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2.
Int J Urol ; 2024 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-38708677

RESUMO

OBJECTIVES: We investigated the background of patients who underwent contact laser vaporization of the prostate (CVP) surgery and the learning curve of the operators. METHODS: A total of 207 patients who underwent CVP surgery for benign prostatic hyperplasia between August 2018 and March 2023 were included in this study. Patient background, perioperative results, pre- and postoperative urinary flow tests, and complications were collected retrospectively. RESULTS: We enrolled 12 doctors who were divided into expert (five doctors) and novice (seven doctors) groups based on the number of TURP experiences before CVP. The median patient age was 73 years (51-92 years) and prostate volume was 56 cc (15-190 cc) with no difference between the expert and novice groups. Complications included urinary retention (eight cases), hematuria (four), urinary tract infection (four), intraoperative perforation (two), and postoperative stricture (one). Both cases of intraoperative perforation occurred in the novice group. The expert group had a significantly shorter operative time (38 vs. 66 min) and a higher operative efficacy of prostate volume divided by operative time (1.43 vs. 0.88 cc/min). Postoperatively, IPSS, quality of life scores, and postvoid residual urine volume decreased, and maximal flow rate increased; however, there was no significant difference between the groups. The expert group showed stable operative time and operative efficacy after about five to eight cases, while the novice group showed stable after about 15 cases. CONCLUSIONS: Our findings suggest that CVP was safely performed at our hospital, and operators with limited experience in TURP can achieve stable perioperative results.

3.
Artigo em Inglês | MEDLINE | ID: mdl-38687023

RESUMO

Recent advancements in medical equipment have led to the use of exoscopes in neurosurgery, thereby replacing conventional operating microscopes.1,2 These devices enable surgeons to work comfortably, even in situations requiring a tilted visual axis, and their effectiveness in carotid endarterectomy (CEA) for carotid artery stenosis has been reported.3,4 However, the placement of 3-dimensional (3D) monitoring devices is challenging.3,4 To address this issue, we present a case in which CEA was performed using ORBEYE with a 3D head-mounted display. This device allows continuous 3D observation of the surgical field on the preocular screen. Case: A 79-year-old man who had undergone chemoradiotherapy for left maxillary cancer 5 years earlier was referred to our department to undergo treatment for left internal carotid artery stenosis. Computed tomography angiography revealed severe left internal carotid artery stenosis with hypoechoic vulnerable plaques on carotid ultrasound. Carotid artery stenting was considered to be a better option than CEA. However, CEA yields better outcomes, especially in patients with vulnerable soft plaques.5 Left CEA was performed using ORBEYE with a 3D head-mounted display (HOGY Medical Co., Ltd.). The procedure was successfully performed under the observation of the head-mounted display, from skin incision to closure. Postoperatively, the patient had no neurological deficits but experienced transient hoarseness. Using an exoscope under the guidance of a head-mounted display represents a next-generation surgical technique that overcomes the limitations of traditional exoscopic surgery. The patient consented to the procedure, and the participants and any identifiable individuals consented to publication of his/her image. Our institutional review board approved this publication (#B230184).

4.
Radiol Case Rep ; 19(6): 2418-2421, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38585394

RESUMO

Herein, we report a unique case of nontraumatic direct carotid-cavernous fistula presenting with intracerebral hemorrhage without any ocular symptoms. A 90-year-old woman was found unconscious and vomiting due to a subcortical hemorrhage in the temporal lobe. Magnetic resonance angiography revealed a direct carotid-cavernous fistula of Barrow type A. Extensive cortical venous reflux from the superficial middle cerebral vein was observed and identified as a probable contributor to the cerebral hemorrhage. We performed successful embolization using combined transarterial and transvenous approaches. We first occluded the dangerous venous drainage via the transvenous approach, followed by selective occlusion of the direct carotid-cavernous fistula via the transarterial approach. This strategy provided that the dangerous venous drainage was completely occluded first in case complete obliteration could not be achieved with the transarterial approach.

5.
J Neurosurg Case Lessons ; 7(10)2024 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-38437674

RESUMO

BACKGROUND: The treatment of vertebrobasilar junction (VBJ) aneurysms is challenging. Although flow diverters (FDs) are a possible treatment option, geometrical conditions hinder intervention. VBJ aneurysms possess dual inflow vessels from the bilateral vertebral arteries (VAs), one of which is ideally occluded prior to FD treatment. However, it remains unclear which VA should be occluded. OBSERVATIONS: A 75-year-old male with a growing VBJ complex aneurysm exhibiting invagination toward the brainstem and causing perifocal edema required intervention. Preoperative computational fluid dynamics (CFD) analysis demonstrated that left VA occlusion would result in more stagnant flow and less impingement of flow than right VA occlusion. According to the simulated strategy, surgical clipping of the left VA just proximal to the aneurysm was performed, followed by FD placement from the basilar artery trunk to the right VA. The patient demonstrated tolerance of the VA occlusion, and follow-up computed tomography angiography at 18 months after FD treatment confirmed the disappearance of the aneurysm. LESSONS: Preoperative flow dynamics simulations using CFD analysis can reveal an optimal treatment strategy involving a hybrid surgery that combines FD placement and direct surgical occlusion for a VBJ complex aneurysm.

6.
J Neurosurg Case Lessons ; 6(23)2023 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-38048570

RESUMO

BACKGROUND: Exoscopy in neurosurgery offers various advantages, including increased freedom of the viewing axis while the surgeon maintains a comfortable upright position. However, the optimal monitor positioning to avoid interference with surgical manipulation remains unresolved. Herein, the authors describe two cases in which a three-dimensional head-mounted display (3D-HMD) was introduced into a transcranial neurosurgical procedure using an exoscope. OBSERVATIONS: Case 1 was a 50-year-old man who presented with recurrent epistaxis and was diagnosed with an olfactory neuroblastoma that extended from the nasal cavity to the anterior cranial base and infiltrated the right anterior cranial fossa. Case 2 was a 65-year-old man who presented with epistaxis and was diagnosed with a left-sided olfactory neuroblastoma. In both cases, en bloc tumor resection was successfully performed via a simultaneous exoscopic transcranial approach using a 3D-HMD and an endoscopic endonasal approach, eliminating the need to watch a large monitor beside the patient. LESSONS: This is the first report of using a 3D-HMD in transcranial surgery. The 3D-HMD effectively addressed issues with the field of vision and concentration while preserving the effectiveness of traditional microscopic and exoscopic procedures when observed on a 3D monitor. Combining the 3D-HMD with an exoscope holds the potential to become a next-generation surgical approach.

7.
Diagn Cytopathol ; 51(10): E294-E300, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37475580

RESUMO

SMARCB1 (INI1) is one of the switch/sucrose nonfermentable (SWI/SNF) complexes whose loss is associated with several tumors. SMARCB1 (INI1)-deficient intrathoracic neoplasms are extremely rare and known to be highly malignant and lethal. This report presents the case of a patient diagnosed with SMARCB1 (INI1)-deficient intrathoracic neoplasm during chemotherapy for plasma cell myeloma. A 77-year-old male patient complained of cough, bloody sputum, and fever with an enlarged right lung mass and pleural effusion. His cytological examination revealed undifferentiated epithelioid and rhabdoid/plasmacytoid cells with bi- or multinucleation, vacuolization, mitosis, and pleomorphism. However, it was difficult to distinguish the relapse of plasma cell myeloma as atypical plasmacytoid cells were detected. Immunohistochemically, the neoplastic cells showed a loss of SMARCB1 (INI1) expression in the cell block of pleural fluid and in the right lung of the autopsy specimen. Further, the patient was diagnosed with SMARCB1 (INI1)-deficient intrathoracic neoplasm of the right lung based on histological and autopsy findings. To the best of our knowledge, this is the first report of cytomorphology in a SMARCB1 (INI1)-deficient intrathoracic neoplasm.


Assuntos
Mieloma Múltiplo , Tumor Rabdoide , Masculino , Humanos , Idoso , Recidiva Local de Neoplasia , Proteína SMARCB1/genética , Biomarcadores Tumorais/metabolismo , Tumor Rabdoide/patologia
8.
Angew Chem Int Ed Engl ; 62(26): e202303725, 2023 Jun 26.
Artigo em Inglês | MEDLINE | ID: mdl-37014627

RESUMO

Donor-π-acceptor fluorophores that consist of an electron-donating amino group and an electron-accepting triarylborane moiety generally exhibit substantial solvatochromism in their fluorescence while retaining high fluorescence quantum yields even in polar media. Herein, we report a new family of this compound class, which bears ortho-P(=X)R2 -substituted phenyl groups (X=O or S) as a photodissociative module. The P=X moiety that intramolecularly coordinates to the boron atom undergoes dissociation in the excited state, giving rise to dual emission from the corresponding tetra- and tricoordinate boron species. The susceptibility of the systems to photodissociation depends on the coordination ability of the P=O and P=S moieties, whereby the latter facilitates dissociation. The intensity ratios of the dual emission bands are sensitive to environmental parameters, including temperature, solution polarity, and the viscosity of the medium. Moreover, precise tuning of the P(=X)R2 group and the electron-donating amino moiety led to single-molecule white emission in solution.


Assuntos
Boro , Ursidae , Animais , Elétrons , Fluorescência , Corantes Fluorescentes , Ionóforos
9.
J Orthop Sci ; 28(6): 1274-1278, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-36609035

RESUMO

BACKGROUND: The management of pain in patients with rotator cuff tears can be challenging. Neuropathic pain is reportedly associated with pain occurrence in musculoskeletal diseases. However, to date, few studies have reported on the prevalence of neuropathic pain in patients with rotator cuff tears or identified the factors associated with neuropathic pain in a multicenter study. METHODS: A total of 391 patients (205 males and 186 females; median age, 67.7 years; range, 27-92 years) with rotator cuff tears were included in this study. The prevalence of neuropathic pain in rotator cuff tears was investigated using the Japanese version of the painDETECT questionnaire for all patients. In addition, factors significantly associated with the occurrence of neuropathic pain were examined using multivariate logistic regression analysis. RESULTS: Twenty-eight patients (7.2%) were classified into the neuropathic pain group (score ≥19), 97 (24.8%) into the uncertainty regarding neuropathy group (score 13-18), and 266 (68.0%) into the nociceptive pain group (score ≤12). According to the multivariate logistic regression analysis, the independent predictors of neuropathic pain were the VAS score (most severe pain during the past 4 weeks; odds ratio, 1.55; 95% confidence interval [CI], 1.23-2.09) and UCLA shoulder score (odds ratio, 0.81; 95% CI, 0.65-0.97). CONCLUSIONS: Based on the study findings, the prevalence of neuropathic pain in patients with rotator cuff tear was 7.2%. It is important to investigate the presence or absence of neuropathic pain when treating patients with painful rotator cuff tears, because neuropathy associated with rotator cuff tears may adversely affect patient outcomes.


Assuntos
Neuralgia , Lesões do Manguito Rotador , Masculino , Feminino , Humanos , Idoso , Lesões do Manguito Rotador/complicações , Lesões do Manguito Rotador/epidemiologia , Prevalência , Dor de Ombro/diagnóstico , Dor de Ombro/epidemiologia , Dor de Ombro/etiologia , Neuralgia/diagnóstico , Neuralgia/epidemiologia , Neuralgia/etiologia , Causalidade
10.
Vasc Endovascular Surg ; 57(2): 137-148, 2023 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-36189731

RESUMO

BACKGROUND: Among tandem occlusions, atherosclerotic cervical internal carotid artery occlusion (ACICAO) can be technically challenging and associated with its unique complications. We evaluated our experience with endovascular treatment (EVT) of ACICAO in the setting of acute ischemic stroke. METHODS: In total, 154 consecutive patients who underwent EVT for acute anterior circulation stroke at our institute were retrospectively reviewed. Patients with tandem ACICAO were analyzed in this study. Procedures, recanalization rates, complications, and prognoses were evaluated. RESULTS: Ten patients (6%) of all 154 patients had ACICAO. In nine (90%) of the 10 patients, cervical lesions were successfully crossed and intervened upon. Four patients underwent stenting and five underwent angioplasty alone, followed by intracranial procedure. Eight patients (80%) achieved successful recanalization following mechanical thrombectomy for intracranial occlusion. However, one patient had massive subarachnoid hemorrhage during the procedure and another patient developed massive intracranial hemorrhage after EVT, both after stenting. Four of the five patients who initially underwent angioplasty alone subsequently underwent staged endarterectomy or stenting for residual stenosis on or after the next day. The single patient in whom the cervical lesion could not be crossed and another with reocclusion after EVT underwent a rescue bypass procedure due to persistent ischemic symptoms. After 90 days, four patients (40%) were functionally independent (modified Rankin scale score 0-2). CONCLUSIONS: Our experience suggests that EVT for ACICAO is technically feasible; however, it involves the potential risk of several significant complications. To avoid serious hemorrhagic complications, cervical lesions may be better treated with angioplasty alone first.


Assuntos
Doenças das Artérias Carótidas , Estenose das Carótidas , Procedimentos Endovasculares , AVC Isquêmico , Acidente Vascular Cerebral , Humanos , AVC Isquêmico/diagnóstico por imagem , AVC Isquêmico/etiologia , AVC Isquêmico/terapia , Estenose das Carótidas/complicações , Estenose das Carótidas/diagnóstico por imagem , Estenose das Carótidas/terapia , Artéria Carótida Interna/diagnóstico por imagem , Artéria Carótida Interna/cirurgia , Estudos Retrospectivos , Resultado do Tratamento , Acidente Vascular Cerebral/etiologia , Acidente Vascular Cerebral/complicações , Doenças das Artérias Carótidas/complicações , Trombectomia/efeitos adversos , Trombectomia/métodos , Procedimentos Endovasculares/efeitos adversos , Procedimentos Endovasculares/métodos , Stents/efeitos adversos
11.
Angew Chem Int Ed Engl ; 61(42): e202209391, 2022 Oct 17.
Artigo em Inglês | MEDLINE | ID: mdl-36005897

RESUMO

While the range of accessible borylenes has significantly broadened over the last decade, applications remain limited. Herein, we present tricoordinate oxy-borylenes as potent photoreductants that can be readily activated by visible light. Facile oxidation of CAAC stabilized oxy-borylenes (CAAC)(IPr2 Me2 )BOR (R=TMS, CH2 CH2 C6 H5 , CH2 CH2 (4-F)C6 H4 ) to their corresponding radical cations is achieved with mildly oxidizing ferrocenium ion. Cyclovoltammetric studies reveal ground-state redox potentials of up to -1.90 V vs. Fc+/0 for such oxy-borylenes placing them among the strongest organic super electron donors. Their ability as photoreductants is further supported by theoretical studies and showcased by the application as stoichiometric reagents for the photochemical hydrodehalogenation of aryl chlorides, aryl bromides and unactivated alkyl bromides as well as the detosylation of anilines.

12.
Circ J ; 86(10): 1539-1546, 2022 09 22.
Artigo em Inglês | MEDLINE | ID: mdl-35851559

RESUMO

BACKGROUND: Aortic valve stenosis (AS) leads to increased cardiovascular mortality and morbidity, and recent studies reported that even mild-to-moderate AS was associated with poor prognosis in the general population. This study investigated the prognostic impact of mild or moderate AS, defined as 2.0 m/s ≤ peak aortic jet velocity (Vmax) ≤3.9 m/s using echocardiography in acute myocardial infarction (AMI) patients.Methods and Results: This study enrolled 3,049 AMI patients using data from the Mie ACS registry. Patients were divided into 2 groups according to Vmax: Group 1: Vmax <2.0 m/s and/or visually intact aortic valve in which all 3 leaflets are fully and evenly open; Group 2: 2.0 m/s ≤ Vmax ≤ 3.9 m/s. There were 2,976 patients in Group 1and 73 patients in Group 2. The Group 2 patients were older, had a higher percentage of males and had lower body mass index and Killip ≥2 than the Group 1 patients. Angiographic data, door-to-balloon time, and mechanical support were not different between the 2 groups. The Group 2 patients demonstrated a significantly higher all-cause mortality rate (P<0.01) and composite of cardiovascular death and heart failure hospitalization (P<0.01), and Kaplan-Meier analysis showed the same tendency in propensity score-matched patients. CONCLUSIONS: The present study revealed that mild or moderate AS based on Vmax is associated with poor prognosis following AMI.


Assuntos
Estenose da Valva Aórtica , Infarto do Miocárdio , Humanos , Masculino , Infarto do Miocárdio/complicações , Infarto do Miocárdio/diagnóstico por imagem , Prognóstico , Índice de Gravidade de Doença , Volume Sistólico
13.
Spectrochim Acta A Mol Biomol Spectrosc ; 266: 120414, 2022 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-34619511

RESUMO

We investigated the vibrational density of states of sodium carboxymethyl starch (CM-starch) by terahertz (THz) time-domain spectroscopy. The CM-starch showed a broad peak at ∼3 THz. The structure of the peak was similar to those corresponding to glucose-based polymer glasses possessing hydrogen bonds. The boson peak (BP) appeared at 1.16 THz at the lowest temperature and disappeared because of the existence of excess wing at higher temperatures. However, based on our novel BP frequency determination method using the inflection point of the extinction coefficient, the BP frequency showed almost no dependence on temperature. Further, the chain length dependence of the BP frequency of the glucose-based glasses showed that the BP frequency of the polymer glass was slightly lower than that of the monomer glass. The power law behaviour of the absorption coefficient suggested the existence of fractons, and the fractal dimension was estimated to be 2.33.


Assuntos
Espectroscopia Terahertz , Ligação de Hidrogênio , Amido/análogos & derivados , Vibração
14.
J Phys Condens Matter ; 33(27)2021 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-33930889

RESUMO

Amorphous materials exhibit peculiar mechanical and vibrational properties, including non-affine elastic responses and excess vibrational states, i.e., the so-called boson peak (BP). For polymer glasses, these properties are considered to be affected by the bending rigidity of the constituent polymer chains. In our recent work [Tomoshige,et al2019,Sci. Rep.919514], we have revealed simple relationships between the variations of vibrational properties and the global elastic properties: the response of the BP scales only with that of the global shear modulus. This observation suggests that the spatial heterogeneity of the local shear modulus distribution is insensitive to changes in the bending rigidity. Here, we demonstrate the insensitivity of elastic heterogeneity by directly measuring the local shear modulus distribution. We also study transverse sound wave propagation, which is also shown to scale only with the global shear modulus. Through these analyses, we conclude that the bending rigidity does not alter the spatial heterogeneity of the local shear modulus distribution, which yields vibrational and acoustic properties that are controlled solely by the global shear modulus of a polymer glass.

15.
Radiol Case Rep ; 16(4): 835-842, 2021 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-33552335

RESUMO

Intracranial vessel dissection is a procedural complication associated with endovascular treatment. However, there have been few reports on its potential causes and management during mechanical thrombectomy. In approximately 250 cases of mechanical thrombectomy over the past 5 years at our institution, iatrogenic intracranial dissection occurred in 2 patients (0.8%). In this report, we described these 2 cases that were rescued through emergent stenting. Mechanical thrombectomy, using both a stent retriever and an aspiration catheter, was performed for acute middle cerebral artery M2 occlusion in Patient 1 (a 69-year-old man) and for distal M1 occlusion in Patient 2 (an 83-year-old woman). In both cases, recanalization was achieved with the procedure, but irregular stenosis developed at the initially nonoccluded, but mildly arteriosclerotic, M1, after recanalization. During the thrombectomy procedure, the aspiration catheter sifted up to the arteriosclerotic M1. In both cases, the lesions were considered vessel dissection, due to a shift of the aspiration catheter tip into the arteriosclerotic vessel wall. Repeated percutaneous angiography with antithrombotic therapy failed to improve the lesions and to maintain the antegrade blood flow. Finally, lesions in each patient were successfully rescued through the use of emergent stenting. A drug-eluting stent for coronary use was deployed in Patient 1, and an Enterprise stent was applied in Patient 2. Inadvertent shift of the aspiration catheter into arteriosclerotic vessels can cause a serious intracranial vessel dissection. When performing mechanical thrombectomy, intracranial stents need to be available as rescue treatment devices to manage refractory iatrogenic intracranial vessel dissection.

16.
Knee Surg Sports Traumatol Arthrosc ; 29(8): 2587-2594, 2021 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-33459835

RESUMO

PURPOSE: The Stump classification is significantly correlated with a retear after arthroscopic rotator cuff repair. However, no study has evaluated whether or not the stump classification is correlated with retear in the suture-bridge or double-row repair techniques. The aim of this study was to evaluate the relationship between a retear and the stump classification in the suture-bridge and double-row repair techniques. METHODS: Among 389 patients who underwent arthroscopic repairs of full-thickness rotator cuff tears using suture-bridge or double-row repair techniques, 326 patients (median age 67.0 years; range 25-85) were included. There were 51 small, 172 medium, 83 large, and 20 massive tears. Two hundred forty patients were treated with the suture-bridge technique, and 86 patients were treated with the double-row technique. The following variables were analyzed: age, sex, the Cofield classification, anteroposterior and mediolateral tear size on preoperative MRI, global fatty degeneration index, and the stump classification. Cuff integrity was evaluated on magnetic resonance imaging at 6 months after surgery. The patients were divided into the intact and retear groups and the relationship between the variables and retear was evaluated by multivariate logistic regression analysis. RESULTS: The overall retear rate was 10.1%. In the multivariate logistic regression analysis, the independent predictors of a retear were the stump classification type 3 (Odds ratio: 4.71, p = 0.0246), global fatty degeneration index (Odds ratio: 3.87, p = 0.0030), and anteroposterior tear size (Odds ratio: 1.07, p = 0.0077) in the suture bridge technique. In the double-row technique, the independent predictors of retear were stump classification type 3 (Odds ratio: 7.82, p = 0.0348), and age (Odds ratio: 1.22, p = 0.0163). CONCLUSION: The stump classification was significantly correlated with retear in the suture-bridge and double-row repair technique. Stump classification type 3 was indicated to be an important risk factor for predicting retear. LEVEL OF EVIDENCE: III.


Assuntos
Lesões do Manguito Rotador , Manguito Rotador , Adulto , Idoso , Idoso de 80 Anos ou mais , Artroscopia , Humanos , Imageamento por Ressonância Magnética , Pessoa de Meia-Idade , Estudos Retrospectivos , Manguito Rotador/cirurgia , Lesões do Manguito Rotador/cirurgia , Técnicas de Sutura , Suturas , Resultado do Tratamento
17.
J Chem Phys ; 154(1): 014501, 2021 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-33412881

RESUMO

The nature of bosonic excitations in disordered materials has remained elusive due to the difficulties in defining key concepts such as quasi-particles in the presence of disorder. We report on an experimental observation of phonon-polaritons in glasses, including a prominent boson peak (BP), i.e., excess of THz modes over the Debye law. A theoretical framework based on the concept of diffusons is developed to describe the broadening linewidth of the polariton due to disorder-induced scattering. It is shown here for the first time that the BP frequency and the Ioffe-Regel (IR) crossover frequency of the polariton collapse onto the same power-law decay with the diffusivity of the bosonic excitation. This analysis dismisses the hypothesis of the BP being caused by a relic of the van Hove singularity. The presented framework establishes a new methodology to analyze bosonic excitations in amorphous media, well beyond the traditional case of acoustic phonons, and establishes the IR crossover as the fundamental physical mechanism behind the BP.

19.
Spectrochim Acta A Mol Biomol Spectrosc ; 244: 118828, 2021 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-32882654

RESUMO

Paramylon is a long-chain polysaccharide, composed of glucose units connected via ß-(1,3) glycosidic bonds, that spontaneously forms a three-strand helical bundle. Paramylon-esters can be made by partially or fully replacing saccharide chain hydroxide groups with carboxylic functional groups, such as stearoyl (CH3(CH2)16CO) and palmitoyl (CH3(CH2)24CO). The paramylon-ester with carboxylic acids has superior characteristics, including high thermal resistance, stability and transparency under visible light, which are necessary for thermoplastic applications. In this study, the absorption coefficient α(ν) and absorbance spectra of paramylons and paramylon-esters were measured in the 0.3-8.0 THz range and compared with the corresponding spectra of glucose and cellulose. Paramylon and paramylon-ester molecules were found to exhibit unique, so-called fingerprint, α(ν)peaks at 4.0, 6.0 and 8.0 THz, and 2.5 and 5.0 THz, respectively. We speculate that the spectral features observed are owing to intermolecular interaction modes of the weakly coupled polysaccharide chains. The paramylons with different molecular weights show very similar absorption features in the low-frequency side, both in spectral shapes and intensities, indicating that absorption is independent of molecular size. The paramylon-esters with varying degrees of substitution (DS) are similar spectral shapes but different intensities. A linear correlation between α(ν) peak intensity and the DS of paramylon-esters was established with the R2 value above 0.99. This behavior can be used for the detection and identification of novel paramylon-ester molecules.

20.
Phys Rev E ; 102(2-1): 022502, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32942491

RESUMO

The boson peak is a largely unexplained excitation found universally in the terahertz vibrational spectra of disordered systems; the so-called fracton is a vibrational excitation associated with the self-similar structure of monomers in polymeric glasses. We demonstrate that such excitations can be detected using terahertz spectroscopy. In the case of fractal structures, we determine the infrared light-vibration coupling coefficient for the fracton region and show that information concerning the fractal and fracton dimensions appears in the exponent of the absorption coefficient. Finally, using terahertz time-domain spectroscopy and low-frequency Raman scattering, we experimentally observe these universal excitations in a protein (lysozyme) system that has an intrinsically disordered and fractal structure and argue that the system should be considered a single supramolecule. These findings are applicable to amorphous and fractal objects in general and will be valuable for understanding universal dynamics of disordered systems via terahertz light.

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