Exciton polaron formation and hot-carrier relaxation in rigid Dion-Jacobson-type two-dimensional perovskites.

The efficiency of two-dimensional Dion-Jacobson-type materials relies on the complex interplay between electronic and lattice dynamics; however, questions remain about the functional role of exciton-phonon interactions. Here we establish the robust polaronic nature of the excitons in these materials at room temperature by combining ultrafast spectroscopy and electronic structure calculations. We show that polaronic distortion is associated with low-frequency (30-60 cm-1) lead iodide octahedral lattice motions. More importantly, we discover how targeted ligand modification of this two-dimensional perovskite structure manipulates exciton-phonon coupling, exciton polaron population and carrier cooling. At high excitation density, stronger exciton-phonon coupling increases the hot-carrier lifetime, forming a hot-phonon bottleneck. Our study provides detailed insight into the exciton-phonon coupling and its role in carrier cooling in two-dimensional perovskites relevant for developing emerging hybrid semiconductor materials with tailored properties.

What is the association of preoperative biopsy with recurrence and survival in retroperitoneal sarcoma? A systematic review by the Australia and New Zealand Sarcoma Association clinical practice guidelines working party.

Preoperative biopsy for retroperitoneal sarcoma (RPS) enables appropriate multidisciplinary treatment planning. A systematic review of literature from 1990 to June 2022 was conducted using the population, intervention, comparison and outcome model to evaluate the local recurrence and overall survival of preoperative biopsy compared to those that had not. Of 3192 studies screened, five retrospective cohort studies were identified. Three reported on biopsy needle tract seeding, with only one study reporting biopsy site recurrence of 2 %. Two found no significant difference in local recurrence and one found higher 5-year local recurrence rates in those who had not been biopsied. Three studies reported overall survival, including one with propensity matching, did not show a difference in overall survival. In conclusion, preoperative core needle biopsy of RPS is not associated with increased local recurrence or adverse survival outcomes.

Technical considerations for isolated limb perfusion: A consensus paper.

BACKGROUND: Isolated limb perfusion (ILP) is a well-established surgical procedure for the administration of high dose chemotherapy to a limb for the treatment of advanced extremity malignancy. Although the technique of ILP was first described over 60 years ago, ILP is utilised in relatively few specialist centres, co-located with tertiary or quaternary cancer centres. The combination of high dose cytotoxic chemotherapy and the cytokine tumour necrosis factor alpha (TNFα), mandates leakage monitoring to prevent potentially serious systemic toxicity. Since the procedure is performed at relatively few specialist centres, an ILP working group was formed with the aim of producing technical consensus guidelines for the procedure to streamline practice and to provide guidance for new centres commencing the technique. METHODS: Between October 2021 and October 2023 a series of face to face online and hybrid meetings were held in which a modified Delphi process was used to develop a unified consensus document. After each meeting the document was modified and recirculated and then rediscussed at subsequent meeting until a greater than 90% consensus was achieved in all recommendations. RESULTS: The completed consensus document comprised 23 topics in which greater than 90% consensus was achieved, with 83% of recommendations having 100% consensus across all members of the working group. The consensus recommendations covered all areas of the surgical procedure including pre-operative assessment, drug dosing and administration, perfusion parameters, hyperthermia, leakage monitoring and theatre logistics, practical surgical strategies and also post-operative care, response evaluation and staff training. CONCLUSION: We present the first joint expert-based consensus statement with respect to the technical aspects of ILP that can serve as a reference point for both existing and new centres in providing ILP.

The role of radiation therapy in the management of primary retroperitoneal sarcoma: A systematic review and clinical practice guidelines from the Australia and New Zealand Sarcoma Association.

While surgery is the mainstay of treatment for localised retroperitoneal sarcoma, the use of radiotherapy (RT) remains controversial. This systematic review aimed to evaluate the role of RT for retroperitoneal sarcoma. A systematic review using the population, intervention, comparison, and outcome model from 1990 to 2022 identified 66 studies (a mixture of preoperative and postoperative RT); one randomised controlled trial (RCT) with two publications, 18 registry studies, and 46 retrospective studies. In the RCT of preoperative RT, there was no difference in local/abdominal recurrence. The pooled analysis of this RCT and a retrospective study showed a significant abdominal recurrence free survival benefit with preoperative RT in low grade liposarcoma. The RCT and the majority of retrospective series found RT did not improve recurrence free survival (11 of 16 no difference in combined local and distant RFS, 11 of 13 no difference in distant metastasis free survival), disease specific survival (9 of 12 studies) or overall survival (33 of 49 studies). The majority of studies found no association between RT and perioperative morbidity. In summary, preoperative RT may improve local control for low grade (well-differentiated or grades 1-2 dedifferentiated) liposarcoma, but not other histological subtypes. There is no strong evidence that perioperative RT provides an overall survival benefit. Patients with low grade retroperitoneal liposarcoma can be considered for preoperative RT to improve abdominal recurrence free survival. The rationale and level of evidence in this scenario should be carefully discussed by the multidisciplinary team with patients. RT should not be routinely recommended for other histological subtypes.

Comparison of humans versus mobile phone-powered artificial intelligence for the diagnosis and management of pigmented skin cancer in secondary care: a multicentre, prospective, diagnostic, clinical trial.

BACKGROUND: Diagnosis of skin cancer requires medical expertise, which is scarce. Mobile phone-powered artificial intelligence (AI) could aid diagnosis, but it is unclear how this technology performs in a clinical scenario. Our primary aim was to test in the clinic whether there was equivalence between AI algorithms and clinicians for the diagnosis and management of pigmented skin lesions. METHODS: In this multicentre, prospective, diagnostic, clinical trial, we included specialist and novice clinicians and patients from two tertiary referral centres in Australia and Austria. Specialists had a specialist medical qualification related to diagnosing and managing pigmented skin lesions, whereas novices were dermatology junior doctors or registrars in trainee positions who had experience in examining and managing these lesions. Eligible patients were aged 18-99 years and had a modified Fitzpatrick I-III skin type; those in the diagnostic trial were undergoing routine excision or biopsy of one or more suspicious pigmented skin lesions bigger than 3 mm in the longest diameter, and those in the management trial had baseline total-body photographs taken within 1-4 years. We used two mobile phone-powered AI instruments incorporating a simple optical attachment: a new 7-class AI algorithm and the International Skin Imaging Collaboration (ISIC) AI algorithm, which was previously tested in a large online reader study. The reference standard for excised lesions in the diagnostic trial was histopathological examination; in the management trial, the reference standard was a descending hierarchy based on histopathological examination, comparison of baseline total-body photographs, digital monitoring, and telediagnosis. The main outcome of this study was to compare the accuracy of expert and novice diagnostic and management decisions with the two AI instruments. Possible decisions in the management trial were dismissal, biopsy, or 3-month monitoring. Decisions to monitor were considered equivalent to dismissal (scenario A) or biopsy of malignant lesions (scenario B). The trial was registered at the Australian New Zealand Clinical Trials Registry ACTRN12620000695909 (Universal trial number U1111-1251-8995). FINDINGS: The diagnostic study included 172 suspicious pigmented lesions (84 malignant) from 124 patients and the management study included 5696 pigmented lesions (18 malignant) from the whole body of 66 high-risk patients. The diagnoses of the 7-class AI algorithm were equivalent to the specialists' diagnoses (absolute accuracy difference 1·2% [95% CI -6·9 to 9·2]) and significantly superior to the novices' ones (21·5% [13·1 to 30·0]). The diagnoses of the ISIC AI algorithm were significantly inferior to the specialists' diagnoses (-11·6% [-20·3 to -3·0]) but significantly superior to the novices' ones (8·7% [-0·5 to 18·0]). The best 7-class management AI was significantly inferior to specialists' management (absolute accuracy difference in correct management decision -0·5% [95% CI -0·7 to -0·2] in scenario A and -0·4% [-0·8 to -0·05] in scenario B). Compared with the novices' management, the 7-class management AI was significantly inferior (-0·4% [-0·6 to -0·2]) in scenario A but significantly superior (0·4% [0·0 to 0·9]) in scenario B. INTERPRETATION: The mobile phone-powered AI technology is simple, practical, and accurate for the diagnosis of suspicious pigmented skin cancer in patients presenting to a specialist setting, although its usage for management decisions requires more careful execution. An AI algorithm that was superior in experimental studies was significantly inferior to specialists in a real-world scenario, suggesting that caution is needed when extrapolating results of experimental studies to clinical practice. FUNDING: MetaOptima Technology.

Surgery at specialised sarcoma centres improves patient outcomes - A systematic review by the Australia and New Zealand sarcoma association clinical practice guidelines working party.

BACKGROUND: Optimal management of sarcoma requires multidisciplinary team input throughout the process of diagnosis, treatment and follow up. This systematic review aimed to evaluate the impact of surgery performed at specialised sarcoma centres on outcomes. METHODS: A systematic review was conducted using the population, intervention, comparison and outcome (PICO) model. Medline, Embase, Cochrane Central databases were queried for publications that evaluated the local control, limb salvage rate, 30-day and 90-day surgical mortality, and overall survival in patients undergoing surgery in a specialist sarcoma centre compared with non-specialist centre. Each study was screened by two independent reviewers for suitability. A qualitative synthesis of the results was performed. RESULTS: Sixty-six studies were identified. The majority of studies were Level III-3 as assessed by the NHMRC Evidence Hierarchy, whilst just over half of the studies were of good quality. Definitive surgery performed at specialised sarcoma centres was associated with improved local control as defined by lower rate of local relapse, higher rate of negative surgical margins, improved local recurrence free survival and higher limb conservation rate. Available evidences show a favourable pattern of lower 30-day and 90-day mortality rates, and greater overall survival when surgery was performed in specialist sarcoma centres compared with non-specialised centres. CONCLUSIONS: Evidences support better oncological outcomes when surgery is performed at specialised sarcoma centre. Patients with suspected sarcoma should be referred early to a specialised sarcoma centre for multidisciplinary management, which includes planned biopsy and definitive surgery.

Improving Public Health Policy by Comparing the Public Response during the Start of COVID-19 and Monkeypox on Twitter in Germany: A Mixed Methods Study.

Little is known about monkeypox public concerns since its widespread emergence in many countries. Tweets in Germany were examined in the first three months of COVID-19 and monkeypox to examine concerns and issues raised by the public. Understanding views and positions of the public could help to shape future public health campaigns. Few qualitative studies reviewed large datasets, and the results provide the first instance of the public thinking comparing COVID-19 and monkeypox. We retrieved 15,936 tweets from Germany using query words related to both epidemics in the first three months of each one. A sequential explanatory mixed methods research joined a machine learning approach with thematic analysis using a novel rapid tweet analysis protocol. In COVID-19 tweets, there was the selfing construct or feeling part of the emerging narrative of the spread and response. In contrast, during monkeypox, the public considered othering after the fatigue of the COVID-19 response, or an impersonal feeling toward the disease. During monkeypox, coherence and reconceptualization of new and competing information produced a customer rather than a consumer/producer model. Public healthcare policy should reconsider a one-size-fits-all model during information campaigns and produce a strategic approach embedded within a customer model to educate the public about preventative measures and updates. A multidisciplinary approach could prevent and minimize mis/disinformation.

Clinicopathological Characteristics Predicting Further Recurrence and Survival Following Resection of In-Transit Melanoma Metastases.

BACKGROUND: In-transit metastases (ITMs) affect approximately 4% of patients with cutaneous melanoma. This study sought to identify clinical and pathological characteristics that predict further recurrence and survival following resection of ITMs. PATIENTS AND METHODS: Patients (n = 573) who underwent surgical resection of their first presentation of ITM following previous surgical treatment of an American Joint Committee on Cancer (AJCC) stage I-II melanoma between 1969 and 2017 were identified from an institutional database. Clinicopathological predictors of patterns of recurrence and survival following ITM resection were sought. RESULTS: The median time of ITM development was 2.4 years after primary melanoma resection. ITMs were most frequently located on the lower limb (51.0%). The most common melanoma subtype associated with ITM development was nodular melanoma (44.1%). After surgical resection of a first ITM, 65.4% of patients experienced recurrent disease. Most recurrences were locoregional (44.7%), with distant metastasis occurring in 23.9% of patients. Lower limb ITMs were more frequently associated with subsequent ITMs [odds ratio (OR) 2.41, p = 0.0002], and the lowest risk of distant metastasis (p < 0.0001) compared with other primary sites. Primary melanomas and ITM on head and neck, as well as the presence of ulceration, were associated with worse survival. CONCLUSIONS: Recurrence after surgical resection of a first ITM was common. Patterns of recurrence differed according to anatomical site; further ITM recurrences were more likely for lower limb ITMs, which were also associated with longer distant recurrence-free survival. Distant metastasis was more common for ITM on the head and neck, with worse survival.

Treatment of in-transit Merkel cell carcinoma by isolated limb infusion with cytotoxic drugs.

Merkel cell carcinoma of the skin is a rare but aggressive malignancy, which predominantly affects older adults with fair skin. Isolated limb infusion (ILI) using melphalan and actinomycin D was first developed as a minimally invasive treatment option to treat unresectable metastatic melanoma confined to the limb. We report on a 62-year-old male with in-transit metastases (ITMs) treated with ILI to highlight the ongoing role this treatment has when all other therapies have been exhausted. At presentation, the patient had widespread ITMs in the right leg. Positron emission tomography scan demonstrated recurrent disease in the thigh and pelvis, and it was decided to treat the patient with ILI. The patient progressed well in the immediate post-operative period. The patient was able to mobilize from Day 6 post-ILI and was discharged on Day 10. There was an immediate clinical response seen in the lesions, with necrosis developing in the larger lesions.

Trajectory Ensemble Methods Provide Single-Molecule Statistics for Quantum Dynamical Systems.

The emergence of experiments capable of probing quantum dynamics at the single-molecule level requires the development of new theoretical tools capable of simulating and analyzing these dynamics beyond an ensemble-averaged description. In this article, we present an efficient method for sampling and simulating the dynamics of the individual quantum systems that make up an ensemble and apply it to study the nonequilibrium dynamics of the ubiquitous spin-boson model. We generate an ensemble of single-system trajectories, and we analyze this trajectory ensemble using tools from classical statistical mechanics. Our results demonstrate that the dynamics of quantum coherence is highly heterogeneous at the single-system level due to variations in the initial bath configuration, which significantly affects the transient exchange of coherence between the system and its bath. We observe that single systems tend to retain coherence over time scales longer than that of the ensemble. We also compute a novel thermodynamic entanglement entropy that quantifies a thermodynamic driving force favoring system-bath entanglement.

Survival and morbidity outcomes after pelvic exenteration for pelvic sarcoma: an institutional series.

BACKGROUND: To describe our institutional experience in the management of locally advanced primary, and recurrent pelvic sarcoma through pelvic exenteration (PE). METHODS: Patients undergoing PE for locally advanced primary or recurrent pelvic sarcoma between 2003 and 2017 were identified from a prospectively maintained database at a single quaternary referral hospital in Sydney, Australia were eligible for review. The primary outcomes measured were surgical resection margin and survival. Secondary outcome measures included 30-day morbidity, in hospital length of stay (LOS) and return to theatre. RESULTS: There were 29 patients who underwent PE for pelvic sarcoma during the study period, with 55% (n = 16) having advanced primary tumours and 45% (n = 13) having recurrent disease. The R0 resection rate was 52% (n = 15); and five-year-survival of 38% (n = 11). The R0 resection was noted to be higher in patients having primary advanced tumours (56%) compared to those with recurrent disease (46%), however this failed to reach statistical significance in this cohort. There was no recorded 30-day mortality. Grade 3 or higher Clavien-Dindo complications were uncommon (14%), but more likely in patients undergoing surgery for recurrent disease (75%). CONCLUSION: In our cohort of patients with locally advanced and recurrent disease, more than 50% achieved an R0 resection. Recurrent disease makes R0 resection more difficult and can lead to higher morbidity, need for 30-day re-intervention and longer in hospital LOS. PE surgery remains the only curative option for locally advanced, and recurrent sarcoma in the pelvis, and can be performed with acceptable survival and morbidity outcomes.

Influence of solution phase environmental heterogeneity and fluctuations on vibronic spectra: Perylene diimide molecular chromophore complexes in solution.

Ensembles of ab initio parameterized Frenkel-exciton model Hamiltonians for different perylene diimide dimer systems are used, together with various dissipative quantum dynamics approaches, to study the influence of the solvation environment and fluctuations in chromophore relative orientation and packing on the vibronic spectra of two different dimer systems: a π-stacked dimer in aqueous solution in which the relative chromophore geometry is strongly confined by a phosphate bridge and a side-by-side dimer in dichloromethane involving a more flexible alkyne bridge that allows quasi-free rotation of the chromophores relative to one another. These entirely first-principles calculations are found to accurately reproduce the main features of the experimental absorption spectra, providing a detailed mechanistic understanding of how the structural fluctuations and environmental interactions influence the vibronic dynamics and spectroscopy of solutions of these multi-chromophore complexes.

Analytic and numerical vibronic spectra from quasi-classical trajectory ensembles.

The truncated Wigner approximation to quantum dynamics in phase space is explored in the context of computing vibronic line shapes for monomer linear optical spectra. We consider multiple model potential forms including a shifted harmonic oscillator with both equal and unequal frequencies on the ground and excited state potentials as well as a shifted Morse potential model. For the equal-frequency shifted harmonic oscillator model, we derive an analytic expression for the exact vibronic line shape that emphasizes the importance of using a quantum mechanical distribution of phase space initial conditions. For the unequal-frequency shifted harmonic oscillator model, we are no longer able to obtain an exact expression for the vibronic line shape in terms of independent deterministic classical trajectories. We show how one can rigorously account for corrections to the truncated Wigner approximation through nonlinear responses of the line shape function to momentum fluctuations along a classical trajectory and demonstrate the qualitative improvement in the resulting spectrum when the leading-order quantum correction is included. Finally, we numerically simulate absorption spectra of a highly anharmonic shifted Morse potential model. We find that, while finite quantization and the dissociation limit are captured with reasonable accuracy, there is a qualitative breakdown of the quasi-classical trajectory ensemble's ability to describe the vibronic line shape when the relative shift in Morse potentials becomes large. The work presented here provides clarity on the origin of unphysical negative features known to contaminate absorption spectra computed with quasi-classical trajectory ensembles.

Modeling Nonperturbative Field-Driven Vibronic Dynamics: Selective State Preparation and Nonlinear Spectroscopy.

The partially linearized density matrix formalism for nonadiabatic dynamics is adapted to incorporate a classical external electromagentic field into the system Hamiltonian. This advancement encompasses the possibility of describing field-driven dynamics and computing a variety of linear and nonlinear spectroscopic signals beyond the perturbative limit. The capabilities of the developed approach are demonstrated on a simple two-state vibronic model coupled to a bath, for which we (a) perform an exhaustive search in the field parameter space for optimal state preparation and (b) compute time-resolved transient absorption spectroscopy to monitor the effect of different pulse shapes on measurable experimental signals. While no restrictions on the form of the field have to be assumed, we focus here on Gaussian shaped (linearly) chirped pulses.

Quantum biology revisited.

Photosynthesis is a highly optimized process from which valuable lessons can be learned about the operating principles in nature. Its primary steps involve energy transport operating near theoretical quantum limits in efficiency. Recently, extensive research was motivated by the hypothesis that nature used quantum coherences to direct energy transfer. This body of work, a cornerstone for the field of quantum biology, rests on the interpretation of small-amplitude oscillations in two-dimensional electronic spectra of photosynthetic complexes. This Review discusses recent work reexamining these claims and demonstrates that interexciton coherences are too short lived to have any functional significance in photosynthetic energy transfer. Instead, the observed long-lived coherences originate from impulsively excited vibrations, generally observed in femtosecond spectroscopy. These efforts, collectively, lead to a more detailed understanding of the quantum aspects of dissipation. Nature, rather than trying to avoid dissipation, exploits it via engineering of exciton-bath interaction to create efficient energy flow.

Liver resection as a component of en-bloc multivisceral resection for upper abdominal tumors is associated with increased morbidity.

BACKGROUND AND METHODS: Complex en-bloc multivisceral and oncovascular resections for upper abdominal tumors remain rare, but there is increasing interest in their role. We analyze complications and survival for these operations. We performed a retrospective cohort study of patients who underwent en-bloc upper abdominal resections for tumors involving multiple organs. Primary outcomes were complications as per the Clavien-Dindo Classification and Comprehensive Complication Index (CCI). Secondary outcome was overall survival (OS). RESULTS: We identified 60 consecutive patients who underwent resection from 2011 to 2018. Histopathology was heterogeneous, the most common being renal cell carcinoma. Eighteen patients had major complications. Mean (interquartile range) CCI was 29.6 (9.6-43.9). Liver resection was significantly associated with an increased CCI and increased the odds of a major complication (odds ratio: 4.67, 95% confidence interval [CI]: 1.31-16.59; P = .017). Charlson Comorbidity Score was significantly associated with the presence of at least one major complication. Mean OS was 47.1 months (95% CI: 37.6-56.6). CONCLUSION: In appropriately selected patients, and when undertaken in centers with appropriate subspecialist surgical teams and intensive care services, en-bloc multivisceral resection of upper abdominal tumors is safe, but liver resection is associated with an increase in major complications.