicene. The homogeneously π-extended helicenes can be regarded as helically fused oligo-phenanthrenes. The HOMO-LUMO gap decreased significantly from 2.14 to 1.15 eV with increasing helical length, suggesting the large effective conjugation length (ECL) of the π-extended helical framework. The large ECL of π-extended helicenes is attributed to the large orbital interactions between the phenanthrene subunits at the 9- and 10-positions, which form a polyene-like electronic structure. Based on the experimental results and DFT calculations, the ultrafast decay dynamics on the sub-picosecond timescale were attributed to the low-lying conical intersection.

19.
Chemistry ; 28(27): e202201141, 2022 May 11.
Artículo en Inglés | MEDLINE | ID: mdl-35481888

RESUMEN

Invited for the cover of this issue are Ryuto Yasui, Daiki Shimizu, and Kenji Matsuda at Kyoto University. The image depicts a comparison of the molecular conductance of radical-substituted and non-radical-substituted molecular wires evaluated by STM. Read the full text of the article at 10.1002/chem.202104242.

20.
Surg Open Sci ; 8: 69-74, 2022 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-35463847

RESUMEN

Background: The population affected by colorectal cancer is growing, and there is an increasing need for prevention of functional decline following treatment. We proposed that the Kihon Checklist published by the Japanese Ministry of Health, Labor, and Welfare would be an appropriate means of frailty assessment for prediction of postoperative complications in older patients with colorectal cancer. This prospective cohort study aims to identify the factors influencing postoperative frailty. Methods: We prospectively enrolled consecutive patients with colorectal cancer and aged ≥ 65 year (N = 500) between May 2017 and December 2018. Eligible patients were assessed with the Kihon Checklist prior to surgery and 30 days after surgery. The main measures were variables related to postoperative change in view of frail status. Results: According to the Kihon Checklist questionnaire, 164 patients were frail preoperatively and 172 patients were frail postoperatively, whereas 38 patients changed from "nonfrail" before surgery to postoperative "frail." Overall complications were counted in 97 patients (19.4%), and 5 patients died. Performance status ≥ 2, history of laparotomy, open surgery, complication, ostomy creation, and delirium were significantly associated with changing postoperative "frail" (P = .014, P = .023, P = .006, P < .001, P = .023, and P = .024, respectively). In multivariate analysis, independent related factors of changing postoperative "frail" were complication (odds ratio 2.69, 95% confidence interval 1.19-6.09, P = .018) and ostomy creation (odds ratio 2.32, 95% confidence interval 1.01-5.33, P = .047). Conclusion: The Kihon Checklist questionnaire could identify the factors related to postoperative change of frailty status in older patients with colorectal cancer. This cohort concluded that whether postoperative complication occurred or not was closely associated with perioperative change of frailty status.

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